Curable organosiloxane-modified reaction resin

Abstract

The present invention relates to a curable composition made from a reaction resin containing polymerizable functional cyanate ester groups and a linear poly(imidodiorganosiloxane) copolymer, a method for producing the same, and a curable material and composite material obtained therefrom that having high fracture resistance.

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(imide-diorganosiloxane) copolymer, a method for producing the same, and a curable material having high fracture toughness and composite materials that can be used therefrom. [Background technology]

[0002] The steady increase in demand for high-temperature resistant composite materials, materials for high-speed data communication, or materials for new technologies for electricity and hydrogen storage is driving an accelerated movement toward the use of high-performance polymers that combine advantages such as thermoelasticity, high mechanical strength, high glass transition temperature, and chemical resistance at low weight, compared to metallic materials. Among such materials, epoxy (EP) resins and epoxy resin systems are used in many applications and are now established as one of the most commonly used high-performance polymers, for example, in composite materials combined 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, and reactive resin mixtures such as bis(benzocyclobutenimide)bismaleimide, cyanate ester / epoxide, or bismaleimide / cyanate ester have become increasingly important in recent years as matrix resins for fiber composite materials in industry, automotive construction, and aerospace. Compared to epoxy resins, polymer matrix resins based on CE, BMI, or PI, for example, combine high mechanical strength with high glass transition temperature, high thermoelasticity, and high long-term stability, thereby greatly expanding the possible uses of these thermosetting resins, especially in the high-temperature range. Furthermore, cyanate ester resins are characterized in particular by low water absorption and dielectric constant in the cured state and good processability in the uncured state. CE resins are also the best alternative to most other resin systems in terms of toxicological properties and flame and smoke properties. This unique combination of properties makes the use of CE resins ideal for a wide range of possible applications.

[0003] However, thermosetting resin systems based on CE resin also have drawbacks. During thermosetting, the cyanate ester resin undergoes crosslinking through the trimerization of cyanate ester (N≡CO-) groups, forming a thermally stable cyanurate ring and resulting in a polycyanurate network with a high crosslink density. While this highly crosslinked state results in a cured thermosetting resin with high mechanical stability, the network is brittle, i.e., has low fracture toughness / impact resistance.

[0004] Therefore, for these CE-reactive resins already on the market, it is desirable to provide suitable modifiers that are stable at high temperatures and contribute to higher fracture toughness in the cured thermosetting resin network, so that they can be commercially used in demanding applications, such as matrix resins for automotive construction, the aerospace industry, and hydrogen storage and transport. [Overview of the project] [Problems that the invention aims to solve]

[0005] Therefore, the object of the present invention is to provide a cured thermosetting resin with higher fracture toughness (K) after the molding and curing process. Ic The objective is to modify the organic cyanate ester resin such that it has improved aging resistance, while advantageous properties inherent to thermosetting resins, such as thermal oxidation stability, high glass transition temperature, and high mechanical strength, are largely preserved even in the modified thermosetting resin.

[0006] Chinese Patent Application Publication No. 105331104 relates to a modified thermosetting resin and a method for producing the same, and more specifically, to a fluorine-containing thermosetting resin modified with a polyimide-polysiloxane block copolymer and a method for producing the same.

[0007] Chinese Patent Application Publication No. 111500247 discloses an adhesive, more specifically an adhesive for packaging solution-type electrochromic devices.

[0008] Korean Published Patent No. 20170038741 relates to modified polyimide, adhesive compositions, resin-coated copper foil, copper-clad laminates, printed circuit boards, and multilayer substrates. This adhesive composition is particularly suitable for the manufacture of multilayer substrates (MLBs).

[0009] The fracture toughness of cyanate ester resins is known to be improved by a second organic or inorganic phase, and effective modifiers with proven usefulness include, for example, thermoplastic resins, elastomers, core / shell particles, and block copolymers.

[0010] The authors of RSC Adv., 2016, 6, 49436-49447 (doi.org / 10.1039 / C6RA08229G) highlight the potential to improve the impact resistance of cyanate ester resins by adding block copolymers having terminal amine groups as modifiers, the polymer backbone of which consists of “rod-like” polyimide blocks and “helical” poly(dimethylsiloxane) blocks with an average chain length of approximately 15 siloxane units. As the proportion of flexible poly(dimethylsiloxane) blocks increases, the block copolymer modifiers in the cured cyanate resin matrix tend to form relatively large spherical and even “worm-like” micelles, both of which, according to the authors, contribute to improved impact resistance. However, the disclosed block copolymers also have several drawbacks. Firstly, the synthesis of the polyimide blocks uses aromatic diamines, some of which are classified as CMR substances and are therefore of toxicological concern. Further drawbacks include the strong promotion of the crosslinking reaction of the cyanate ester groups by the terminal amine groups, resulting in the curing of the cyanate ester resin mixture becoming more uncontrollable as the proportion of the modifier increases, and consequently, the reduced storage stability of the mixture. Moreover, the amine groups contribute to higher water absorption and increased breakdown of the polycyanurate network due to aminolysis, which manifests as a higher hydrolysis rate of the cured resin mixture. A further limitation is that as the proportion of poly(dimethylsiloxane) blocks, which have a favorable effect on toughness, increases, the miscibility with the cyanate resin decreases, thus limiting the proportion of the modifier in the cyanate resin and thus limiting the possibility of imparting toughness.

[0011] The above problems can be overcome by copolymerizing aromatic dianhydrides with short-chain siloxanes having terminal amine groups and aromatic monoanhydrides or aromatic monoamines. Surprisingly, these poly(imide-siloxane) copolymers, which do not have a block copolymer structure, have been found to significantly improve the fracture toughness of cured cyanate ester thermosetting resins. [Means for solving the problem]

[0012] The present invention (A) At least one organic compound (A) which does not contain siloxy (≡Si-O) units having at least two cyanate ester (-OC≡N) groups (also referred to herein as "cyanate ester resin"), preferably substituted and / or containing at least one heteroatom, (B) Formula (I) that does not contain a cyanate ester group

[0013] [ka] and / or formula (II)

[0014] [ka] at least one linear poly(imide-diorganosiloxane) copolymer and Includes, During the ceremony, R may be the same or different, and represents a methyl, vinyl, or phenyl group. R 1 , R 2 , R 3 and R 4 These represent monovalent, optionally substituted hydrocarbon groups that are identical or different. R 5 This represents a monovalent, optionally substituted hydrocarbon group that is either identical or different. Y may be the same or different, and represents a methylene (-CH2-), ethylene (-(CH2-)2), or propylene (-(CH2-)3) group. Z is the same or different and is a covalent bond, or -C≡C-, -CR 6 =CR 6 -, -CR 6 2-, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -OC(=O)O-, -C(=O)O-, -C(=O)O-(C6H4)-OC(=O)-, -O-(C6H4)-CR 6 2-(C6H4)-O-, -O-(C6H4)-CR 6 2-(C6H4)-CR 6 represents a divalent group selected from the group consisting of 2-(C6H4)-O-, or a bicyclo[2.2.1]heptanediyl group such as tricyclo[5.2.1.0 2,6 decandiyl and bicyclo[2.2.1]heptanediyl, etc., represents a divalent cycloalkanediyl group, R 6 is the same or different and is a hydrogen atom, a halogen atom, or a monovalent optionally substituted hydrocarbon group having 1 to 30 carbon atoms optionally interrupted by at least one heteroatom and optionally bonded to any of the substituents or other groups R 6 to form a cyclic unit, m is equal to 1 to 15, preferably 1 to 10, more preferably 1 to 5, particularly 1, n is equal to 1 to 20, preferably 1 to 15, more preferably 1 to 10, particularly 1 to 5, A curable composition is provided.

[0015] Group R 6 Examples are monovalent groups such as methyl, ethyl, trifluoromethyl, phenyl and fluorenyl groups; ring structures consisting of two groups R 6 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, anthracen-9(10H)-one-10,10-diyl, 9,10-dihydroanthracene-9,9-diyl and 3,3,5-trimethylcyclohexane-1,1-diyl groups.

[0016] The heteroatoms may be selected from the group consisting of O, S, N, P, and Si, and are preferably O and S.

[0017] 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).

[0018] In this invention, the notation "1-propenyl" refers to a "-CH=CH-CH3" group, the notation "2-propenyl" or "allyl" refers to a "-CH2-CH=CH2" group, and the notation "propenyl" refers to a 1- or 2-propenyl group.

[0019] To avoid an excessive number of pages in the description of this application, only preferred embodiments of individual features are specified.

[0020] However, expert readers should clearly understand that this type of disclosure also means that all combinations of different preference levels are also explicitly disclosed and explicitly desired, i.e., all combinations both within a single compound / feature and between different compounds / features.

[0021] Cyanate ester resin (A) These are organic compounds that do not contain 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.

[0022] Preferably, compound (A) is an aromatic hydrocarbon compound that is optionally 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.

[0023] More preferably, each molecule of compound (A) comprises at least two optionally substituted and / or optionally containing at least one heteroatom, each containing a cyanate ester group bonded to an aromatic carbon atom, and in particular, the optionally substituted and / or optionally containing at least one heteroatom, each containing a cyanate ester group bonded to an aromatic carbon atom, is covalently bonded, or -CR 7 2-, -CR 7 =CR 7 -, -C (=CR 7 2) -, -O-, -S-, -N=N-, -CR 7 =N-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -S(=O)-, -S(=O)2-, O=P(O-)3, ≡P(=O), -SiR 7 2-, divalent aromatic hydrocarbon groups, such as phenylene, trilene, biphenylene and naphthylene, or divalent cycloalkanediyl groups, such as 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.

[0024] base R 7 Here, R is independent in each case. 6 This is a list of the basics.

[0025] Examples of compounds (A) according to 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 ("bisphenol dicyanates"), 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-methoxymethylphenyl)methane and 1,1-bis(3-methyl-4-cyanatophenyl)cyclo Hexane (bisphenol Z cyanate ester); cyanate esters of propenyl-substituted bisphenols, e.g., 2,2-bis(3-(2-propenyl)-4-cyanatophenyl)propane, bis{[4-[(3-allyl-4-cyanatophenyl)isopropylidene]phenoxy]phenyl}sulfone and bis{4-[4-cyanato-3-(2-propenyl)phenoxy]phenyl}sulfone; cyanate esters of biphenyls, e.g., 4,4'-dicyanatobiphenyl (CAS 1219-14-3), 2,4'-dicyanatobiphenyl and 2,2'-dicyanatobiphenyl;Phenol-dicyclopentadiene cyanate resins, for example, 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, for example, resol cyanate esters or novolac cyanate esters (for example, 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(R) PT-15, PT-30, PT-60, PT-90 and CT-90, as well as AroCy(R) ​​XU-371); Cyanate esters of fluoroalkanediols, e.g., 1,8-dicyanatoperfluorooctane; Cyanate esters of naturally occurring 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; further, a polymer resin having terminal cyanate ester groups and composed of at least two identical or different repeating units, wherein the backbone of each repeating unit is at least one divalent aromatic hydrocarbon group, such as phenylene, biphenylene and naphthylene, or 9H-fluorene-9,9-diyl, and -CR; 8 2-, -CR 8 =CR 8 -, -C (=CR 8 2) -, -O-, -S-, -N=N-, -CR 8 =N-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -S(=O)-, -S(=O)2-, O=P(O-)3, ≡P(=O), -SiR 8 At least one crosslinking unit selected from the group consisting of 2, or a divalent cycloalkanediyl group, for example, tricyclo[5.2.1.0 2,6It is a polymer resin containing decanediyl and bicyclo[2.2.1]heptanediyl.

[0026] Examples of repeating units in cyanate ester polymer resins are arylene ethers, arylene ether sulfones, or arylene ether ketones.

[0027] base R 8 In each case, R 6 This is a list of the basics.

[0028] Preferably, compound (A) is a cyanate ester of 2,2-bis(4-cyanatophenyl)propane, 1,1-bis(4-cyanatophenyl)ethane, bis(4-cyanatophenyl)methane, 1,3-bis(2-(4-cyanatophenyl)propan-2-yl)benzene, 2,2-bis(3-(2-propenyl)-4-cyanatophenyl)propane, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, phenol-dicyclopentadiene cyanate ester resin, or phenol-formaldehyde resin. More preferably, component (A) is a cyanate ester of 2,2-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, 1,1-bis(4-cyanatophenyl)ethane, 1,3-bis(2-(4-cyanatophenyl)propan-2-yl)benzene, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, phenol-dicyclopentadiene cyanate ester resin, or phenol-formaldehyde resin. In particular, compound (A) is a novolac cyanate ester of 1,1-bis(4-cyanatophenyl)ethane, 1,3-bis(2-(4-cyanatophenyl)propan-2-yl)benzene, or cresol or phenol.

[0029] The compositions of the present invention may comprise just one cyanate ester resin (A) or a mixture of different cyanate ester resins (A), or may comprise a prepolymer of one cyanate ester resin (A) or a prepolymer of different cyanate ester resins (A), or a mixture of cyanate ester resin prepolymers or a mixture of a cyanate ester resin prepolymer and one or more cyanate ester resins (A).

[0030] An example of a prepolymer of cyanate ester resin (A) is bisphenol A dicyanate homopolymer (CAS 25722-66-1, example of a trade name: Primaset(R) BA-200).

[0031] Compound (B) At least one compound (B) of the present invention is further a linear poly(imide-diorganosiloxane) copolymer of general formula (I) and / or general formula (II) as described above (hereinafter also referred to as "copolymer").

[0032] Compound (B) may be solid or liquid at 23°C and 1013 hPa, and poly(bisphenol diorganosiloxane) copolymer (B) is preferably solid at 23°C and 1013 hPa.

[0033] At least one compound (B) of the present invention has a weight-average molar mass Mw of preferably 700 to 20000 g / mol, preferably 1000 g / mol to 15000 g / mol, more preferably 1000 g / mol to 10000 g / mol, and particularly 1000 g / mol to 8000 g / mol.

[0034] At least one compound (B) of the present invention has a number-average molar mass Mn of preferably 500 g / mol to 10000 g / mol, preferably 500 g / mol to 6000 g / mol, more preferably 1000 g / mol to 5000 g / mol, and particularly 1000 g / mol to 3500 g / mol.

[0035] In the context of this invention, the number-average molar mass Mn and weight-average molar mass Mw are, in both cases, rounded to the nearest 10th in units of g / mol according to DIN 1333:1992-02, Section 4, and are determined by calibrating a column array with a maximum size cutoff of 450,000 g / mol, consisting of three columns with different pore size distributions of 10,000 Å, 500 Å, and 100 Å, based on polystyrene-kodivinylbenzene as the stationary phase, with size exclusion chromatography (SEC / GPC) according to DIN 55672-1 / ISO 160414-1 and ISO 160414-3, against a polystyrene standard. The analysis is carried out using THF as the eluent. The analysis is carried out at a column temperature of 45 ± 1 °C using a refractive index detector.

[0036] Monovalent, optionally substituted hydrocarbon group R 1 , R 2 , R 3 and R 4 Examples include alkyl groups, e.g., methyl, ethyl, propyl, butyl, pentyl, and octyl groups; cycloalkyl groups, e.g., cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl groups; unsaturated hydrocarbon groups, e.g., vinyl, propenyl, cyclohexenyl, 2-(3-cyclohexenyl)ethyl, bicyclo[2.2.1]hepten-2-yl, dicyclopentenyl, 4-vinylcyclohexyl, norborneyl, vinylphenyl, and propenylphenyl groups; aryl groups, e.g., phenyl, biphenyl, cumylphenyl, benzylphenyl The following groups are involved: 1, naphthyl, anthryl, methoxyphenyl, phenyloxyphenyl, phenylmercaptophenyl, phenylsulfonylphenyl, phenoxycarbonylphenyl, benzoylphenyl, benzoyloxyphenyl, phenyloxycarbonyloxyphenyl, and phenanthryl groups; alkaryl groups, such as tolyl, xylyl, tert-butylphenyl, and ethylphenyl groups; aralkyl groups, such as benzyl, cumyl, and α- and β-phenylethyl groups; and heterocyclic aromatic hydrocarbon groups, such as pyridyl, quinolinyl, and furyl groups.

[0037] Although not expressed in equation (I), the base R 1 and R 2 And / or base R 3 and R 4 This can form one or more ring structures in succinimide, 3-allylsuccinimide, cyclohexane-1,2-dicarboximide, 4-cyclohexene-1,2-dicarboximide, 1,2,3,6-tetrahydrophthalimide, 3,4,5,6-tetrahydrophthalimide, phthalimide, 4-phenoxyphthalimide, 4-benzoylphthalimide, 4-phenylsulfonylphthalimide, maleimide, bicyclo[2.2.1]hepta-5-ene-2,3-dicarboximide, bicyclo[2.2.1]heptane-2,3-dicarboximide, 3,6-epoxy-1,2,3,6-tetrahydrophthalimide, bicyclo[2.2.2]octa-5-ene-2,3-dicarboximide, tetrafluorosuccinimide, tetrafluorophthalimide, 3-phenylsuccinimide, and naphthalene-2,3-dicarboximide, among others.

[0038] Preferably, base R 1 and R 2 And / or base R 3 and R 4 This forms a ring structure in phthalimide, succinimide, and bicyclo[2.2.1]hepta-5-ene-2,3-dicarboximide, more preferably in phthalimide.

[0039] Monovalent, optionally substituted hydrocarbon group R 5 An example is R 1 , R 2 , R 3 and R 4 The groups listed above, as well as carbonyl functional groups, such as benzoyl and phenoxycarbonyl groups.

[0040] Preferably, base R 5This is a phenyl, benzylphenyl, cumylphenyl, tert-butylphenyl, phenoxyphenyl, phenylmercaptophenyl, phenylsulfonylphenyl, or benzoylphenyl group, more preferably a phenyl, benzoylphenyl, or benzylphenyl group.

[0041] Preferably, group Z is a covalent bond or a -O-, -C(=O)-, -C(CF3)2-, -S(=O)2-, or -O-(C6H4)-C(CH3)2-(C6H4)-O- group.

[0042] An example of copolymer (B) used in accordance with the present invention is:

[0043] [ka] Therefore, Mw = 4860 g / mol and Mn = 2350 g / mol.

[0044] [ka] Therefore, Mw = 7730 g / mol and Mn = 3410 g / mol.

[0045] [ka] Therefore, Mw = 4790 g / mol, Mn = 1950 g / mol, and

[0046] [ka] Therefore, Mw = 5170 g / mol and Mn = 2080 g / mol. Here, x is preferably equal to 3 to 10.

[0047] Preferably, the compound (B) used in accordance with the present invention is the compound of formula (I). More preferably, the compound (B) of formula (I) does not contain aliphatic carbon-carbon multiple bonds and aromatic heteroatoms.

[0048] Compound (B) used in accordance with the present invention can be prepared by standard chemical methods. Preferably, compound (B) is prepared by first reacting a bis-anhydride and optionally a mono-anhydride with an aminoalkyl-functionalized poly(diorgano)siloxane and optionally an aromatic monoamine in an inert solvent such as tetrahydrofuran to form an amide functional group, and then heating the mixture under reduced pressure to 150°C to 220°C, preferably 170°C to 190°C, to carry out a ring-closing reaction to remove water and form an imide functional group. The degree of polymerization depends on the ratio of the reagent bis-anhydride and aminoalkyl-terminated poly(diorgano)siloxane and the mono-anhydride and aromatic monoamine.

[0049] For the preparation of compound (B), it is possible to react a single bis-anhydride or a mixture of different bis-anhydrides with one or more different aminoalkyl-terminated poly(diorgano)siloxanes and one or more different monoanhydrides or one or more different aromatic amines.

[0050] Preferably, compound (B) is prepared from a bis-anhydride, an aminoalkyl-terminated poly(diorgano)siloxane, and a monoanhydride or aromatic amine; more preferably, compound (B) is prepared from a monoanhydride, a bis-anhydride, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane.

[0051] The compositions of the present invention may comprise only one compound (B) or a mixture of different compounds (B), preferably only one compound (B).

[0052] The composition of the present invention comprises, in each case, 100 parts by weight of component (A) and at least one compound (B) in an amount preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, and particularly 5 to 35 parts by weight.

[0053] In addition to at least one compound (A) and (B), the composition 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).

[0054] In preferred embodiments, the composition of the present invention comprises the following compounds: (C) at least one denaturing agent (C), (D) at least one reactive resin (D), (E) at least one filler (E), (F) at least one curing accelerator (F), (G) at least one solvent (G), and / or (H) at least one adjuvant (H) It further includes, 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).

[0055] 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.

[0056] In this 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).

[0057] Compound (C) At least one optional denaturing agent (C) is preferably, formula R 9 h (OR 10 ) i SiO (4-h-i) / 2 (III) It is an organosilicon compound (C1) containing the unit, In the formula, R 9 This represents a monovalent SiC-bonded, optionally substituted hydrocarbon group that is identical or different and may be interrupted by a hydrogen atom or at least one heteroatom. R 10 These are identical or different, and represent a monovalent aliphatic hydrocarbon group having a hydrogen atom or 1 to 12 carbon atoms. h is 0, 1, 2, or 3, preferably 1, 2, or 3. i is 0, 1, 2, or 3, preferably 0, 1, or 2, more preferably 0 or 1, particularly 0, however, In equation (III), the sum h+i ≤ 3, compound (C1) contains 2 to 20 units of equation (III), and compound (C1) does not contain an imide (-N(-C(=O)-)²) bond.

[0058] A monovalent SiC bonded, optionally substituted hydrocarbon group R, optionally interrupted by at least one heteroatom. 9 An example is R 1 , R 2 , R 3 and R 4The listed groups are: epoxy groups, e.g., 3-glycidoxypropyl, 4-(oxiran-2-yl)phenyl, oxiran-2-yl, and 2-(3,4-epoxycyclohexyl)ethyl groups; acrylate and methacrylate groups, e.g., 3-methacryloyloxypropyl, acryloyloxymethyl, and methacryloyloxymethyl groups; amine groups, e.g., aminophenyl, 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl, and N-phenylaminomethyl groups; hydroxy substituents, e.g., hydroxyphenyl and hydroxypropyl groups; halogenated groups, e.g., trifluoromethyl, fluorophenyl, chlorophenyl, bromophenyl, and trifluoromethylphenyl groups; and polycaprolactone, polycaprolactam, cyanatophenyl, 3-cyanatopropyl, isocyanatophenyl, and 3-isocyanatopropyl groups.

[0059] Preferably, base R 9 This is a hydrogen atom or a phenyl or methyl group.

[0060] Preferably, base R 10 This is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, or isobutyl group, particularly a methyl or ethyl group.

[0061] 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-epoxycyclohexa-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)O2 / 2 ) 66 (PhSi(OMe)2O 1 / 2 ) 14 and organopolysiloxane with weight-average molar mass Mw = 2190 g / mol, average composition (PhSiO 3 / 2 ) 75 (Me3SiO 1 / 2 ) 25 and organopolysiloxanes with a weight-average molar mass 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 These are 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.

[0062] Optionally, at least one modifier (C) is 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, poly(amideimide), polyarylate, polyesterimide, polyetherimide, polyaramid, polyacrylate, polyhydantoin, liquid crystal polymer, polycarbonate, polyester carbonate, and polyethylene terephthalate, as well as mixtures or copolymers thereof. The thermoplastic resin (C2) preferably has either reactive or chemically inert end groups. As a result of the manufacturing process, the reactive end groups remain in the polymerization reaction from the corresponding reactive groups of the polymerizable monomer. These groups are preferably hydroxy, amino, carboxy, or isocyanate groups. Examples of chemically inert terminal groups are methyl or phenyl groups. The thermoplastic resin (C2) has a glass transition temperature of over 100°C, preferably 130°C to 450°C, more preferably 150°C to 400°C, and particularly 180°C to 350°C, and the number-average molar mass Mn of (C2) is preferably 1100 to 100000 g / mol, preferably 2000 to 50000 g / mol, more preferably 2000 to 30000 g / mol, and particularly 3000 to 20000 g / mol.

[0063] At least one optional denaturing agent (C) preferably does not contain siloxy (≡Si-O) units and phenolic hydroxyl groups, and has a general formula (IV) R 11 -OCN(IV) It is an organic monofunctional cyanate ester (C3) having the following properties: In the formula, R 11 This represents a monovalent, optionally substituted aromatic hydrocarbon group, which may be interrupted by at least one heteroatom, wherein the cyanate ester group is directly bonded to the aromatic carbon atom.

[0064] 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-cyanatonolylbenzene, 4-chlorocyanatobenzene, 4-cyanatodiphenylsulfone, 4-cyanatotoluene, 4-cyanatodiphenyl ether, 4-cyanatodiphenylketone, 4-(cyanato)methoxybenzene; and propenyl-substituted monofunctional cyanate esters, such as 4-cumyl-2-(propenyl)cyanatobenzene or 2-(propenyl)cyanatobenzene.

[0065] Compound (C3) has a boiling point at 1013 hPa, preferably at least 150°C, more preferably at least 180°C, and particularly at least 220°C.

[0066] The optional at least one modifying agent (C) is preferably a monomer aromatic hydrocarbon (C4) that does not contain siloxy (≡Si-O) units and epoxy, imide, and cyanate groups, and has at least one phenolic hydroxyl group and optionally one or more aliphatic carbon-carbon multiple bonds.

[0067] The optional aliphatic carbon-carbon multiple bond in compound (C4) is preferably a propenyl group bonded to an aromatic carbon atom, and more preferably, in compound (C4), one phenolic hydroxyl group and optionally one propenyl group are bonded to the aromatic group in each case.

[0068] Examples of compounds (C4) without aliphatic carbon-carbon multiple bonds include monovalent, optionally substituted phenols, e.g., 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, xylenol, or 2,6-dinonylphenol; polyvalent 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 or more (bisphenol) hydroxyphenyl groups, e.g., bis(2-hydroxyphenyl) ) Methane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane (bisphenol C), 1,1-bis(4-hydroxyphenyl)ethane (bisphenol E), 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B), 2,2-bis(4-hydroxyphenyl)hexafluoropropane (bisphenol AF), 9,9-bis(4-hydroxyphenyl)fluorene (bisphenol FL) These are 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.

[0069] Examples of compounds (C4) having 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 These are 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.

[0070] The compound (C4) is preferably 4-phenylphenol, 2-methoxy-4-(2-propenyl)-phenol, 4-cumylphenol, 4-isopropylphenol, 4-tert-butylphenol, 2-tert-butylphenol, bisphenol, 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-t The compounds are ert-butyl-2-(2-methyl-2-propenyl)phenol or 2-(2-propenyl)phenol, and are 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.

[0071] If the composition of the present invention contains at least one modifying agent (C), it is possible to use either just one modifying agent (C1) to (C4) or two or more different modifying agents (C1) to (C4) in the mixture.

[0072] If the composition of the present invention contains at least one modifying agent (C), the at least one modifying agent (C) is present in each case in an amount of preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight, and particularly 1 to 10 parts by weight, based on 100 parts by weight of the total of components (A) and (B).

[0073] Compound (D) At least one optional reactive resin (D) is preferably an optionally substituted aromatic hydrocarbon compound selected from the group consisting of epoxides (D1) and imides (D2), which do not contain siloxy (≡Si-O-) units and cyanate esters and phenolic hydroxyl groups, and are optionally interrupted by at least one heteroatom, wherein the epoxide (D1) comprises at least two optionally substituted polymerizable glycidyloxy, glycidyloxycarbonyl, glycidylamino, diglycidylamino or oxiran-2-yl groups per molecule, preferably at least two such groups bonded to an aromatic carbon atom, and the imides (D2) comprises at least two optionally substituted polymerizable 5-ethynylphthalimide, 5-(phenylethynyl)phthalimide, najimide, benzocyclobutenephthalimide or maleimide groups per molecule, preferably at least two such groups bonded to an aromatic carbon atom; particularly preferably maleimide, glycidyloxy, glycidylamino and diglycidylamino groups.

[0074] Preferably, the at least one optional reactive resin (D) comprises at least two optionally substituted aromatic hydrocarbon groups, each comprising a maleimide, glycidyloxy, glycidyloxycarbonyl, glycidylamino, or diglycidylamino group, each optionally interrupted by at least one heteroatom and bonded to an aromatic carbon atom. More preferably, (D) is a compound comprising at least two optionally substituted aromatic hydrocarbon groups, each comprising at least one heteroatom and each comprising a maleimide, glycidyloxy, glycidylamino, or diglycidylamino group, each optionally comprising at least one heteroatom and bonded to an aromatic carbon atom, wherein the optionally substituted aromatic hydrocarbon group comprising at least one heteroatom is covalently bonded or -CR 12 2-, -CR 12 =CR 12 -, =C=CR 12 2、 -O-, -S-, -N=N-, -CR 12=N-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -S(=O)2-, O=P(O-)3, -SiR 12 2-, phenylene, arylene, biphenylene, biarylene, naphthylene or cycloalkanediyl group, for example tricyclo[5.2.1.0 2.6 They are linked to each other via a crosslinking unit containing at least one functional group selected from the group consisting of decanediyl or bicyclo[2.2.1]heptanediyl.

[0075] base R 12 In each case, R 6 This is a list of the basics.

[0076] Preferably, at least one reactive resin (D) contains an aromatic ring structure that does not contain heteroatoms.

[0077] Preferably, the epoxy resin (D1) is copolymerizable with the cyanate ester resin (A).

[0078] Preferably, the imide resin (D2) is not copolymerizable with the cyanate ester resin (A).

[0079] 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 phenol-, naphthol-, naphthalenediol-, bisphenol- or cresol-formaldehyde condensation products, e.g., cresol novolac glycidyl ether (CAS 29690-82-2), phenol novolac glycidyl ether (CAS 9003-36-5, CAS 28064-14-4, CAS 158163-01-0) and bisphenol A-epichlorohydrin-formaldehyde copolymer (CAS 28906-96-9); glycidyl ethers of phenol- or cresol-dicyclopentadiene condensation products, 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); 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), m-(glycidyloxy)-N,N-diglycidylaniline (CAS 71604-74-5); glycidyl-terminated thermoplastic polymers that can be produced by reacting an amino-terminated or hydroxy-terminated thermoplastic resin (C2) with epichlorohydrin, such as glycidyloxy-terminated or diglycidylamino-terminated polysulfones; homopolymerizable or copolymerizable epoxy resins, such as bisphenol A-epichlorohydrin copolymer (CAS 25036-25-3), 2,2',6,6'-tetrabromobisphenol A-epichlorohydrin copolymer (CAS 40039-93-8), and reaction products of diglycidylbisphenol A and m-phenylenebis(methylamine) (CAS 110839-13-9); and a mixture of different epoxy resins (D1);

[0080] 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 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), which can be produced, for example, by the reaction of an amino-terminated thermoplastic resin (C2) with maleic anhydride, for example, a maleimide-terminated polysulfone ether; and mixtures of different maleimide resins (D2).

[0081] Preferably, at least one compound (D) is a monomer compound that does not contain a thermoplastic homopolymer or copolymer.

[0082] If the composition of the present invention contains at least one reactive resin (D), the at least one reactive resin is present in each case in an amount of preferably 1 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly 1 to 20 parts by weight, based on 100 parts by weight of the total of components (A) and (B).

[0083] If the composition of the present invention contains at least one polymerizable imide (D2), it is preferably present 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) having a propenyl group bonded to an aromatic carbon atom, a modifier (C3) or a modifier (C4), or from an aromatic hydrocarbon compound containing, on a molecular basis, one or two hydroxyl groups bonded to an aromatic carbon atom and one or two polymerizable imide groups, preferably maleimide groups, such as N-(4-hydroxyphenyl)maleimide (CAS 7300-91-6).

[0084] When the composition of the present invention includes at least one polymerizable imide resin (D2) in combination with the components listed in the preceding paragraph, the molar ratio of the total imide groups to the total 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.

[0085] Compound (E) At least one optional filler (E) in the composition of the present invention may be any desired conventionally known granular filler.

[0086] At least one optional filler (E) according to the present invention is preferably a filler that dissolves in toluene to less than 1% by weight at 23°C and 1000 hPa.

[0087] Examples of fillers are non-reinforcing particulate fillers, i.e., preferably fillers having a BET surface area of at most 50 m 2 / g, such as quartz, glass, cristobalite, diatomaceous earth; water-insoluble silicates, such as calcium silicate, calcium metasilicate, magnesium silicate, zirconium silicate, talc, mica, feldspar, kaolin, zeolite; metal oxides, such as oxides of aluminum, titanium, iron, boron or zinc or mixed oxides thereof; barium sulfate, calcium carbonate, marble powder, gypsum, silicon nitride, silicon carbide, boron nitride, plastic powders, such as polyacrylonitrile or polyetherimide powders; reinforcing fillers, i.e., fillers having a BET surface area of more than 50 m 2 / g, such as fumed silica, precipitated silica, precipitated chalk, carbon black, such as furnace black and acetylene black and silicon-aluminum mixed oxides having a large BET surface area; aluminum trihydroxide, magnesium hydroxide, hollow spherical fillers, such as glass microballoons, glass spheres, phenolic thermospheres or ceramic microspheres, such as hollow spherical fillers obtainable under the trade name Zeeosphere from 3M Deutschland GmbH, Neuss, Germany; fibrous fillers, such as wollastonite, montmorillonite, basalt, bentonite and shredded and / or ground glass fibers (glass short fibers) or mineral wool; fibers composed of metal, metal oxide, glass, ceramic, carbon or plastic; natural fibers composed of cellulose, linen, hemp, wood or sisal.

[0088] Any optional at least one filler (E) according to the invention may be present in the composition of the invention as a single filler or as any desired mixture of at least two different fillers (E).

[0089] Component (E) is a component selected from fibrous semi-finished products (E2) containing fibers (E1) up to 5 cm in length and fibers over 5 cm in length, preferably particulate fillers containing fibrous semi-finished products (E2).

[0090] At least one optional filler (E2) is preferably any conventionally known fiber-forming material made from polypropylene, polyethylene, polytetrafluoroethylene or polyester; steel metal fibers; oxidized and non-oxidized ceramics, e.g., silicon carbide, aluminum oxide, silicon dioxide, boron oxide; glass, quartz, carbon, aramid, asbestos, graphite, acrylonitrile, poly(benzothiazole), poly(benzimidazole), poly(benzoxazole), titanium dioxide, boron, and aromatic polyamide fibers, e.g., poly(p-phenylene terephthalamide).

[0091] At least one of the listed fillers (E) may optionally be surface-treated, for example, hydrophobized, by treatment with an organosilane or organosiloxane, stearic acid, or one or more modifiers (C). The filler surface may also be modified, for example, by oxidation or treatment with an acid or base, to enable chemical bonding to the cured resin matrix. Preferably, at least one filler (E2) is surface-treated.

[0092] If the composition of 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, more preferably 10 to 400 parts by weight, and particularly 15 to 150 parts by weight, based on 100 parts by weight of the total of components (A) and (B) in each case.

[0093] If the composition of 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, more preferably 60 to 900 parts by weight, and particularly 100 to 400 parts by weight, based on 100 parts by weight of the total of components (A) and (B) in each case.

[0094] At least one filler (E2) may be present in the composition of the present invention in different forms, for example, as a continuous rope containing 1,000 to 400,000 individual filaments, woven fabrics, non-crimped woven fabrics, knitted fabrics, braids, mats, nonwoven fabrics, whiskers, chopped short fibers, or random fiber felts.

[0095] The composition of the present invention preferably comprises at least one filler (E), and the at least one filler (E) more preferably consists mostly, and especially entirely, of a filler (E2).

[0096] Preferably, the composition of the present invention comprises a fibrous fabric, a non-crimped fibrous fabric, a knitted fabric, or a braided fabric as the filler (E2) rope, more preferably consisting of carbon fibers, aromatic polyamide fibers, ceramic fibers, and / or glass fibers, and each fiber and / or rope, and the fibrous fabric, non-crimped fibrous fabric, knitted fabric, or braided fabric produced therefrom, is particularly surface-treated. Very preferably, each fiber is surface-treated.

[0097] In either case, the optional woven fiber fabric (E2) or non-crimped woven fiber fabric (E2) according to the present invention is preferably used in multiple layers.

[0098] In a preferred embodiment, component (E2) comprises at least 80% by weight, more preferably at least 90% by weight, of a woven fiber, non-crimped fiber, knitted fiber, or braided fiber fabric, based on 100% by weight of component (E2).

[0099] Compound (F) The compositions of the present invention can be cured in the presence of at least one curing accelerator (F), for example, a curing accelerator known from the prior art. Suitable curing accelerators (F1) include, for example, acids and bases, such as hydrochloric acid, phosphinic acid, phosphonic acid, phosphoric acid, aliphatic and aromatic amines, such as triethylamine, N,N-dimethylaniline and pyridine; 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 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, and copper(II) acetylacetone.

[0100] If at least one curing accelerator (F1) is used to cure the composition of the present invention, this is preferably a combination of an organometallic compound and a co-accelerator having at least one active proton, more preferably a combination of an organometallic compound and a phenol (C4), such as nonylphenol.

[0101] If the composition of the present invention contains at least one curing accelerator (F1), the amount contained is preferably 0.00001 to 5 parts by weight based on 100 parts by weight of component (A), and the organometallic compound (F1) is more preferably used in an amount of 0.0001 to 0.02 parts by weight based on 100 parts by weight of component (A).

[0102] 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 formation curing accelerator (F2) such as an organic peroxide, e.g., dicumyl peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, 1,1-bis(tert-butylperoxy)cyclohexane and tert-butyl perbenzoate; or an azo compound, e.g., azobis(isobutyronitrile), can be used alone or in addition to (F1). If the composition of the present invention contains a free radical formation curing accelerator (F2), the amount contained 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). It is preferable not to use a free radical formation curing accelerator (F2).

[0103] 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 and glycerol; ethers, e.g., methyl tert-butyl ether, di-tert-butyl ether Ethers, and di-, tri- or tetraethylene glycol dimethyl ethers; saturated hydrocarbons, e.g., n-hexane, cyclohexane, n-heptane, n-octane and isomer octane, e.g., 2-ethylhexane, 2,4,4-trimethylpentane, 2,2,4-trimethylpentane, 2-methylheptane and trichloroethylene, and mixtures of saturated hydrocarbons having a boiling point range of 60-300°C, available under trade names such as Exxsol(trademark), Hydrosesol(R) or Shellsol(R); aromatic solvents, e.g., benzene, toluene N, 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; carbonates, e.g., 1,3-dioxolan-2-one, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, propylene glycol carbonate and ethylene carbonate; ketones, e.g., acetone, methyl isopropyl Tylketones, methyl ethyl ketone, methyl isoamyl ketone, diisobutyl ketone, acetone, cyclohexanone; esters, such as ethyl acetate, n-butyl acetate, ethylene glycol diacetate, gamma-butyrolactone, 2-methoxypropyl acetate (MPA), dipropylene glycol dibenzoate, and ethyl ethoxypropionate; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone; acetonitrile; and dimethyl sulfoxides.

[0104] At least one solvent (G) is preferably an aromatic hydrocarbon or ketone.

[0105] If the composition of the present invention contains at least one solvent (G), the amount contained is preferably 10 to 300 parts by weight, more preferably 10 to 100 parts by weight, and particularly 10 to 50 parts by weight, based on 100 parts by weight of the total of components (A) and (B) in each case. The composition of the present invention preferably does not contain solvent (G).

[0106] Compound (H) The optional at least one auxiliary agent (H) according to the present invention is preferably a pigment, dye, fragrance, processing aid, such as an agent for affecting tackiness, a lubricant, a mold release agent, an anti-blocking agent or dispersant; a stabilizer against hydrolysis, light, oxidation, heat, or discoloration; a flame retardant or plasticizer.

[0107] If the composition of the present invention contains at least one auxiliary agent (H), then the at least one auxiliary agent (H) is present in each case in an amount of preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and particularly 0.1 to 10 parts by weight, based on 100 parts by weight of the total of components (A) and (B). The composition of the present invention preferably does not contain further components (H).

[0108] The composition of the present invention, preferably, (A) at least one cyanate ester resin, (B) at least one poly(imido-diorganosiloxane) copolymer, (C) at least one denaturing agent, (D) at least one reactive resin, (E2) At least one fiber-reinforced filler, (F) at least one curing accelerator, (G) at least one solvent, and (H) at least one adjuvant (optional) It is a composition containing [the specified ingredient].

[0109] The composition of the present invention, preferably, (A) at least one cyanate ester resin, (B) at least one poly(imido-diorganosiloxane) copolymer, (C) at least one denaturing agent, (D) at least one reactive resin, (E2) At least one fiber-reinforced filler, (F) at least one curing accelerator, (G) at least one solvent, and (H) at least one adjuvant (optional) It is a composition containing [the specified ingredient].

[0110] In a particularly preferred embodiment, the composition of the present invention is (A) at least one cyanate ester resin, (B) at least one poly(imido-diorganosiloxane) copolymer, (C) at least one denaturing agent, (D2) At least one imide resin, (E2) At least one fiber-reinforced filler, (F) at least one curing accelerator, (G) at least one solvent, and (H) at least one adjuvant (optional) It is a composition containing [the specified ingredient].

[0111] In a particularly preferred embodiment, the composition of the present invention is (A) at least one cyanate ester resin, (B) at least one poly(imido-diorganosiloxane) copolymer, (C) at least one denaturing agent, (D2) At least one maleimide resin, (E2) At least one fiber-reinforced filler, (F) at least one curing accelerator, (G) at least one solvent, and (H) at least one adjuvant, Includes, However, the composition is provided that at least one component (A), (C3), or (C4) has a propenyl group bonded to an aromatic carbon atom.

[0112] The compositions of the present invention preferably do not contain any further components other than components (A) and (B), optionally selected components (C) to (H), and impurities typical of any raw materials, such as catalyst residues, such as sodium chloride or potassium chloride, impurities in industrial-grade cyanate ester resin monomers, and any reaction products of the components used that are formed during mixing / storage.

[0113] In the compositions of the present invention, the above-mentioned components may be used individually or in the form of a mixture of at least two of the components.

[0114] The compositions of the present invention can be produced according to known methods, for example, by mixing the individual components in any desired order or in a known manner.

[0115] The present invention further provides a method for producing the composition of the present invention by mixing the individual components in any desired order.

[0116] In the method of the present invention, mixing may 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. Very preferably, when mixing at ambient temperature, the mixing may be carried out at a temperature resulting from the temperature of the raw materials plus the temperature rise due to the energy input during mixing, and the mixture may be heated or cooled as necessary.

[0117] Mixing can be carried out at ambient pressure, i.e., about 900–1100 hPa. Mixing can also be carried out under intermittent or continuous reduced pressure to remove volatile substances and / or air, for example, at an absolute pressure of 30–500 hPa, or at a positive pressure such as an absolute pressure of 1100–3000 hPa, particularly in continuous process mode, if these pressures are established in a closed system, for example, as a result of the pressure during pumping and as a result of the vapor pressure at high temperatures of the materials used.

[0118] The method of the present invention can be carried out continuously, discontinuously, or semi-continuously, preferably discontinuously.

[0119] In a preferred embodiment of the method of the present invention for producing the composition of the present invention, the individual components, excluding component (E), are premixed in any desired order, and then the filler (E2) is impregnated with the premix by known processing techniques, such as prepreg processing (from molten, solution or suspension), sheet molding compound (SMC), filament winding, compression molding, pultrusion, fiber spraying and injection molding, such as resin transfer molding or vacuum injection, and processed into a molded article while avoiding air bubbles.

[0120] The compositions of the present invention can be used for all purposes in which organic reactive resin systems or their prepolymers have been previously used for subsequent curing of thermosetting products.

[0121] In one variant of the method of the present invention, components (A) and (B) and optionally selected 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, woven fabric, non-crimped woven fabric, knitted fabric or braid, is optionally impregnated with the premix under pressure and optionally degassed. In the case of a multilayer woven fabric or non-crimped woven fabric (E2), impregnation and degassing may be carried out individually for each layer or together for all layers.

[0122] In a more preferred modification of the method of the present invention, components (A) and (B) and optionally selected 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, woven fabric, non-crimped woven fabric, knitted fabric or braid, preferably with degassing performed simultaneously with the injection step.

[0123] In a more preferred modification of the method of the present invention, components (A) and (B) and optionally selected 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, and then 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).

[0124] The compositions of the present invention can be formed into any desired shape by ambient temperature or, optionally, by mechanical pressure at high temperatures.

[0125] The composition of the present invention is preferably moldable, and more preferably molded and cured in a mold cavity or around a mold plate.

[0126] Therefore, the present invention further provides the use of the composition of the present invention for manufacturing molded articles.

[0127] Therefore, the present invention further provides a method for producing a molded article by molding and then curing the composition of the present invention.

[0128] Therefore, the present invention further provides molded articles that can be obtained from the composition of the present invention by molding and curing.

[0129] The composition according to the present invention / composition manufactured in accordance with the present invention is preferably degassed before curing, more preferably after molding and before curing.

[0130] The curing according to the present invention is preferably carried out at a temperature in the range of 50 to 350°C, more preferably 100 to 300°C, and particularly 120 to 270°C. Very preferably, the curing according to the present invention is carried out in steps at a temperature of 120 to 270°C.

[0131] Curing can be accelerated by increasing the temperature, which means that molding and curing can also be performed in a single step.

[0132] The molded article according to the present invention is preferably made of a fiber composite material (or fiber-reinforced plastic "FRP").

[0133] Therefore, the present invention further provides the use of the composition of the present invention for manufacturing fiber composite materials.

[0134] The present invention further provides a method for producing a fiber composite material by molding and then 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 an air pressure of 1013 hPa, and is preferably liquid at 100°C and 1013 hPa.

[0137] When the composition of the present invention is a liquid at 100°C and 10¹³ hPa, the composition of the present invention in any case has a kinematic viscosity at 100°C and 10¹³ hPa 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.

[0138] In the context of the present invention, unless otherwise specified, the kinematic viscosity is determined in accordance with DIN 53019 at a temperature of 23 °C and an air pressure of 1013 hPa. The measurement is carried out with a "Physica MCR 300" rotational rheometer manufactured by Anton Paar. For viscosities of 1 to 200 mPa·s, a coaxial cylinder measurement system (CC 27) with an annular measurement gap of 1.13 mm is used, and for viscosities exceeding 200 mPa·s, a cone-plate measurement system (Searle system equipped with a CP 50-1 measurement cone) is used. The shear rate is adjusted according to the polymer viscosity (100 s -1 for viscosities of 1 to 99 mPa·s; 200 s-1 for viscosities of 100 to 999 mPa·s; 120 s -1 for viscosities of 1000 to 2999 mPa·s; 80 s -1 for viscosities of 3000 to 4999 mPa·s; 62 s -1 for viscosities of 5000 to 9999 mPa·s; 50 s -1 for viscosities of 10000 to 12499 mPa·s; 38.5 s -1 for viscosities of 12500 to 15999 mPa·s; 33 s -1 for viscosities from 16000 to 19999 mPa·s; 25 s -1 for viscosities of 20000 to 24999 mPa·s; 20 s -1 for viscosities of 25000 to 29999 mPa·s; 17 s -1 for viscosities of 30000 to 39999 mPa·s; 10 s -1 for viscosities of 40000 to 59999 mPa·s; 5 s -1 for viscosities of 60000 to 149999; 3.3 s -1 for viscosities of 150000 to 199999 mPa·s; 2.5 s -1 for viscosities of 200000 to 299999 mPa·s; 1.5 s -1 for viscosities of 300000 to 1000000 mPa·s.

[0139] Once the system for measuring kinematic viscosity is thermally equilibrated at the measurement temperature, a three-stage measurement program consisting of a run-in phase, preliminary shearing, and viscosity measurement is used. The run-in phase involves gradually increasing the shear rate over one minute until the shear rate corresponding to the desired viscosity, as described above, is reached, at which point the measurement will be taken. Once the shear rate is achieved, preliminary shearing is performed at a constant shear rate for 30 seconds, followed by 25 individual measurements of 4.8 seconds each for viscosity determination, and the results are averaged. The average value corresponds to the kinematic viscosity reported in mPa·s.

[0140] The critical stress intensity factor K for each cured unmodified cyanate ester resin (A) of the cured composition of the present invention, which consists of 85 parts by weight of cyanate ester resin (A) and 15 parts by weight of compound (B). Ic The ratio, measured at 23°C in each case, is preferably greater than 1.4, more preferably greater than 1.5, and particularly greater than 1.6.

[0141] For example, the curing composition of the present invention, comprising 85 parts by weight of a cyanate ester resin (A) and 15 parts by weight of a compound (B), preferably has a glass transition temperature of over 200°C, more preferably over 230°C, and particularly over 260°C.

[0142] For example, the cured composition of the present invention, comprising 85 parts by weight of a cyanate ester resin (A) and 15 parts by weight of a compound (B), exhibits a weight loss that is preferably 80% or less, preferably 60% or less, more preferably 40% or less, and particularly 20% or less, higher than the corresponding unmodified cyanate ester resin (A) after storage at 240°C for 200 hours.

[0143] The composition of the present invention has the advantage that copolymer (B) can be mixed with cyanate ester resin (A) without the addition of further solvents, and that copolymer (B) does not leach out during curing due to the thermosetting network.

[0144] The composition of 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 having ).

[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 composed of purely organic cyanate ester resins, the molded articles according to the present invention have the advantages of being thermally stable and having a low 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 compositions of the present invention have the advantage that their processing does not result in harmful emissions to the extent typically associated with organic cyanate ester resins used according to the prior art.

[0149] Exemplary Embodiments The following examples, carried out at ambient pressure, i.e., about 10¹³ hPa, and room temperature, i.e., about 23°C, or at temperatures established by combining the reactants at room temperature without additional heating or cooling, illustrate how the invention can be carried out in principle, but is not limited to what is disclosed therein.

[0150] Manufacturing of test specimens First, for better processability, the cyanate ester resin (A) was heated to 80°C while being thoroughly mixed. Next, copolymer (B) was added, and the mixture was homogenized in a rotary evaporator at 110°C for 1 hour, then 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 2-part screw-closure aluminum mold preheated to 160°C. The mold hole dimensions for producing test specimens for determining fracture toughness and thermal oxidation stability and for performing dynamic mechanical analysis (DMA) were 200 mm × 100 mm × 6.5 mm (length × width × height). To prevent sticking and leakage, the mold hole surface was treated inside the mold with a release agent (Loctite Frekote HMT-2; commercially available from Henkel AG&Co.KGaA, Düsseldorf, Germany), and a 2 mm thick round cord of fluororubber with a hardness of 75 Shore A was placed around the mold hole. For curing, the filled mold is subjected to the following temperature program, i.e., 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 It was stored in a convection oven according to the instructions.

[0151] Next, the specimens were cooled to ambient temperature in the mold and then demolded. For further use, the top 10 mm of the cured sides of the specimens, which had been exposed to air during curing in the mold, were cut off and discarded. Then, specimens for fracture toughness and thermal oxidation stability measurements, as well as for DMA, were cut from a large cured specimen slab with a height of 6.5 mm using a diamond saw of appropriate length × width dimensions.

[0152] Fracture toughness K Ic Fracture toughness / Critical stress intensity factor K ICThe measurement was performed at 23°C and 50% relative humidity, as described in the publication "Reactive and Functional Polymers 142(2019)159-182," and the thickness of the test specimen was 6.5 mm. Table 1 shows MN×m -3 / 2 Fracture toughness K reported IC The value was rounded to two decimal places according to DIN 1333:1992-02, Section 4.

[0153] Dynamic mechanical analysis (DMA) Measurement conditions: • Measuring device: ARES rheometer (TA Instruments) Temperature range: -100℃ to 400℃ • Heating speed: 4K / min via nitrogen flushing • Frequency: 1Hz • Distortion: Initially 0.03%, automatically increases when the measured signal falls below the threshold.

[0154] The test was performed using a rectangular parallelepiped specimen with dimensions of length × width × height = 40 mm × 6 mm × 3 mm, and the resulting clamp length was 25 mm.

[0155] In this 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 reported in Table 1 G The value was rounded to an integer according to DIN 1333:1992-02, Section 4.

[0157] thermal oxidative stability In this invention, the thermal oxidation stability of test specimens was determined by gravimetric analysis after storage 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, and the accuracy of the weight determination was ±0.1 mg. The test specimens were first dried to a constant weight in a vacuum oven at 70°C and 30 mbar, and their weight was determined at 24-hour intervals. If no further weight loss was measured over 48 hours, the test specimens were considered "dry." Next, the test specimens were stored in a convection oven at 240°C. After 200 hours, the test specimens were removed, and their weight was determined again. The weight loss was...

[0158]

number

[0159] 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 leaching or seepage of component (B) from the cured mixture, and "-" = insufficient compatibility, i.e., visible leaching or seepage of the siloxane component from the cured mixture and / or the surface of the test specimen is oily and / or sticky.

[0160] Poly(imide-diorganosiloxane) copolymer 1 Mix 40.0 g (129 mmol) of 4,4'-oxydiphthalic anhydride (CAS 1823-59-2, Sigma-Aldrich Chemie GmbH, 82024 Taufkirchen, commercially available from Germany) and 13.3 g (90 mmol) of phthalic anhydride (CAS 85-44-9, Sigma-Aldrich Chemie GmbH, 82024 Taufkirchen, commercially available from Germany) in 150 ml of anhydrous tetrahydrofuran (Sigma-Aldrich Chemie GmbH, 82024 Taufkirchen, commercially available from Germany). Then, add dropwise a solution containing 43.2 g (347 mmol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (CAS 2469-55-8, Sigma-Aldrich Chemie GmbH, 82024 Taufkirchen, commercially available from Germany) in 50 ml of anhydrous tetrahydrofuran. The mixture is stirred at 40°C for 1 hour, then the solvent is removed by distillation using a rotary evaporator, and the residue is defolated first at 150°C and ambient pressure for 1 hour, then at 180°C and a pressure of 5 mbar for 2 hours, while constantly and completely mixing. Copolymer 1 has a weight-average molar mass Mw of 4600 g / mol and a number-average weight-mollar mass Mn of 2020 g / mol. [Examples]

[0161] [Example Ex1] (A) 85 g of 2,2-bis(4-cyanatophenyl)propane (CAS 1156-51-0; TCI Deutschland GmbH, 65760 Eschborn, commercially available from Germany) as component (A) was mixed with 15 g of poly(imide-diorganosiloxane) copolymer 1 as component (B), and then processed as described in the section "Preparation of Test Specimens".

[0162] The results are shown in Table 1.

[0163] Comparative Example C1 The procedure described in Example 1 was repeated with the modification that component (B) was not added to component (A).

[0164] [Table 1] *1 Unrated

Claims

1. A curable composition, (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) General formula (I) that does not contain a cyanate ester group 【Chemistry 1】 and / or General Formula (II) 【Chemistry 2】 at least one linear poly(imide-diorganosiloxane) copolymer and Includes, During the ceremony, R may be the same or different, and represents a methyl, vinyl, or phenyl group. R １ , R ２ , R ３ and R ４ These are either identical or different, and represent a monovalent hydrocarbon group. R ５ These are either identical or different, and represent a monovalent hydrocarbon group. Y is the same or different and is a methylene (—CH ２ —), ethylene (—(CH ２ —) ２ ), or propylene (—(CH ２ —) ３ ), group, Z is either identical or different, covalent, or -C≡C-, -CR ６ =CR ６ -, -CR ６ ２ -, -O-, -S-, -S(=O)-, -S(=O) ２ -, -C(=O)-, -OC(=O)O-, -C(=O)O-, -C(=O)O-(C ６ H ４ )-OC(=O)-, -O-(C ６ H ４ )-CR ６ ２ - (C ６ H ４ )-O-, -O-(C ６ H ４ )-CR ６ ２ - (C ６ H ４ )-CR ６ ２ - (C ６ H ４ ) -O- indicates a divalent group selected from the group consisting of or tricyclo[5.2.1.0 ２，６ This represents a divalent cycloalkanediyl group such as decanediyl and bicyclo[2.2.1]heptanediyl. During the ceremony, R ６ These are identical or different, and represent a monovalent hydrocarbon group having a hydrogen atom, a halogen atom, or 1 to 30 carbon atoms. m is between 1 and 15. n is between 1 and 20. Curable composition.

2. The curable composition according to claim 1, wherein 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, each containing a cyanate ester group bonded to an aromatic carbon atom.

4. Aromatic hydrocarbon groups, each containing a cyanate ester group bonded to an aromatic carbon atom, are covalently bonded or -CR ７ ２ -, -CR ７ =CR ７ -, -C (=CR ７ ２ )-, -O-, -S-, -N=N-, -CR ７ =N-, -C(=O)-, -C(=O)O-, -OC(=O)O-, -S(=O)-, -S(=O) ２ -, O = P(O-) ３ , ≡P(=O), -SiR ７ ２ - Divalent aromatic hydrocarbon groups, such as phenylene, torylene, biphenylene and naphthylene, or divalent cycloalkanediyl groups, such as tricyclo[5.2.1.0 ２．６ Linked to each other via at least one crosslinking unit selected from the group consisting of ]decanediyl and bicyclo[2.2.1]heptanediyl, In the formula, R ７ In each case, R ６ The following lists the bases: The curable composition according to claim 3.

5. At least one compound (B) Weight-average molar mass Mw of 700 to 20000 g / mol, and / or Number-average molar mass Mn 500-10000 g / mol A curable composition according to any one of claims 1 to 4, having the following characteristics.

6. group R １ and R ２ And / or Base R ３ and R ４ However, these form one or more ring structures in succinimide, 3-allylsuccinimide, cyclohexane-1,2-dicarboximide, 4-cyclohexene-1,2-dicarboximide, 1,2,3,6-tetrahydrophthalimide, 3,4,5,6-tetrahydrophthalimide, phthalimide, 4-phenoxyphthalimide, 4-benzoylphthalimide, 4-phenylsulfonylphthalimide, maleimide, bicyclo[2.2.1]hepta-5-ene-2,3-dicarboximide, bicyclo[2.2.1]heptane-2,3-dicarboximide, 3,6-epoxy-1,2,3,6-tetrahydrophthalimide, bicyclo[2.2.2]octa-5-ene-2,3-dicarboximide, tetrafluorosuccinimide, tetrafluorophthalimide, 3-phenylsuccinimide, and naphthalene-2,3-dicarboximide, etc. A curable composition according to any one of claims 1 to 5.

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

8. The following compounds, (C) at least one denaturing agent (C), (D) at least one reactive resin (D), (E) at least one filler (E), (F) at least one curing accelerator (F), (G) at least one solvent (G), and / or (H) at least one 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 (B). A curable composition according to any one of claims 1 to 7.

9. (E2) At least one fiber-reinforced filler A curable composition according to any one of claims 1 to 7, further comprising the above.

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

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 the above.

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

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

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

15. A molded article or fiber composite material obtained by the method described in claim 12.

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