Curable organic siloxane-modified reactive resin

Abstract

The present invention relates to a curable composition of a reactive resin having polymerizable cyanate ester functional groups and a poly(diorgano)siloxane having phenolic hydroxyl groups, a method for producing the same, and cured materials and composite materials obtained therefrom that exhibit low water absorption and high fracture toughness. Note: The invention on which this patent application is based originates from a project funded by the German Federal Ministry of Education and Research, grant number 03XP0170C. The applicant is solely responsible for the content of this patent application.

Description

[Technical Field]

[0001] The present invention relates to a curable composition of a reactive resin having polymerizable cyanate ester functional groups and a poly(diorgano)siloxane having phenolic hydroxyl groups, a method for producing the same, and cured materials and composite materials obtained therefrom that exhibit low water absorption and high fracture toughness. [Background technology]

[0002] Epoxy (EP) resins and epoxy resin systems are used in a wide variety of applications and are now established as one of the most commonly used classes of thermosetting resins in combination with composite materials, such as glass fibers, carbon fibers (CRP), or aramid fibers. Furthermore, high-performance organic reactive resins such as 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 / epoxy, or bismaleimide / cyanate ester (BT resins), have recently gained increasing importance as matrix resins for fiber composite materials in industrial, automotive, and aerospace fields. 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 heat resistance, and long-term stability, significantly expanding the usability of these thermosetting resins, especially in high-temperature ranges.

[0003] However, thermosetting resin systems based on CE resins also have drawbacks. During thermosetting, reactive cyanate ester groups ("N≡CO-") trimerize to form cyclic triazine rings, thereby creating a polycyanurate network with high crosslinking density. While the cured cyanate ester resin has high mechanical stability due to its highly crosslinked state, the network is consequently brittle, i.e., has low fracture toughness / impact resistance. A further significant drawback of cyanate ester resin systems is that both the uncrosslinked resin and the cured polycyanurate are sensitive to hydrolysis: water penetrating the cured thermosetting network causes network degradation (hydrolysis degradation), which leads to a deterioration of the material's properties. In particular, highly crosslinked, relatively polar thermosetting resins based on novolac-cyanate esters have relatively high water absorption and hydrolysis rates among CE resins.

[0004] Therefore, for these CE-reactive resins already on the market, it is desirable to provide suitable modifiers that are stable at high temperatures. These modifiers contribute to both reduced water absorption and higher fracture toughness in the cured thermosetting network, enabling their commercial use as matrix resins in demanding composite material applications at high temperatures, preferably in the aerospace industry. Importantly, the modifier must be compatible with the cyanate ester resin, meaning it can be processed into a homogeneous mixture, and the cured thermosetting mixture must not show signs of separation, such as leaching or exudation of siloxane components from the polycyanurate network, or a sticky surface. These are undesirable because separation alters the material's properties and impairs the matrix-fiber bond.

[0005] Several methods have been developed to modify polycyanurate networks using poly(diorgano)siloxanes ("silicones") that have reactive functional groups copolymerizable with cyanate ester resins.

[0006] U.S. Patent No. 5,539,041 (corresponding to European Patent No. 0518,654) claims a composition of a silicone with a reactive, copolymerizable cyanate ester resin. In the examples, only amine-functionalized linear siloxanes are disclosed as modifiers for the cyanate ester resin. A significant drawback of using amine-functionalized modifiers is that they significantly accelerate the crosslinking reaction of cyanate ester groups, making the curing of cyanate ester resin mixtures with a relatively high proportion of amino group-containing modifiers uncontrollable. Furthermore, the amino groups contribute to increased water absorption, leading to increased degradation of the polycyanurate network due to amino decomposition, which manifests as an increased hydrolysis rate.

[0007] Japanese Patent Publication No. 2014-012759 and European Patent Application Publication No. 4056371 describe, in examples, the preparation of a mixture of a cyanate ester resin having at least two cyanate ester groups and an incompatible, relatively high molecular weight poly(dimethyl)siloxane having terminal phenolpropyl groups. To prevent phase separation of the incompatible component, the mixture is thermally pre-crosslinked in solution (Japanese Patent Publication No. 2014-012759) or without a solvent (European Patent Application Publication No. 4056371) in the presence of a catalyst that promotes the co-reaction between the cyanate ester groups and phenol OH groups to produce a prepolymer. In this context, "pre-crosslinked prepolymer" is understood to mean an oligomer obtained by partial trimerization of the cyanate ester groups containing the phenol functional groups of the siloxane. That is, both reactions between cyanate ester groups and co-reactions between phenol groups and cyanate ester groups occur, and similarly, a triazine ring is formed. The significant drawbacks of these methods include the bonding of phenol groups to siloxanes via thermally unstable propyl radicals; the use of organic solvents, which are problematic for economic, toxic, and waste disposal reasons (Japanese Patent Publication No. 2014-012759); and the formation of pre-crosslinked prepolymers that are unsuitable for solvent-free processing due to their high viscosity, and unsuitable for all processing methods, including infusion methods, even when solvent-based processing is used, as these pre-crosslinked prepolymers have relatively low storage stability. None of the literature discloses how modification of cyanate ester resins with phenolpropyl-terminated poly(diorgano)siloxanes affects properties such as water absorption and fracture toughness of the cured mixture, nor does it disclose the extent to which low molecular weight, relatively short-chain phenol-terminated siloxanes are compatible with cyanate ester resins without pre-crosslinking. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] U.S. Patent No. 5539041 [Patent Document 2] European Patent No. 0518654 [Patent Document 3] Japanese Patent Publication No. 2014-012759 [Patent Document 4] European Patent Application Publication No. 4056371 [Overview of the project] [Problems that the invention aims to solve]

[0009] The object of the present invention is to provide an organic resin having a reactive cyanate ester group in which the water absorption rate is reduced after the molding and curing process, thereby improving hydrolysis resistance and high fracture toughness (K IcIt is to be modified so as to obtain a crosslinkable thermosetting resin having the following. By this modification, excellent properties inherent to the cyanate ester resin, such as thermal oxidation stability and high mechanical strength, are largely retained even in the thus-modified thermosetting resin.

[0010] According to the present invention, by using a linear poly(diorgano)siloxane having a Si-bonded aromatic group containing at least one phenolic hydroxyl group, this object is achieved, which is compatible with an organic cyanate ester resin without preliminary crosslinking in the presence of a catalyst, that is, it can be processed into a homogeneous single-phase mixture, and the thermosetting mixture after curing does not show signs of separation such as bleeding or exudates of the siloxane component from the polycyanurate network or a sticky surface. Surprisingly, by using the linear poly(diorgano)siloxane having a Si-bonded phenol group of the present invention, the cured mixture has a lower water absorption rate (and reduction of network degradation due to hydrolysis related thereto), higher fracture toughness, and higher thermal oxidation stability more advantageously than those known in the prior art so far. It has been found that it is possible to modify an organic cyanate ester resin.

Means for Solving the Problems

[0011] The present invention relates to (A) at least one organic compound (A) (also referred to herein as "cyanate ester resin") having no siloxy (≡Si-O-) unit and having at least two cyanate ester (-O-C≡N) groups, the compound (A) is preferably substituted and / or contains at least one heteroatom, and (B) General formula (I) R a R 1 3-a Si-O-(R d R 1 2-d Si-O-) b -SiR c R 1 3-c (I) (In the formula, R is either the same or different. Ether (≡COC≡) group, hydroxyl (-OH) group and / or epoxy (=C) group -O- A monovalent, SiC-bonded aliphatic hydrocarbon group that may contain a C=) group, or A monovalent, SiC-bonded aromatic hydrocarbon group that lacks a phenolic OH group and may be interrupted by at least one heteroatom. This represents, R 1 They are either the same or different. Represents a monovalent, aromatic hydrocarbon group having at least one phenolic hydroxyl group, which may be interrupted by a heteroatom. a is 2 or 3, preferably 2. b is an integer between 1 and 18, preferably between 1 and 13, more preferably between 1 and 8, and particularly between 1 and 3. c is 2 or 3, preferably 2. d is 1 or 2, preferably 2. It is at least one type of poly(diorgano)siloxane, however, One or two groups R per poly(diorgano)siloxane molecule (B) of general formula (I) 1 Preferably two groups R 1 Poly(diorgano)siloxane exists. The present invention provides a curable composition containing [a specific compound / component].

[0012] The compositions according to the present invention are preferably curable without the addition of a catalyst, particularly a catalyst for pre-crosslinking components (A) and (B).

[0013] Therefore, in one particular embodiment, the condition also applies that no pre-crosslinking of components (A) and (B) occurs in the presence of the catalyst, and / or, without the addition of a solvent and in the absence of the catalyst, components (A) and (B) exist in liquid form as a stable and homogeneous mixture at a temperature of 100°C, and this stable and homogeneous mixture is characterized in that, in particular, after storing the mixture at 100°C for at least 15 minutes, no macroscopic separation visible to the naked eye occurs as a result of the formation of a phase interface, i.e., due to biphasicity.

[0014] Furthermore, a further characteristic of the stability of the mixture according to the present invention is that the thermosetting mixture obtained after curing does not exhibit macroscopic separation of the siloxane component (B) from the polycyanurate network in the form of visible leaching or oiling, or a sticky surface. [Modes for carrying out the invention]

[0015] In the present invention, the name "1-propenyl" represents the "-CH=CH-CH3" group, the name "2-propenyl" or "allyl" represents the "-CH2-CH=CH2" group, and the name "propenyl" represents the 1- or 2-propenyl group.

[0016] In this invention, "phenolic hydroxyl group" means an aromatic hydroxyl compound in which a hydroxyl group is directly bonded to an aromatic carbon atom.

[0017] In the present invention, the name "component (A)" refers to the entirety of at least one compound (A), and the name "component (B)" refers to the entirety of at least one compound (B).

[0018] To avoid making the specification of this application excessively long, only preferred embodiments of each feature will be described. However, expert readers should clearly understand that this type of disclosure means that all combinations of different priorities, namely combinations within a single compound / feature and combinations between different compounds / features, are explicitly disclosed and explicitly intended.

[0019] Cyanate ester resin (A) These are organic compounds that lack siloxy (≡Si-O-) units and have at least two cyanate ester (-OC≡N) groups per molecule. Compound (A) may be substituted and / or contain at least one heteroatom.

[0020] Preferably, compound (A) is an aromatic hydrocarbon compound which may be substituted and / or contains at least one heteroatom, and at least two cyanate ester (-OC≡N) groups per molecule of compound (A) are preferably bonded to an aromatic carbon atom.

[0021] More preferably, each molecule of compound (A) comprises at least two aromatic hydrocarbon groups, each of which may be substituted and / or contain at least one heteroatom, and each comprises a cyanate ester group bonded to an aromatic carbon atom; in particular, the aromatic hydrocarbon groups may be substituted and / or contain at least one heteroatom, and each comprises a cyanate ester group bonded to an aromatic carbon atom, which are covalently bonded or -CR 2 2-,-CR 2 =CR 2 -,-C(=CR 2 2) -, -O-, -S-, -N=N-, -CR 2 =N-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -S(=O)-, -S(=O)2-, O=P(O-)3, -SiR 2 2-, divalent aromatic hydrocarbon groups, e.g., phenylene, trilene, biphenylene, naphthylene, etc.; or divalent cycloalkanediyl groups, e.g., tricyclo[5.2.1.0 2,6They are linked to each other via at least one crosslinking unit selected from the group consisting of decanediyl and bicyclo[2.2.1]heptanediyl, etc.

[0022] base R 2 In each case, independently, is a hydrogen atom, a halogen atom, or a monovalent, possibly substituted hydrocarbon group having 1 to 30 carbon atoms, and a substituent or other group R 2 They may be connected to form a ring-shaped unit.

[0023] base R 2 Examples include monovalent groups such as methyl, ethyl, trifluoromethyl, phenyl, and fluorenyl groups; and bivalent groups such as 1,1-cyclohexanediyl, cyclohexene-1,2-diyl, 9H-fluorene-9,9-diyl, N-phenyl-1-isoindrinone-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 groups. 2 It is a ring structure consisting of [the specified elements].

[0024] The heteroatom may be selected from the group consisting of O, S, N, P, and Si, and preferably from the group consisting of O and S.

[0025] Examples of components (A) used in the present invention include di- and polycyanate esters of monoaromatic hydrocarbons, e.g., 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, e.g., 2,2-bis(4-cyanatophenyl)butane, 2,2-bis(4-cyanatophenyl)propane (CAS 1129-80-2); 1156-51-0, Bisphenol A cyanate ester; trade names: AroCy(R)B10, PRIMASET(R)BADCy, and CYTESTER(R)TA), 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane (CAS 32728-27-1, Bisphenol A 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(R)L-10, PRIMASET(R)LECy, CYTESTER(R)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, Tetramethylbisphenol F cyanate ester), 1,3-Bis(2-(4-cyanatophenyl)propan-2-yl)benzene (CAS 127667-44-1, Bisphenol M cyanate ester);Product Name: AroCy(R)XU 366), Bis(4-cyanatophenyl)thioether, Bis(4-cyanatophenyl)ether, 1,1-bis(4-cyanatophenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-cyanatophenyl)cyclohexane, 9,9-bis(4-cyanatophenyl)fluorene (bisphenol FL cyanate ester), Bis(4-cyanatophenyl)sulfone (CAS 2918-28-7; Bisphenol S cyanate ester), bis(4-cyanatophenyl) ketone, bis(4-(4-cyanatophenoxy)phenyl) ketone, bis(4-(4-cyanatophenoxy)phenyl) sulfone, bis(4-cyanatophenoxy) sulfoxide, bis(4-(4-cyanatophenoxy)phenyl)(phenyl)phosphine oxide, bis(4-cyanatophenyl)(methyl)phosphine oxide, 1,1-dibromo-2,2-bis(4-cyanatophenyl)ethylene, 1,1-dichloro-2,2-bis(4-cyanatophenyl)ethylene, 3,3-bis(4-cyanatophenyl)-N-phenylphthalimide, 3,3-bis(4-cyanatophenyl)-1(3H)-isobenzofuranone (CAS 32728-31-7), 3,3-bis(4-cyanatophenyl)-2-benzofuran-1-one, 10,10-bis(4-cyanatophenyl)anthracene-9(10H)-one, 1-ethyl-2-methyl-3-(4-cyanatophenyl)-5-cyanatoindan, 1,1-dimethyl-3-methyl-3-(4-cyanatophenyl)cyanatoindan, bis(2-cyanato-3-methoxy-5-methylphenyl)methane and 1,1-bis(3- Methyl-4-cyanatophenyl)cyclohexane(bisphenol Z cyanate ester), etc.; 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, etc.;Cyanate esters of biphenyls, e.g., 4,4'-dicyanatobiphenyl (CAS 1219-14-3), 2,4'-dicyanatobiphenyl and 2,2'-dicyanatobiphenyl; cyanate ester resins of phenol-dicyclopentadienes, e.g., dicyclopentadienylbis(phenol cyanate ester) (CAS 135507-71-0; trade name: AroCy(R)XU-71787.02); cyanate esters of phenol-formaldehyde resins produced by acid- or alkali-catalyzed condensation of phenol, naphthol, naphthalenediol, xylenol or cresol with formaldehyde, e.g., cyanate esters of resol or cyanate esters of novolac (e.g., CAS 87397-54-4, CAS 153191-90-3, CAS 268734-03-8, CAS Examples of trade names: Primaset(R) PT-15, PT-30, PT-60, PT-90 and CT-90, and AroCy(R) ​​XU-371; cyanate esters of fluoroalkanediols, e.g., 1,8-dicyanatoperfluorooctane; cyanate esters of naturally derived polyphenols, e.g., trans-3,5,4'-tricyanatostilbene; cyanate esters of bisphenolsilanes, e.g., dimethylbis(4-cyanatophenyl)silane; 1,1,1-tris(4-cyanatophenyl)ethane (CAS 113151-22-7), 1,2,3-tris(4-cyanatophenyl)propane; and an end-terminated cyanate ester polymer resin 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, naphthylene, or 9H-fluorene-9,9-diyl, and -CR; 3 2-, -CR 3 =CR 3 -, -C (=CR 3 2) -O-, -S-, -N=N-, -CR 3=N-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -S(=O)-, -S(=O)2-, O=P(O-)3, -SiR 3 2- or divalent cycloalkanediyl groups, e.g., tricyclo[5.2.1.0 2,6 The cyanate ester polymer resin contains at least one bridging unit selected from the group consisting of decanediyl and bicyclo[2.2.1]heptanediyl. Examples of repeating units in the cyanate ester polymer resin include arylene ether, arylene ether sulfone, or arylene ether ketone.

[0026] base R 3 In either case, R is independent. 2 It includes the group shown in [reference].

[0027] Preferably, component (A) includes cyanate ester resins of 2,2-bis(4-cyanatophenyl)propane, 1,1-bis(4-cyanatophenyl)ethane, bis(4-cyanatophenyl)methane, 1,3-bis(2-(4-cyanatophenyl)propane-2-yl)benzene, 2,2-bis(3-(2-propenyl)-4-cyanatophenyl)propane, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, phenol-dicyclopentadiene, and phenol-formaldehyde resins. More preferably, component (A) includes 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, a cyanate ester resin of phenol-dicyclopentadiene, or a cyanate ester of phenol-formaldehyde resin. In particular, component (A) includes 1,1-bis(4-cyanatophenyl)ethane, 1,3-bis(2-(4-cyanatophenyl)propan-2-yl)benzene, and a novolac cyanate ester of cresol or phenol.

[0028] It is possible to use only one type of cyanate ester resin (A) or a mixture of different cyanate ester resins (A); or to use a prepolymer of one type of cyanate ester resin (A) or a prepolymer of different cyanate ester resins (A), and to use a mixture of prepolymeric cyanate ester resins or a mixture of prepolymeric cyanate ester resins and one or more types of cyanate ester resins (A).

[0029] An example of a prepolymer of cyanate ester resin (A) is bisphenol A dicyanate homopolymer (CAS 25722-66-1, trade name Primaset(R) BA-200).

[0030] Compound (B) The compound (B) used in the present invention is a linear poly(diorgano)siloxane of the general formula (I) described above.

[0031] Poly(diorgano)siloxane(B) may be a solid or a liquid at 23°C and 1013 hPa, but poly(diorgano)siloxane(B) is preferably a liquid at 23°C and 1013 hPa.

[0032] When the poly(diorgano)siloxane (B) used in the present invention is a liquid, its kinematic viscosity is preferably 5 mPa·s to 100,000 mPa·s, more preferably 5 mPa·s to 10,000 mPa·s, and particularly preferably 10 mPa·s to 1,000 mPa·s at 23°C in all cases.

[0033] In the context of this invention, unless otherwise specified, kinematic viscosity is measured according to DIN 53019 at a temperature of 23°C and a pressure of 1013 hPa. Measurements are performed using an Anton Paar rotational rheometer, "Physica MCR 300". For viscosities of 1 to 200 mPa·s, a coaxial cylindrical measuring system (CC27) with a 1.13 mm annular measuring gap 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 adjusted according to the polymer viscosity (100 s). -1 1-99 mPa·s; 200s -1 At 100-999 mPa·s; 120s -1 At 1000-2999 mPa·s; 80s -1 At 3000-4999 mPa·s; 62s -1 5000~9999 mPa·s; 50s -1 At 10000~12499 mPa·s; 38.5s -1 At 12500~15999 mPa·s; 33s -1 At 16000~19999 mPa·s; 25s -1 At 20000~24999 mPa·s; 20s-1 At 25000~29999 mPa·s; 17s -1 At 30000~39999 mPa·s; 10s -1 40000~59999 mPa·s; 5s -1 60000~149999 mPa·s; 3.3s -1 150,000 to 199,999 mPa·s; 2.5s -1 200,000 to 299,999 mPa·s; 1.5s -1 (300,000 to 1,000,000 mPa·s).

[0034] After the measurement system has been thermally equilibrated at the measurement temperature, a three-stage measurement program is implemented, consisting of a break-in phase, preliminary shearing, and viscosity measurement. The break-in phase involves gradually increasing the shear rate over one minute until it reaches the measurement shear rate corresponding to the predicted viscosity. After reaching the predetermined shear rate, preliminary shearing is performed at a constant shear rate for 30 seconds, followed by 25 individual viscosity measurements of 4.8 seconds each, and the results are averaged. This average value corresponds to the kinematic viscosity and is reported in mPa·s units.

[0035] The poly(diorgano)siloxane (B) used in the present invention preferably has a weight-average molecular weight Mw of 300 to 3000 g / mol, more preferably 300 g / mol to 2000 g / mol, and even more preferably 300 g / mol to 1000 g / mol.

[0036] The poly(diorgano)siloxane (B) used in the present invention preferably has a number-average molecular weight Mn of 300 to 2000 g / mol, more preferably 300 g / mol to 1500 g / mol, and even more preferably 300 g / mol to 1000 g / mol.

[0037] Examples of monovalent SiC-bonded aliphatic hydrocarbon groups R include ether (COC)- groups and / or epoxy (C) groups. -O-C) may contain alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl, neopentyl and tert-pentyl group, hexyl groups such as n-hexyl group, heptyl groups such as n-heptyl group, n-octyl group and isooctyl group such as 2,4,4-trimethylpentyl group and 2,2,4-trimethylpentyl group, nonyl groups such as n-nonyl group, n-decyl group, etc. Examples include decyl groups, such as n-dodecyl groups, hexadecyl groups such as n-hexadecyl groups, and octadecyl groups such as n-octadecyl groups; cycloalkyl groups, such as cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, and methylcyclohexyl groups; alkenyl groups, such as vinyl groups, allyl groups, cyclopentenyl groups, and cyclohexenyl groups; and epoxy groups, such as 3-glycidoxypropyl groups, oxiran-2-yl groups, and 2-(3,4-epoxycyclohexyl)ethyl groups.

[0038] Examples of monovalent SiC-bonded aromatic hydrocarbon groups R that lack a phenolic OH group and may be interrupted by at least one heteroatom include aryl groups, e.g., phenyl, biphenyl, cumylphenyl, benzylphenyl, naphthyl, anthryl, phenanthryl; alkaryl groups, e.g., tolyl, xylyl, ethylphenyl; aralkyl groups, e.g., benzyl, cumyl, α- and β-phenylethyl; alkoxyaryl groups, e.g., methoxyphenyl; aryloxyaryl groups, e.g., phenyloxyphenyl; haloaryl groups, e.g., fluorophenyl, chlorophenyl, bromophenyl, trifluoromethylphenyl; and heterocyclic aromatic hydrocarbon groups, e.g., pyridyl, pyrazinyl, quinolinyl, furyl, and (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl)ethyl.

[0039] The group R preferably comprises a monovalent SiC-bonded alkyl group and / or aryl group having 1 to 8 carbon atoms, and more preferably comprises a methyl group and / or phenyl group.

[0040] A monovalent aromatic hydrocarbon group R having at least one phenolic hydroxyl group, which may be interrupted by a heteroatom. 1 is equation (II) [ka] (In the formula, R 4 , R 5 , R 6 , R 7 and R 8 In each case, independently, represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 18 carbon atoms, which may have a hydroxyl group and may be interrupted by at least one heteroatom. However, in equation (II), at least one base R 4 , R 5 , R 6 , R 7 or R 8 (This is either a phenolic hydroxyl group or contains a phenolic hydroxyl group.) It can be represented by:

[0041] Although not explicitly shown in formula (II), in further embodiments of the present invention, two or more groups R 4 , R 5 , R 6 , R 7 and R 8 This can mean a divalent hydrocarbon group which may have a hydroxyl group and may be interrupted by at least one heteroatom, and together they may form one or more ring structures. For example, R 5 and R 6 These can together form a ring, such as 5,6,7,8-tetrahydro-1-naphthol or 1-naphthol.

[0042] Preferably, base R 4 , R 5 , R6 , R 7 and R 8 In each case, independently, it is a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 8 carbon atoms, which may have a hydroxyl group and may be bonded via an oxy (-O-) unit.

[0043] Preferably, base R 6 It is a hydroxyl group, and the group R 4 , R 5 , R 7 and R 8 In each case, it is a hydrocarbon group having 1 to 12 carbon atoms, which may be independently bonded via hydrogen atoms or oxy groups (-O-).

[0044] More comfortable, base R 6 It is a hydroxyl group, and the group R 4 , R 5 , R 7 and R 8 In each case, these are independently hydrocarbon groups having a hydrogen atom or 1 to 4 carbon atoms.

[0045] Particularly preferred, base R 6 It is a hydroxyl group, and the group R 4 , R 5 , R 7 and R 8 It is a hydrogen atom.

[0046] Hydrocarbon group R may be substituted 1Examples include hydroxyphenyl group [-C6H4(OH)]-, hydroxy(methyl)phenyl group [-C6H3(OH)(CH3)]-, hydroxy(dimethyl)phenyl group [-C6H2(OH)(CH3)2]-, hydroxy(ethyl)phenyl group [-C6H3(OH)(CH2CH3)]-, hydroxy(methyl)(isopropyl)phenyl group [-C6H3(OH)(CH3)(CH(CH3)2)]-, hydroxy(methoxy)phenyl group [-C6H3(OH)(OCH3)]-, hydroxy(phenyloxy)phenyl group [-C6H3(OH)(OC6H5)]-, (hydroxyphenyl)phenyl group [-C6H4(C6H4(OH))]-, hydroxynaphthyl group [-C 10 H6(OH)]-, hydroxy(phenyl)phenyl group [-C6H3(OH)(C6H5)]-, hydroxy(benzyl)phenyl group [-C6H3(OH)(CH2(C6H5))]- and (hydroxycumyl)phenyl group [-C6H3(C(CH3)2)(C6H4(OH))].

[0047] Group R 1 Preferably includes hydroxyphenyl group, hydroxy(methyl)phenyl group, hydroxy(dimethyl)phenyl group, hydroxy(ethyl)phenyl group and hydroxy(methyl)(isopropyl)phenyl group, more preferably includes hydroxyphenyl group.

[0048] Examples of at least one compound (B) used according to the present invention preferably include formulas (III) to (XII):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0049] At least one compound (B) used in accordance with the present invention preferably includes compounds of formula (III), formula (VI), formula (X), and formula (XI), and more preferably includes compounds of formula (III), formula (X), and formula (XI).

[0050] Preferably, in formulas (III) to (XI), m is 1 to 14, more preferably 1 to 9, and particularly 1 to 4.

[0051] Preferably, in formula (XII), the sum n+o is 1 to 14, more preferably 1 to 9, and particularly 1 to 4.

[0052] More preferably, at least one compound (B) used in accordance with the present invention includes those of formula (III), (X), or (XI) where m is 1 to 9.

[0053] Particularly preferably, at least one compound (B) used in accordance with the present invention includes those of formulas (III) and (X), where m is 1 to 4.

[0054] The poly(diorgano)siloxane (B) used according to the present invention is a commercial product or can be produced by standard chemical methods. For example, "ACS Symposium Series, vol. 729, Silicones and Silicone-Modified Materials, Chapter 9, 164-169 (DOI: 10.1021 / bk-2000-0729.ch009)" and "ACS Polymer Preprints 1992, 33(1), 988-989" describe methods for preparing bis[1,3-(4-hydroxyphenyl)]tetramethyldisiloxane. The reaction is carried out via a Grignard reaction of 4-bromophenyl pyranyl ether with dimethyldichlorosilane or dimethyldiethoxysilane, followed by hydrolysis and condensation reactions. Similarly, longer-chain siloxanes can also be prepared, for example, by a Grignard reaction of 4-bromophenyl pyranyl ether with an α,ω-dichloropoly(diorgano)siloxane 9 2SiO) 1-19 SiR 9 2Cl], 1-chloro-ω-triorganosilyl-poly(diorgano)siloxane [Cl(SiR 9 2O) 1-19 SiR 9 3], or a monochloro-substituted poly(diorgano)siloxane having a terminal triorganosilyl group [(SiR 9 3O) 1-p (ClSiR 9 2O)(SiR 9 3O) 1-q , where R 9 has the definition of R and the sum p + q is 19, and can be prepared by a Grignard reaction with a poly(diorgano)siloxane and subsequent removal of the tetrahydropyranyl protecting group. It is also possible to use other phenol-OH protecting groups, such as trimethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, methyl, tert-butyl, triphenylmethyl, benzyl, allyl, methoxymethyl, benzoyloxymethyl or methoxybenzyl protecting groups.

[0055] It is possible to use only one type of poly(diorgano)siloxane (B), or a mixture of different poly(diorgano)siloxanes (B).

[0056] The composition of the present invention contains poly(diorgano)siloxane (B) in all cases, preferably in an amount of 1 to 70 parts by mass, more preferably 5 to 50 parts by mass, and particularly 5 to 30 parts by mass, based on 100 parts by mass of component (A).

[0057] In addition to components (A) and (B), the compositions of 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).

[0058] In a preferred embodiment, the present invention composition is composed of 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 excipient (H) The mixture further comprises, where 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) is different from at least one compound (A) and (B).

[0059] The composition of the present invention: • A single compound (C) or a mixture of different compounds (C), preferably a single compound (C); • A single compound (D) or a mixture of different compounds (D), preferably a single compound (D); • A single compound (E) or a mixture of different compounds (E), preferably a single compound (E); • A single compound (F) or a mixture of different compounds (F), preferably a single compound (F); · A single compound (G) or a mixture of different compounds (G), preferably a single compound (G); and / or • A single compound (H) or a mixture of different compounds (H), preferably a single compound (H) It may include.

[0060] In the present invention, the name "component (C)" represents the entirety of at least one compound (C), the name "component (D)" represents the entirety of at least one compound (D), the name "component (E)" represents the entirety of at least one compound (E), the name "component (F)" represents the entirety of at least one compound (F), the name "component (G)" represents the entirety of at least one compound (G), and the name "component (H)" represents the entirety of at least one compound (H).

[0061] Compound (C) At least one optional modifier (C) is preferably of the formula R 10 i (OR 11 ) j SiO (4-i-j) / 2 (XIII) (In the formula, R 10 This represents a monovalent, SiC bond, optionally substituted hydrocarbon group, which is identical or different and can be interrupted by a hydrogen atom or at least one heteroatom. R 11 This represents a monovalent hydrocarbon group having 1 to 18 carbon atoms, which are identical or different and may be interrupted by a hydrogen atom or at least one heteroatom. i is 0, 1, 2, or 3, preferably 1, 2, or 3. j is 0, 1, 2, or 3, preferably 0, 1, or 2, more preferably 0 or 1, particularly 0. However, in formula (XIII), the sum i + j is 3 or less, compound (C1) contains 2 to 20 units of formula (XIII), and compound (C1) does not contain a phenolic hydroxyl group. It contains organosilicon compounds (C1) that include the unit.

[0062] A monovalent, SiC bonded, substituted hydrocarbon group R which may be interrupted by at least one heteroatom 10 Examples of R include the groups mentioned; unsaturated hydrocarbon groups, such as vinyl, propenyl, 5-hexenyl, cyclohexenyl, 2-(3-cyclohexenyl)ethyl, bicyclo[2.2.1]hepten-2-yl, dicyclopentenyl, 7-octenyl, 10-undecenyl, 4-vinylcyclohexyl, 3-norborneyl, vinylphenyl, propenylphenyl, ethynyl, propynyl, butynyl, arylethynyl, ethynylphenyl, etc.; imide groups, such as N-(5-ethynylphthalimide)phenyl, N-(5-(phenylethynyl)phthalimide)phenyl, najimidophenyl, maleimidophenyl, 3-maleimidophenyl Ropil groups, etc.; epoxy groups, e.g., 3-glycidoxypropyl group, 4-(oxiran-2-yl)phenyl group, oxiran-2-yl group, 2-(3,4-epoxycyclohexyl)ethyl group, etc.; acrylate groups, e.g., 3-methacryloyloxypropyl group, acryloyloxymethyl group, methacryloyloxymethyl group, etc.; amine groups, e.g., aminophenyl group, 3-aminopropyl group, N-(2-aminoethyl)-3-aminopropyl group, N-phenylaminomethyl group, etc.; hydroxyalkyl groups, e.g., hydroxypropyl group, etc.; and polycaprolactone, polycaprolactam, cyanatophenyl, 3-cyanatopropyl, isocyanatophenyl, 3-isocyanatopropyl group.

[0063] Preferably, base R 10 This is a hydrogen atom, or a phenyl group or a methyl group.

[0064] Preferably, base R 11It comprises an aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, or isobutyl group, and particularly a methyl group or an ethyl group.

[0065] 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), 1,3-bis(norbornenylethyl)-1,1,3,3-tetramethyldisiloxane, average composition (PhSiO 3 / 2 ) 20 (PhSi(OMe)O 2 / 2 ) 66 (PhSi(OMe)2O 1 / 2 ) 14 , an organopolysiloxane with a weight-average molecular weight Mw = 2190 g / mol, average composition (PhSiO 3 / 2 ) 75 (Me3SiO 1 / 2 ) 25, organopolysiloxanes with a weight-average molecular weight Mw = 1380 g / mol, octa(epoxycyclohexyl)-POSS (CAS 187333-74-0), octaphenyl-POSS (CAS 5256-79-1), octaphenylcyclotetrasiloxane (CAS 546-56-5), 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane (CAS 77-63-4), 1,1,3,3,5,7-hexamethyl-5,7-diphenylcyclotetrasiloxane, 1,1,3,3-tetramethyl-5,5,7,7-tetraphenylcyclotetrasiloxane (CAS 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.

[0066] The optional at least one modifier (C) is preferably a thermoplastic organic polymer ("thermoplastic resin") (C2) having 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, polyamideimide, polyarylate, polyesterimide, polyetherimide, polyaramid, polyacrylate, polyhydantoin, liquid crystal polymer, polycarbonate, polyester carbonate, and polyethylene terephthalate, and mixtures or copolymers thereof. The thermoplastic resin (C2) has either reactive or chemically inert end groups. In polymerization reactions, reactive end groups remain from the corresponding reactive groups of the monomers as a result of the formation. These groups are preferably hydroxyl, amino, carboxyl, or isocyanate groups. Examples of chemically inert end groups include methyl or phenyl groups. The thermoplastic resin (C2) has a glass transition temperature of 100°C or higher, preferably 130°C to 450°C, more preferably 150°C to 400°C, and particularly 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, even more preferably 2000 to 30000 g / mol, and particularly 3000 to 20000 g / mol.

[0067] At least one optional modifier (C) is preferably free of siloxy (≡Si-O-) units and phenolic hydroxyl groups, and has the general formula (XIV) R 12 -OCN (XIV) (In the formula, R 12(wherein is a monovalent, substituted aromatic hydrocarbon group that can be interrupted by at least one heteroatom, except in the case of a cyanate ester group that is directly bonded to an aromatic carbon atom.) It is an organic monofunctional cyanate ester having [a certain characteristic].

[0068] Examples of compounds (C3) include cyanatobenzene (CAS 1122-85-6), 1-cyanato-4-cumylbenzene (CAS 110215-65-1), 1-cyanato-4-tert-butylbenzene, 1-cyanato-2-tert-butylbenzene, 4-cyanatobiphenyl, 1-cyanatonaphthalene, 2-cyanatonaphthalene, 4-cyanatononylbenzene, 4-chlorocyanatobenzene, 4-cyanatodiphenylsulfone, 4-cyanatotoluene, 4-cyanatodiphenyl ether, 4-cyanatodiphenylketone, and 4-(cyanato)methoxybenzene; also, propenyl-substituted monofunctional cyanate esters such as 4-cumyl-2-(propenyl)cyanatobenzene or 2-(propenyl)cyanatobenzene.

[0069] The compound (C3) preferably has a boiling point at 10¹³ hPa at least 150°C, more preferably at least 180°C, and particularly at least 220°C.

[0070] The optional at least one modifier (C) is preferably a monomeric aromatic hydrocarbon (C4) that lacks siloxy (≡Si-O-) units, epoxy groups, imide groups, and cyanate groups, has at least one phenolic hydroxyl group, and may have one or more aliphatic carbon-carbon multiple bonds.

[0071] The optional aliphatic carbon-carbon multiple bond in compound (C4) is preferably a propenyl group bonded to an aromatic carbon atom, and more preferably, one phenolic hydroxyl group and optionally one propenyl group are bonded to the aromatic group in compound (C4).

[0072] Examples of compounds without aliphatic carbon-carbon multiple bonds (C4) include monovalent, 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, 2,4-bis(α,α-dimethylbenzyl)phenol, nonylphenol Phenols, xylenols or 2,6-dinonylphenols; polyhydric phenols, e.g., 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; aromatic compounds containing two hydroxyphenyl groups (bisphenol) or two or more hydroxyphenyl groups, e.g., bis(2-Hy) 1,1-bis(4-hydroxyphenyl)ethane (bisphenol C), 2,2-bis(4-hydroxyphenyl)propane (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 F Examples include L), 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.

[0073] 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.

[0074] The compound (C4) is preferably 4-phenylphenol, 2-methoxy-4-(2-propenyl)phenol, 4-cumylphenol, 4-isopropylphenol, 4-tert-butylphenol, 2-tert-butylphenol, bisphenols, 2,2-bis(3-(2-propenyl)-4-hydroxyphenyl)propane, 4-(1-(4-hydroxy-3-propenylphenyl)propyl)-2-propenylphenol, 4-cumyl-2-(2-propenyl)phenol, 4-cumyl-2-(2-methyl-2-propenyl)phenol, 4-tert-butyl-2-(2-propenyl) Lopenyl)phenol, 4-tert-butyl-2-(2-methyl-2-propenyl)phenol or 2-(2-propenyl)phenol, 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 and S.

[0075] If the composition of the present invention contains at least one modifier (C), the mixture may contain only one of modifiers (C1) to (C4), or two or more different modifiers (C1) to (C4).

[0076] If the composition of the present invention contains at least one modifier (C), the at least one modifier (C) is present in any case in an amount of preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and particularly 1 to 10 parts by mass, based on 100 parts by mass of the total of components (A) and (B).

[0077] Compound (D) The optional at least one reactive resin (D) is preferably an aromatic hydrocarbon compound that is free of siloxy (≡Si-O-) units, cyanate ester groups, and phenolic hydroxyl groups, and may be interrupted or substituted by at least one heteroatom selected from the group consisting of epoxides (D1) and imides (D2), wherein the epoxide (D1) comprises at least two substituted polymerizable glycidyloxy groups, glycidyloxycarbonyl groups, glycidylamino groups, diglycidylamino groups, or oxiran-2-yl groups per molecule, preferably at least two such groups bonded to an aromatic carbon atom; the imides (D2) comprises at least two polymerizable 5-ethynylphthalimide groups, 5-(phenylethynyl)phthalimide, najimide, benzocyclobutenephthalimide, or maleimide groups per molecule, preferably at least two such groups bonded to an aromatic carbon atom; particularly preferred are maleimide groups, glycidyloxy groups, glycidylamino groups, and diglycidylamino groups.

[0078] Preferably, the at least one reactive resin (D) comprises at least two aromatic hydrocarbon groups per molecule, which may be interrupted or substituted by at least one heteroatom, and each group comprises a maleimide group, a glycidyloxy group, a glycidyloxycarbonyl group, a glycidylamino group, or a diglycidylamino group bonded to an aromatic carbon atom. More preferably, (D) comprises a compound comprising at least two aromatic hydrocarbon groups, which may be interrupted or substituted by at least one heteroatom, and each group comprises a maleimide group, a glycidyloxy group, a glycidylamino group, or a diglycidylamino group bonded to an aromatic carbon atom, and the group is covalently bonded or -CR 13 2-, -CR 13 =CR 13 -, =C=CR 13 2, -O-, -S-, -N=N-, -CR 13 =N-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -S(=O)2-, O=P(O-)3, -SiR 132-, phenylene, arylene, biphenylene, biarylene, naphthylene or cycloalkanediyl group, e.g., tricyclo[5.2.1.0 2,6 They are linked to each other via crosslinking units selected from the group consisting of decanediyl or bicyclo[2.2.1]heptanediyl, etc.

[0079] base R 13 In all cases, R is independent. 2 This is the basis stated for [the subject].

[0080] The reactive resin (D) preferably contains an aromatic ring structure that does not contain heteroatoms.

[0081] Preferably, the epoxy resin (D1) is copolymerizable with the cyanate ester resin (A).

[0082] Preferably, the imide resin (D2) does not copolymerize with the cyanate ester resin (A).

[0083] 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); glycidyl ethers of condensation products of phenol, naphthol, naphthalenediol, bisphenol or cresol with formaldehyde, e.g., cresol novolac glycidyl ether (CAS 29690-82-2), phenol novolac glycidyl ether (CAS 9003-36-5, CAS 27610-48-6); 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, 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), 1,2,3-benzenetricarboxylic acid triglycidyl, 1,2,4-benzenetricarboxylic acid triglycidyl (CAS 7237-83-4), 1,3,5-benzenetricarboxylic acid triglycidyl (CAS 7176-19-4); 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 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-end-terminated thermoplastic polymers, such as those that can be prepared by the reaction of amino or hydroxy-end-terminated thermoplastic resins (C2) with epichlorohydrin, glycidyloxy or diglycidylamino-end-terminated polysulfones, etc.; homopolymerized or copolymerized epoxy resins, such as bisphenol A-epichlorohydrin copolymer (CAS 25036-25-3), 2,2',6,6'-tetrabromobisphenol A-epichlorohydrin copolymer (CAS Examples include 40039-93-8), and the reaction product of diglycidylbisphenol A and m-phenylenebis(methylamine) (CAS 110839-13-9); as well as mixtures of various epoxy resins (D1).

[0084] 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); reaction products of condensation products of formaldehyde and aniline with maleic anhydride (CAS 28630-26-4, CAS 67784-74-1); bis(4-maleimidophenyl) ether, 2,2-bis[4-(maleimidophenoxy)phenyl]propane (CAS 79922-55-7), bis(4-maleimidophenyl) sulfone (CAS Examples include maleimide-terminated thermoplastic polymers (D2), such as 13102-25-5), bis(4-maleimidephenyl)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-maleimidephenoxy)diphenylsulfone, or maleimide-terminated thermoplastic polymers (D2), which can be produced, for example, by the reaction of an amino-terminated thermoplastic resin (C2) with maleic anhydride, such as maleimide-terminated polysulfone ethers, and mixtures of different maleimide resins (D2).

[0085] Preferably, the at least one compound (D) is a monomeric compound that does not contain a thermoplastic homopolymer or copolymer.

[0086] If the composition of 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 mass, more preferably 1 to 30 parts by mass, and particularly 1 to 20 parts by mass, based on 100 parts by mass of the total of components (A) and (B).

[0087] If the composition of the present invention contains at least one polymerizable imide (D2), it is preferably in combination with a component copolymerizable with both a cyanate ester group and an imide group, and preferably with both a cyanate ester group and a maleimide group. These components are selected from cyanate esters (A), modifiers (C3), or modifiers (C4) in which a propenyl group is bonded to an aromatic carbon atom; or selected from aromatic hydrocarbon compounds containing one or two hydroxyl groups bonded to an aromatic carbon atom per molecule and one or two polymerizable imide groups, preferably maleimide groups, bonded to an aromatic carbon atom, such as N-(4-hydroxyphenyl)maleimide (CAS 7300-91-6).

[0088] When the composition of 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, more preferably 55:45 to 90:10, and particularly 65:45 to 80:20.

[0089] Compound (E) At least one filler (E) in the composition of the present invention may be a desired conventionally known particulate filler.

[0090] The present invention preferably provides for at least one optional filler (E) that dissolves in toluene at 23°C and 1000 hPa in an amount of less than 1% by mass.

[0091] Examples of fillers include non-reinforcing particulate fillers, i.e., those with a BET specific surface area of ​​preferably 50 m². 2 Fillers up to 50 m² / g, for example, fillers consisting of quartz, glass, cristobalite, and diatomaceous earth; water-insoluble silicates such as calcium silicate, calcium metasilicate, magnesium silicate, zirconium silicate, talc, mica, feldspar, kaolin, and zeolite; metal oxides or mixed oxides thereof such as oxides of aluminum, titanium, iron, boron, or zinc; barium sulfate, calcium carbonate, marble flour, gypsum, silicon nitride, silicon carbide, boron nitride, and plastic powders (for example, polyacrylonitrile or polyetherimide powder); reinforcing fillers, i.e., with a BET specific surface area of ​​50 m². 2 Fillers exceeding / g, e.g., fumed silica, precipitated silica, precipitated chalk, carbon black (e.g., furnace black and acetylene black), silicon-aluminum mixed oxides with a large BET specific surface area; aluminum hydroxide, magnesium hydroxide, hollow spherical fillers, e.g., glass microballoons, glass spheres, phenolic thermospheres, ceramic microspheres, e.g., Zeeospheres from 3M Deutschland GmbH in Neuss, Germany. TM Available under trade names; fibrous fillers, such as wollastonite, montmorillonite, basalt, bentonite, chopped and / or crushed glass fibers (short glass fibers), or mineral wool; metal fibers, metal oxides, glass, ceramics, carbon or plastic fibers; and natural fibers made of cellulose, flax, hemp, wood or sisal.

[0092] At least one filler (E) of the present invention may be present in the composition of the present invention as a single filler or as any desired mixture of at least two different fillers (E).

[0093] Component (E) is selected from particulate fillers (E1) containing fibers up to 5 cm in length and fiber semifinished products (E2) containing fibers longer than 5 cm in length, and is preferably fiber semifinished products (E2).

[0094] The optional at least one filler (E2) preferably includes any conventionally known fiber-forming material made of polypropylene, polyethylene, polytetrafluoroethylene or polyester; metal fibers made 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, polybenzothiazole, polybenzimidazole, polybenzoxazole, titanium dioxide, boron, and aromatic polyamide fibers, such as poly-p-phenylene terephthalamide.

[0095] The at least one filler (E) described may be surface-treated, for example, by hydrophobization, or by treatment with an organosilane or organosiloxane, stearic acid, or one or more modifiers (C). Furthermore, the filler surface can be modified, for example, by oxidation or treatment with an acid or base, so that it can chemically bond with the cured resin matrix. Preferably, the at least one filler (E2) is surface-treated.

[0096] When the composition of the present invention contains at least one filler (E1), the content of the at least one filler (E1) is preferably 5 to 900 parts by mass, more preferably 10 to 400 parts by mass, and particularly 15 to 150 parts by mass, based on 100 parts by mass of the total of components (A) and (B).

[0097] When the composition of the present invention contains at least one filler (E2), the content of the at least one filler (E2) is preferably 20 to 900 parts by mass, more preferably 60 to 900 parts by mass, and particularly 100 to 400 parts by mass, based on 100 parts by mass of the total of components (A) and (B).

[0098] The at least one filler (E2) may exist in different forms in the composition of the present invention, for example, as a continuous rope, fabric, noncrimp fabric, knitted fabric, braid, mat, nonwoven fabric, whisker, chopped staple fiber, or random fiber felt, each containing 1,000 to 400,000 individual filaments.

[0099] The composition of the present invention preferably comprises at least one filler (E), the at least one filler (E) more preferably mainly, and especially entirely, consists of a filler (E2).

[0100] Preferably, the composition of the present invention comprises a rope, textile fabric, non-crimped textile fabric, knitted textile or braided textile as a filler (E2), more preferably consisting of carbon fiber, aromatic polyamide fiber, ceramic fiber and / or glass fiber, and each of the respective fibers and / or ropes, textile fabrics, non-crimped textiles, knitted textiles or braided textiles made from them are particularly surface-treated. Particularly preferably, each fiber is surface-treated.

[0101] The optional textile fabric (E2) or laminated fiber fabric (E2) according to the present invention is preferably used in multiple layers.

[0102] In a preferred embodiment, component (E2) comprises at least 80% by mass, more preferably at least 90% by mass, of a fibrous fabric, laminated fibrous cloth, knitted fibrous fabric, or braided fibrous fabric, based on 100% by mass of component (E2).

[0103] Compound (F) The compositions of the present invention can be cured in the presence of at least one curing accelerator (F), for example, those 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, 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 metal-organic compounds, such as metal alkoxides, metal carboxylates, or metal chelate complexes of aluminum, copper, zinc, titanium, iron, manganese, cobalt, chromium, or nickel. Examples of metal-organic 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) octoate, zinc(II) acetylacetonate, iron(III) acetylacetonate, cobalt(II) acetylacetonate, chromium(III) acetylacetonate, aluminum(III) acetylacetonate, and copper(II) acetylacetonate.

[0104] When at least one curing accelerator (F1) is used to cure the composition of the present invention, this is preferably a combination of a metal-organic compound and a co-accelerator having at least one active proton, and more preferably a combination of a metal-organic compound and a phenol (C4), such as nonylphenol.

[0105] If the composition of the present invention contains at least one curing accelerator (F1), the amount is preferably 0.00001 to 5 parts by mass based on 100 parts by mass of component (A), and more preferably the amount of the metal organic compound (F1) is 0.0001 to 0.02 parts by mass based on 100 parts by mass of component (A).

[0106] If the composition of the present invention contains a free radical polymerizable functional group, such as an aliphatic carbon-carbon multiple bond, a free radical-forming curing accelerator (F2), such as an organic peroxide, such as dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, tert-butylperbenzoate, etc., or an azo compound, such as azobis(isobutyronitrile), etc., can be used alone or in addition to (F1). If the composition of the present invention contains a free radical-forming curing accelerator (F2), the amount is preferably 0.1 to 2 parts by mass based on 100 parts by mass of the total of the imide group-containing modifier (C1) and the imide resin (D2). It is preferable not to use a free radical-forming curing accelerator (F2).

[0107] Compound (G) Examples of at least one optional 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, glycerol, etc.; ethers, e.g., methyl tert-butyl ether, di-tert-butyl ether, di-, tri- or tetraethylene glycol dimethyl ether, etc.; saturated hydrocarbons, e.g., n-hexane, cyclohexane, n-heptane, n-octane, and isomer octanes, e.g., 2-ethylhexane, 2,4,4-trimethylpentane, 2,2,4-trimethylpentane and 2-methylheptane, etc.; trichloroethylene; and mixtures of saturated hydrocarbons having a boiling point in the range of 60 to 300°C, Exxsol TM Hydroroseal (R) Shellsol (R)Available under trade names; aromatic solvents, e.g., benzene, toluene, styrene, o-, m-, or p-xylene, solvent naphtha, dimethyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, mesitylene, chlorobenzene, etc.; aldehyde acetals, e.g., methylal, ethylhexylal, butyral, 1,3-dioxolane, glycerol formal, etc.; carbonate esters, e.g., 1,3-dioxolan-2-one, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, propylene glycol carbonate, ethylene carbonate, etc.; ketones, e.g., acetone, Examples include methyl isobutyl ketone, methyl ethyl ketone, methyl isoamyl ketone, diisobutyl ketone, acetone, cyclohexanone, etc.; esters, such as ethyl acetate, n-butyl acetate, ethylene glycol diacetate, γ-butyrolactone, 2-methoxypropyl acetate (MPA), dipropylene glycol dibenzoate, ethyl ethoxypropionate; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone; acetonitrile; and dimethyl sulfoxides. The at least one solvent (G) is preferably an aromatic hydrocarbon or a ketone.

[0108] If the composition of the present invention contains at least one solvent (G), the amount is preferably 10 to 300 parts by mass, more preferably 10 to 100 parts by mass, and particularly 10 to 50 parts by mass, based on 100 parts by mass of the total of components (A) and (B). The composition of the present invention preferably does not contain solvent (G).

[0109] Compound (H) The optional at least one auxiliary agent (H) according to the present invention preferably includes pigments, dyes, fragrances, processing aids such as tackifiers, lubricants, mold release agents, antiblocking agents or dispersants; stabilizers against hydrolysis, light, oxidation, heat, and discoloration; and flame retardants or plasticizers.

[0110] If the composition of 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 mass, more preferably 0.1 to 10 parts by mass, and particularly 0.1 to 10 parts by mass, based on 100 parts by mass of the total of components (A) and (B). The composition of the present invention preferably does not contain auxiliary agent (H).

[0111] The composition of the present invention, preferably: (A) at least one type of cyanate ester resin, (B) At least one poly(diorgano)siloxane, (C) At least one modifier, (D) At least one reactive resin, (E2) At least one fiber-reinforced filler, (F) At least one type of curing accelerator, (G) optionally at least one solvent, and (H) Other components (optional) It is a composition containing [the specified ingredient].

[0112] The composition of the present invention, preferably: (A) at least one type of cyanate ester resin, (B) At least one poly(diorgano)siloxane, (C) at least one modifier, (D) At least one reactive resin, (E2) At least one fiber-reinforced filler, (F) At least one type of curing accelerator, (G) optionally at least one solvent, and (H) Other components (optional) It is a composition containing [the specified ingredient].

[0113] In a particularly preferred embodiment, the composition of the present invention is: (A) at least one type of cyanate ester resin, (B) At least one poly(diorgano)siloxane, (C) At least one modifier, (D1) At least one type of epoxy resin, (E2) At least one fiber-reinforced filler, (F) At least one type of curing accelerator, (G) optionally at least one solvent, and (H) Other components (optional) It is a composition containing [the specified ingredient].

[0114] In a particularly preferred embodiment, the composition of the present invention is: (A) at least one type of cyanate ester resin, (B) At least one poly(diorgano)siloxane, Optionally, at least one modifier selected from the group (C1) to (C4), (D2) At least one maleimide resin, (E2) At least one fiber-reinforced filler, (F) At least one type of curing accelerator, (G) optionally at least one solvent, and (H) Other components as desired, A composition containing the above, provided that at least one component (C4) is present, which is either component (A), (C3), or an aromatic carbon atom with a propenyl group directly bonded to it. The compositions of the present invention preferably contain no components other than components (A) and (B), any components (C) through (H), and raw-material-typical impurities, such as catalyst residues, such as sodium chloride and potassium chloride, impurities in technical-grade cyanate ester resin monomers, and reaction products of the components used that are formed during mixing / storage.

[0115] In the composition of the present invention, each of the above components can be used alone or as a mixture of at least two components.

[0116] The present invention further provides a method for producing the composition of the present invention by mixing the individual components in any order.

[0117] In the method according to the present invention, mixing can be carried out at a temperature preferably in the range of 20 to 150°C, more preferably in the range of 50 to 130°C, and particularly in the range of 60 to 120°C. Particularly preferably, mixing is carried out at a temperature that would occur when mixing at room temperature, i.e., the temperature of the raw materials plus the temperature rise due to the energy input during mixing, and the mixture can be heated or cooled as necessary.

[0118] Mixing can be carried out at ambient atmospheric pressure, i.e., a pressure of approximately 900–1100 hPa. Mixing can also be carried out under intermittent or continuous reduced pressure, for example, at an absolute pressure of 30–500 hPa, to remove volatile components and / or air. It can also be carried out under positive pressure, particularly at an absolute pressure of 1100–3000 hPa, such as in a continuous process mode, where these pressures are established within a closed system, for example, as a result of the pressure during pumping and the vapor pressure of the materials used at high temperatures.

[0119] The method of the present invention can be carried out continuously, discontinuously, or semi-continuously, and is preferably carried out discontinuously.

[0120] In one preferred embodiment of the method of the present invention for producing the composition of the present invention, the individual components except component (E) are premixed in any desired order, and then the filler (E2) is impregnated with the premix in a way that does not generate bubbles, by known processing techniques such as prepreg (from a molten, solution or suspension), sheet molding compound (SMC), filament winding, compression molding, pultrusion, fiber injection, and injection molding, for example, resin transfer molding or vacuum injection, and processed into a molded article.

[0121] The composition of the present invention can be used in any conventional application in which an organic reactive resin system or its prepolymer subsequently hardens into a thermosetting resin.

[0122] In one modified example of the method of the present invention, components (A) and (B), as well as optional components (C), (D), (G), and (H), are preferably first 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 this premix, either under pressure or while degassing. 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.

[0123] In a further preferred variation of the method of the present invention, components (A) and (B), along with optional components (C), (D), (G), and (H), are first 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. Degassing is preferably performed simultaneously with the injection step.

[0124] In a further preferred variation of the method of the present invention, components (A) and (B), along with optional components (C), (D), (G), and (H), are first mixed in any desired order to form a premix, which is then applied to a release liner. Subsequently, component (E2), preferably an oriented rope, woven fabric, non-crimped woven fabric, knitted fabric, or braid, is pressed between two coated paper sheets and passed through a series of heated rollers to ensure complete wetting of component (E2).

[0125] The composition of the present invention can be formed into any desired shape by mechanical pressure at room temperature or, if necessary, at high temperatures.

[0126] The compositions of the present invention are preferably moldable, and more preferably molded and cured in a mold cavity or around a molding template.

[0127] Therefore, the present invention further provides the use of the compositions of the present invention for manufacturing molded articles or fiber composite materials.

[0128] Therefore, the present invention further provides a method for producing a molded article by curing a composition after molding it.

[0129] Therefore, the present invention further provides molded articles that can be obtained from the composition of the present invention by molding and curing.

[0130] The composition produced according to the present invention is preferably degassed before curing, and more preferably degassed after molding and before curing.

[0131] The crosslinking according to the present invention is preferably carried out at a temperature in the range of 50 to 350°C, more preferably in the range of 100 to 300°C, and particularly in the range of 120 to 270°C. Very preferably, the crosslinking according to the present invention is carried out in steps at a temperature of 120 to 270°C.

[0132] Since crosslinking can be accelerated by increasing the temperature, it is possible to perform molding and crosslinking in a single process.

[0133] The molded article according to the present invention is preferably made of a fiber composite material (or fiber-reinforced plastic "FRP").

[0134] The present invention further provides a method for producing a fiber composite material, characterized by molding and curing the composition of the present invention.

[0135] Therefore, the present invention further provides a fiber composite material that can be obtained from the composition of the present invention by molding and curing.

[0136] The composition of the present invention may be solid or liquid at a temperature of 100°C and a pressure of 1013 hPa, and is preferably liquid at 100°C and 1013 hPa.

[0137] When the compositions of the present invention are liquid at 100°C and 10¹³ hPa, they have a kinematic viscosity of preferably 1 to 5000 mPa·s, preferably 1 to 2000 mPa·s, more preferably 1 to 1000 mPa·s, and particularly 1 to 500 mPa·s at both 100°C and 10¹³ hPa.

[0138] The critical stress concentration coefficient K for the corresponding cured unmodified cyanate ester resin (A) of the cured composition of the present invention, for example, a composition comprising 85 parts by mass of cyanate ester resin (A) and 15 parts by mass of poly(diorgano)siloxane (B). Ic In all cases, the ratio, measured at 23°C, is preferably greater than 1.0, more preferably greater than 1.1, and particularly greater than 1.2.

[0139] After storage in water at 70°C for 1600 hours, the cured composition of the present invention, for example, a composition comprising 85 parts by mass of cyanate ester resin (A) and 15 parts by mass of compound (B), exhibits a water absorption rate that is preferably at least 20%, preferably at least 30%, more preferably at least 40%, and particularly at least 50% lower than that of the corresponding unmodified cyanate ester resin (A).

[0140] The curing composition of the present invention, for example, a composition comprising 85 parts by mass of cyanate ester resin (A) and 15 parts by mass of poly(diorgano)siloxane (B), preferably has a glass transition temperature greater than 170°C, more preferably greater than 200°C, and particularly greater than 230°C.

[0141] After storage at 240°C for 200 hours, the cured composition of the present invention, for example, a composition consisting of 85 parts by mass of cyanate ester resin (A) and 15 parts by mass of poly(diorgano)siloxane (B), exhibits a weight loss of preferably 300% or less, preferably 200% or less, more preferably 100% or less, and particularly 80% or less, compared to the corresponding unmodified cyanate ester resin (A).

[0142] The composition according to the present invention has the advantage that the cyanate ester resin (A) is miscible with poly(diorgano)siloxane (B) without the addition of further solvents and without pre-crosslinking in the presence of a catalyst, and that the cured thermosetting mixture of components (A) and (B) does not exhibit any macroscopic separation of the siloxane component from the polycyanurate network in the form of leaching, seepage, or a sticky surface.

[0143] The composition of the present invention has the advantage that the cyanate ester resin (A) can be mixed with poly(diorgano)siloxane (B) without the addition of an additional solvent, and that the poly(diorgano)siloxane (B) does not leach out of the thermosetting network during or after curing.

[0144] The composition of the present invention has the advantage of reduced water absorption and improved hydrolysis resistance in the cured state compared to the corresponding unmodified cyanate ester resin.

[0145] The composition of the present invention has the further advantage of having high thermal oxidation stability in the cured state.

[0146] Compared to composite materials made from pure organic cyanate ester resins, the molded articles according to the present invention have the advantages of being thermally stable and having a reduced fire load.

[0147] The composition of the present invention has the advantage of being able to be manufactured by a simple method from readily available raw materials.

[0148] The composition of the present invention has the advantage that its processing does not produce harmful emissions to the extent typically generated by organic cyanate ester resins used according to the prior art. [Examples]

[0149] Examples of Work The following examples, carried out at atmospheric pressure, i.e., about 1013 hPa, and room temperature, i.e., about 23°C, or the temperature established when the reactants are combined at room temperature without additional heating or cooling, illustrate how the present invention can be carried out in principle, but is not limited to what is disclosed herein.

[0150] Molar masses In the context of this invention, the weight-average molecular weight Mw and the number-average molecular weight Mn are in units of g / mol and rounded to the nearest 10 according to Section 4 of DIN 1333:1992-02. A column array consisting of three columns with different pore size distributions in the order of 10,000 Å, 500 Å, and 100 Å, based on polystyrene-kodivinylbenzene, is used as the stationary phase, and the array has a size cutoff greater than 450,000 g / mol. The analysis is performed by size exclusion chromatography (SEC / GPC) according to DIN 55672-1 / ISO 16014-1 and ISO 16014-3, using tetrahydrofuran (THF) as the eluent, after calibration against a polystyrene standard. The analysis is performed at a column temperature of 45 ± 1 °C using a refractive index detector.

[0151] Manufacturing of test specimens First, to improve workability, the cyanate ester resin (A) was heated to 80°C while being thoroughly stirred. Then, poly(diorgano)siloxane (B) was added, and the mixture was homogenized at 110°C for 1 hour, followed by degassing at 110°C and a pressure of 10 mbar for 1 hour. After releasing the vacuum with nitrogen, the mixture was immediately poured while still hot into a two-part screw-top aluminum mold preheated to 160°C. The mold cavity dimensions for producing test specimens for fracture toughness, water absorption, thermal oxidation stability, and dynamic viscoelastic analysis (DMA) were 200 mm × 100 mm × 6.5 mm (length × width × height). To prevent adhesion and leakage, the mold cavity surface was treated with a release agent (Loctite Frekote HMT-2; commercially available from Henkel AG&Co. KGaA, Düsseldorf, Germany) on the inside of the mold, and 2mm diameter circular cords made of fluororubber with a Shore A hardness of 75 were placed around the mold cavity. For 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) Cure at 240°C for 2 hours.

[0152] The specimens were then cooled to room temperature in the mold before being removed. For further use, the top 10 mm of the hardened surface of the specimens, which had been exposed to air during curing in the mold, was cut off and discarded. Subsequently, specimens for measuring fracture toughness, water absorption, thermal oxidation stability, and DMA were cut from a large 6.5 mm high hardened sample slab using a diamond saw to the appropriate length × width dimensions. For measuring water absorption, 2.00 mm thick specimens were cut from a piece previously cut from the inner portion using a diamond hole saw, so that all six sides of the specimen were cut surfaces.

[0153] Fracture toughness K Ic Fracture toughness / critical stress strength coefficient K IcMeasurements were performed at 23°C and 50% relative humidity, as described in the literature "Reactive and Functional Polymers 142 (2019) 159-182". The specimen thickness was 6.5 mm. The MN×m values ​​reported in Table 1 are shown below. -3 / 2 Fracture toughness K Ic The value was rounded to two decimal places according to Section 4 of DIN 1333:1992-02.

[0154] Dynamic viscoelastic analysis (DMA) Measurement conditions: Measuring device: ARES rheometer (TA Instruments) Temperature range: -100℃ to 300℃ Heating rate: 4K / min with nitrogen flow Frequency: 1Hz Strain: Initially 0.03%, automatically increases when the measured signal falls below the threshold. The test was conducted using a rectangular parallelepiped specimen with dimensions of length × width × height = 40 mm × 6 mm × 3 mm. The fixed length was 25 mm. 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. Glass transition temperature T reported in Table 1 G The value is rounded to an integer according to Section 4 of DIN 1333:1992-02.

[0155] Water absorption rate In this invention, the water absorption rate was measured by gravimetric analysis after storing the test specimen in temperature-controlled water. A rectangular parallelepiped test specimen with dimensions of length × width × thickness = 30.00 mm × 17.00 mm × 2.00 mm was used. The accuracy of the gravimetric analysis was ±0.01 mg. The test specimen was first dried in a vacuum dryer at 70°C and 30 mbar, with its weight measured every 24 hours until it reached a constant weight. The test specimen was considered "dry" when no further weight loss was measured for more than 48 hours. Subsequently, in all cases, one dried test specimen was immersed in 45 ml of deionized water in a suitable sealed container. The sealed container was placed in a convection oven preheated to 70°C and maintained at this temperature throughout the test period. After 1600 hours, the test specimen was removed, cooled to room temperature, wiped dry, and its weight was remeasured. The water absorption rate (or weight increase rate) was calculated according to ("Weight after water storage (g)" ÷ "Weight after drying and before water storage (g)") - 1. Table 1 reports the percentage values ​​of the water absorption rate, rounded to two decimal places in accordance with Section 4 of DIN 1333:1992-02.

[0156] thermal oxidative stability In this invention, thermal oxidation stability was measured by gravimetric analysis 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 analysis was ±0.1 mg. First, the test specimens were dried in a vacuum dryer at 70°C and 30 mbar, with the weight measured every 24 hours until a constant weight was reached. The test specimens were considered "dry" when no further weight loss was measured for more than 48 hours. Subsequently, the test specimens were stored in a convection oven at 240°C. After 200 hours, the test specimens were removed and their weight was measured again. The weight loss rate was calculated according to ("Weight after storage at 240°C (g)" ÷ "Weight after drying and before storage at 240°C (g)") - 1. Table 1 reports the percentage weight loss values, rounded to two decimal places in accordance with Section 4 of DIN 1333:1992-02.

[0157] compatibility The compatibility between compound (B) and cyanate ester resin (A) was visually evaluated based on the criteria shown in Table 1: Before curing after storage of the mixture at 100°C for 15 minutes: "+" indicates that the mixture is single-phase, and "-" indicates that the mixture is two-phase; After curing: "+" indicates good compatibility, meaning no leaching or seepage of compound (B) from the cured mixture is visible to the naked eye, while "-" indicates poor compatibility, meaning leaching or leakage of component (B) from the cured mixture is observed. Furthermore, the tackiness or oiliness of the air-side surface is determined by the LDPE film (CAS: 9002-88-4) and filter paper (Whatman). TM The surface tackiness / oiliness was evaluated by pressing the film or filter paper (Type 589 / 2) onto the surface and then peeling it off. As reported in Table 1, the surface tackiness / oiliness was divided into "+" (test specimen surface was dry, with no tackiness or oiliness (dry filter paper)) and "-" (test specimen surface was soft, with tackiness and / or oiliness (wet filter paper)).

[0158] Preparation of bis[1,3-(4-hydroxyphenyl)]-1,1,3,3-tetramethyldisiloxane (CAS 24602-62-8, hereinafter referred to as modifier "M1") The siloxane was prepared according to the synthesis procedure described in "ACS Polymer Preprints 1992, 33(1), 988-989".

[0159] Example E1 As described in the section "Preparation of Test Specimens", 2,2-bis(4-cyanatophenyl)propane (CAS 1156-51-0; Arxada Ltd., CH-4002 Basel) is used in Primaset (R) 85g of BADCy (commercially sold under the product name) was used as ingredient (A), and it was mixed with 15g of the pre-prepared modifier "M1" as ingredient (B), and then processed.

[0160] The results are shown in Table 1.

[0161] Example E2 In example E1, replace 2,2-bis(4-cyanatophenyl)propane with polyphenol cyanate resin (CAS 87397-54-4; Arxada Ltd., CH-4002 Basel, Primaset). (R) The process was repeated with the addition of using the commercially available product known as PT-15.

[0162] The results are shown in Table 1.

[0163] Comparative Example C1 The procedure described in Example E1 was repeated with the modification that component (B) was not added to component (A).

[0164] The results are shown in Table 1.

[0165] Comparative Example C2 The procedure described in Example E2 was repeated with the modification that component (B) was not added to component (A).

[0166] The results are shown in Table 1.

[0167] [Table 1]

Claims

1. (A) at least one organic compound (A) having no siloxy (≡Si-O-) units and having at least two cyanate ester (-O-C≡N) groups; and (B) General formula (I): R ａ R １ ３－ａ Si-O-(R ｄ R １ ２－ｄ Si-O-) ｂ -SiR ｃ R １ ３－ｃ (I) (In the formula, R represents a monovalent, SiC-bonded aliphatic hydrocarbon group, which may be identical or different; or a monovalent, SiC-bonded aromatic hydrocarbon group that lacks a phenolic OH group. R １ These are identical or different and represent a monovalent aromatic hydrocarbon group having at least one phenolic hydroxyl group. a is 2 or 3, b is an integer between 1 and 18. c is 2 or 3, d is either 1 or 2. Represented by, however, one or two groups R per poly(diorgano)siloxane molecule (B) of general formula (I) １ There exists at least one type of poly(diorgano)siloxane. A curable composition containing the following:

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

3. The curable composition according to claim 1 or 2, wherein each molecule of compound (A) contains at least two aromatic hydrocarbon groups, and each group comprises a cyanate ester group bonded to an aromatic carbon atom.

4. Each of the aromatic hydrocarbon groups contains a cyanate ester group bonded to an aromatic carbon atom, and is covalently bonded or -CR ２ ２ -, -CR ２ =CR ２ -, -C (=CR) ２ ２ )-, -O-, -S-, -N=N-, -CR ２ =N-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -S(=O)-, -S(=O) ２ -, O = P(O-) ３ , -SiR ２ ２ - Divalent aromatic hydrocarbon groups, such as phenylene, trilene, biphenylene, naphthylene, etc.; or divalent cycloalkanediyl groups, such as tricyclo[5.2.1.0 ２．６ They are connected to each other via at least one crosslinking unit selected from the group consisting of ]decanediyl and bicyclo[2.2.1]heptanediyl, where R ２ The curable composition according to claim 3, wherein in each case, independently represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group having 1 to 30 carbon atoms.

5. The curable composition according to any one of claims 1 to 4, wherein the at least one compound (B) has a weight-average molecular weight Mw of 300 to 3000 g / mol; and / or a number-average molecular weight Mn of 300 to 2000 g / mol.

6. The curable composition according to any one of claims 1 to 5, wherein the monovalent SiC-bonded aliphatic hydrocarbon group R is selected from alkyl groups, cycloalkyl groups, and epoxy groups; and / or the monovalent SiC-bonded aromatic hydrocarbon group R without a phenolic OH group is selected from aryl groups, alkaryl groups, aralkyl groups, alkoxyaryl groups, aryloxyaryl groups, haloaryl groups, and heterocyclic aromatic hydrocarbon groups.

7. R １ However, the following equation (II): 【Chemistry 1】 (In the formula, R ４ , R ５ , R ６ , R ７ and R ８ In each case, independently, R represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 18 carbon atoms, except in formula (II), where at least one group R ４ , R ５ , R ６ , R ７ or R ８ (However, it is either a phenolic hydroxyl group or contains a phenolic hydroxyl group.) A curable composition according to any one of claims 1 to 6, which represents units according to the following.

8. R ６ However, it is a hydroxyl group, and the group R ４ , R ５ , R ７ and R ８ The curable composition according to claim 7, wherein in each case, it independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

9. The above-mentioned at least one compound (B) is of formula (III) to (XII): 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 or 【Chemistry 11】 (In the formula, Me is a methyl group, Ph is a phenyl group, m is between 1 and 19. n is between 1 and 18. o is between 1 and 18. However, the sum n + o is between 2 and 19. A curable composition according to any one of claims 1 to 8, selected from compounds corresponding to one of the above.

10. A curable composition according to any one of claims 1 to 9, comprising 1 to 70 parts by mass of at least one compound (B) based on 100 parts by mass of the total amount of at least one compound (A).

11. 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 auxiliary agent (H) It further includes, Herein, the curable composition according to any one of claims 1 to 10, 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 agent (H) is different from the at least one compound (A) and (B).

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 curing a curable composition according to any one of claims 1 to 11 after molding 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 according to claim 13.

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