Ternary resin blend

Abstract

The present disclosure discloses a ternary resin blend that can be cured to form a cured resin material for use as a matrix in a composite material. The ternary resin blend comprises a polyfunctional cyanate ester, an asymmetric bisphenol-derived cyanate ester, and a compound of formula (I), wherein R1, R2, R3, R4, R5, and R6 are as defined in the specification. The present disclosure also discloses a cured resin material prepared by curing the ternary resin blend, a composite material comprising the cured resin material, an article comprising the cured resin material or the composite material, and methods for preparing the ternary resin blend, the cured resin material, the composite material, and the article. #imgabs0#

Description

Technical Field

[0001] The present disclosure relates to ternary resin blends (i.e., resin blends comprising at least three different components). The ternary resin blends can be cured to form a resin material that can be used as a matrix in a composite material. The present disclosure also relates to cured resin materials prepared by curing the ternary resin blends disclosed herein, composite materials comprising the cured resin materials, and articles comprising the cured resin materials or the composite materials. The present disclosure further relates to methods for preparing the ternary resin blends, cured resin materials, composite materials, and articles disclosed herein. Background Art

[0002] Composite materials comprising an organic matrix are widely used for a variety of purposes. The chemical composition of the organic matrix can be selected according to the desired properties of the composite material.

[0003] Cyanate is a molecule in which the hydrogen atom of a phenolic OH group has been replaced by a cyanide (C≡N) group. Cyanate can be cured by heating, for example, by heating alone at high temperatures or by heating at a lower temperature in the presence of a catalyst. The resulting cured resin material has a relatively high glass transition temperature and a low dielectric constant, thereby providing good long-term thermal stability, good toughness, and good fire resistance, smoke resistance and anti-toxic properties at high temperatures. A blend of two or more cyanate can be prepared, or a blend of one or more cyanate and one or more other components, to fine-tune one or more properties of the material before and / or after curing. Such properties may include, for example, processability / fluidity / viscosity, thermomechanical properties (such as glass transition temperature), heat and thermooxidative stability, reactivity, flame retardancy and hygroscopicity before curing.

[0004] It would therefore be desirable to provide new resin blends, particularly new resin blends comprising one or more cyanate esters. Summary of the Invention

[0005] According to a first aspect, there is provided a composition comprising:

[0006] (a) polyfunctional cyanate esters;

[0007] (b) an asymmetrical bisphenol-derived cyanate ester; and

[0008] (c) Compounds of formula (I):

[0009]

[0010] in:

[0011] R1 and R2 are the same or different and are selected from hydrogen, halogen and other electron withdrawing groups;

[0012] R3, R4, R5 and R6 are the same or different and are selected from hydrogen, halogen and other groups that provide thermally stable compounds of formula (I); and

[0013] At least one of R1 and R2 is halogen.

[0014] In certain embodiments, R1 and R2 are the same or different and are selected from hydrogen and halogen. Alternatively or in addition, in certain embodiments, R3, R4, R5 and R6 are the same or different and are selected from hydrogen, halogen and aromatic groups.

[0015] According to an alternative aspect, there is provided a composition comprising:

[0016] (a) polyfunctional cyanate esters;

[0017] (b) an asymmetrical bisphenol-derived cyanate ester; and

[0018] (c) Compounds of formula (I):

[0019]

[0020] in:

[0021] R1 and R2 are the same or different and are selected from hydrogen, halogen and other electron withdrawing groups;

[0022] R3, R4, R5 and R6 are the same or different and are selected from hydrogen, halogen and aromatic groups; and

[0023] At least one of R1 and R2 is halogen.

[0024] In certain embodiments, R1 and R2 are the same or different and are selected from hydrogen and halogen. Alternatively or in addition, in certain embodiments, R3, R4, R5 and R6 are the same or different and are selected from hydrogen and halogen.

[0025] According to a second aspect, there is provided a cured resin material obtained or obtainable by curing the composition of the first aspect of the present disclosure.

[0026] According to a third aspect, there is provided a composite material comprising the cured resin material of the second aspect of the present disclosure.

[0027] According to a fourth aspect, there is provided an article comprising the cured resin material of the second aspect of the present disclosure.

[0028] According to a fifth aspect, there is provided an article comprising the composite material of the third aspect of the present disclosure.

[0029] According to a sixth aspect, there is provided a method for preparing the composition of the first aspect of the present disclosure, the method comprising mixing a polyfunctional cyanate ester, an asymmetric bisphenol-derived cyanate ester and a compound of formula (I).

[0030] According to a seventh aspect, there is provided a method for preparing the cured resin material of the second aspect of the present disclosure, the method comprising curing the composition of the first aspect of the present disclosure.

[0031] According to an eighth aspect, there is provided a method of preparing the composite material of the third aspect of the present disclosure, the method comprising combining the composition of the first aspect of the present disclosure with a reinforcing material, and subsequently curing the mixture.

[0032] It will be understood by those skilled in the art that, unless mutually exclusive, features described in any one of the above aspects may be applied to any other aspect as appropriately modified. In addition, unless mutually exclusive, any feature described herein may be applied to any aspect and / or combined with any other feature described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Embodiments will now be described, by way of example only, with reference to the accompanying drawings, in which:

[0034] Figure 1 Shows various resin materials per cm 3 Water intake per area (% cm -3 ) time function.

[0035] Figure 2 A method for preparing the composition of the first aspect of the present disclosure is shown, the method comprising the steps of mixing a polyfunctional cyanate ester, an asymmetrical bisphenol-derived cyanate ester and a compound of formula (I).

[0036] Figure 3 The method for preparing the cured resin material of the second aspect of the present disclosure is schematically shown, the method comprising the step of curing a composition comprising a polyfunctional cyanate ester, an asymmetric bisphenol-derived cyanate ester and a compound of formula (I).

[0037] Figure 4 A method for preparing the composite material of the third aspect of the present disclosure is schematically shown, the method comprising the steps of combining a composition comprising a polyfunctional cyanate ester, an asymmetric bisphenol-derived cyanate ester and a compound of formula (I) with a reinforcing material, followed by the step of curing the resulting composition and the reinforcing material, the resulting composition comprising a polyfunctional cyanate ester, an asymmetric bisphenol-derived cyanate ester and a compound of formula (I). DETAILED DESCRIPTION

[0038] Disclosed herein are ternary resin blends (ie, compositions comprising at least three different components) that can be cured to form resin materials that can be used as matrices in composite materials.

[0039] The compositions disclosed herein comprise:

[0040] (a) polyfunctional cyanate esters;

[0041] (b) an asymmetrical bisphenol-derived cyanate ester; and

[0042] (c) Compounds of formula (I):

[0043]

[0044] in:

[0045] R1 and R2 are the same or different and are selected from hydrogen, halogen and other electron withdrawing groups;

[0046] R3, R4, R5 and R6 are the same or different and are selected from hydrogen, halogen and a group that provides a thermally stable compound of formula (I); or

[0047] R3, R4, R5 and R6 are the same or different and are selected from hydrogen, halogen and aromatic groups; and

[0048] At least one of R1 and R2 is halogen.

[0049] In certain embodiments, R1 and R2 are the same or different and are selected from hydrogen and halogen, and / or R3, R4, R5 and R6 are the same or different and are selected from hydrogen, halogen and aromatic groups.

[0050] In certain embodiments, R1 and R2 are the same or different and are selected from hydrogen and halogen, and / or R3, R4, R5 and R6 are the same or different and are selected from hydrogen and halogen.

[0051] Compounds of formula (I)

[0052] As used herein, the term "electron withdrawing group" refers to a substituent that removes electron density from a conjugated π system. Examples of electron withdrawing groups include halogens (e.g., fluorine, chlorine, bromine, iodine), nitroso (-N=O), aminocarbonyl groups (-CONR2, wherein R is the same or different and is selected from H or alkyl), carboxyl groups (-CO2H), alkoxycarbonyl groups (-CO2R, wherein R is alkyl), acyl groups (-CHO), formyl groups (-COR, wherein R is alkyl), haloformyl groups (-COX, wherein X is halogen), trihalomethyl groups (-CX3, wherein each X is the same or different and is halogen), cyano groups (-C≡N), sulfonic acid (-SO3H), sulfonyl groups (-SO2R, wherein R is alkyl), nitro groups (-NO2), ammonium groups (-NH3 + ), substituted ammonium groups (-NR3 + , wherein R is alkyl), a trihalomethylsulfonyl group (-SO2CX3, wherein each X is the same or different and is a halogen, such as fluorine).

[0053] R1 and R2 may, for example, be the same or different and may be selected from hydrogen and halogen. R1 and R2 may, for example, be the same or different and may be halogen.

[0054] R1 and / or R2 may be, for example, halogen. R1 and R2 may be, for example, the same. R1 and R2 may be, for example, the same halogen.

[0055] In the case where one or both of R1 and R2 are halogen, the halogen may be selected from fluorine, chlorine and bromine. For example, in the case where one or both of R1 and R2 are halogen, the halogen may be selected from chlorine and bromine. For example, in the case where one or both of R1 and R2 are halogen, the halogen may be chlorine. For example, R1 and R2 may be chlorine.

[0056] R3 and R5 may be, for example, the same. R4 and R6 may be, for example, the same. For example, R3 and R5 may be the same, and R4 and R6 may be the same.

[0057] As used herein, the term "a group that provides a thermally stable compound of formula (I)" refers to a substituent that results in a compound of formula (I) that loses about 1.0% or less of its mass by weight in air at 250°C when measured by thermogravimetric analysis ASTM E2550-17. This includes, for example, hydrogen, halogens, and aromatic groups.

[0058] R3, R4, R5 and R6 may, for example, be the same or different and may be selected from hydrogen, halogen and aromatic groups.

[0059] The term "aromatic group" refers to a substituent of a ring having a resonant bond, and includes, for example, substituted and unsubstituted phenyl rings, substituted and unsubstituted heteroaromatic rings (e.g., substituted and unsubstituted pyridine, pyrazine, pyrrole, imidazole, pyrazole, oxazole or thiophene) and substituted and unsubstituted fused aromatic rings (e.g., substituted and unsubstituted naphthalene, anthracene or phenanthrene). For example, the aromatic group can be a substituted or unsubstituted phenyl ring. Substituents suitable for aromatic groups include, for example, halogen, amine, carboxylic acid, nitro, hydroxyl, C1-C4 alkyl and C1-C6 alkenyl, which can, for example, be conjugated with the aromatic ring.

[0060] Aromatic groups are relatively bulky and can therefore sterically inhibit the reaction of the OH groups on each phenolic ring of the compound of formula (I) with the other components in the ternary blend. Thus, for example, at most two of R3, R4, R5, and R6 can be aromatic groups. For example, one of R3, R4, R5, and R6 can be an aromatic group. In the case where two of R3, R4, R5, and R6 are aromatic groups, the aromatic groups can, for example, be present on the same phenolic ring (i.e., both R3 and R4 or both R5 and R6 can be aromatic groups), or one aromatic group can be present on each phenolic ring (i.e., one of R3 and R4 is an aromatic group, and one of R5 and R6 is an aromatic group).

[0061] R3, R4, R5 and R6 may, for example, be the same or different and may be selected from hydrogen, halogen and aromatic groups.

[0062] R3, R4, R5 and R6 may, for example, be the same or different and may be selected from hydrogen and halogen.

[0063] At least one of R3, R4, R5, and R6 may be, for example, hydrogen. For example, at least two of R3, R4, R5, and R6 may be hydrogen. For example, at least three of R3, R4, R5, and R6 may be hydrogen. For example, all of R3, R4, R5, and R6 may be hydrogen.

[0064] At least one of R3 and R4 may be, for example, hydrogen. For example, both R3 and R4 may be hydrogen. At least one of R5 and R6 may be, for example, hydrogen. For example, both R5 and R6 may be hydrogen. At least one of R3 and R4 and at least one of R5 and R6 may be, for example, hydrogen. For example, all of R3, R4, R5, and R6 may be hydrogen.

[0065] At least one of R3, R4, R5, and R6 may be, for example, a halogen. For example, at least two of R3, R4, R5, and R6 may be halogen. For example, at least three of R3, R4, R5, and R6 may be halogen. For example, all of R3, R4, R5, and R6 may be halogen.

[0066] At least one of R3 and R4 may be, for example, a halogen. For example, both R3 and R4 may be halogen. At least one of R5 and R6 may be, for example, a halogen. For example, both R5 and R6 may be halogen. At least one of R3 and R4 and at least one of R5 and R6 may be, for example, a halogen. For example, all of R3, R4, R5, and R6 may be halogen.

[0067] In the case where one or more of R3, R4, R5 and R6 are halogen, the halogen may be selected from fluorine, chlorine and bromine. For example, in the case where one or more of R3, R4, R5 and R6 are halogen, the halogen may be selected from chlorine and bromine. For example, in the case where one or more of R3, R4, R5 and R6 are halogen, the halogen may be chlorine.

[0068] R1 and R2 may, for example, be halogen, and R3, R4, R5, and R6 may be hydrogen. For example, R1 and R2 may be selected from fluorine, chlorine, and bromine, and R3, R4, R5, and R6 may be hydrogen. For example, R1 and R2 may be selected from chlorine and bromine, and R3, R4, R5, and R6 may be hydrogen.

[0069] The compound of formula (I) may be, for example, bisphenol C (BPC) having the following structure:

[0070]

[0071] Polyfunctional cyanate esters

[0072] As used herein, the term "cyanate" refers to a molecule in which the hydrogen atom of a phenolic OH group has been replaced by a cyanide (-C≡N) group. A "polyfunctional cyanate" is a cyanate that contains more than one cyanide group.

[0073] Any suitable polyfunctional cyanate ester may be used. For example, when cured, the polyfunctional cyanate ester may have a glass transition temperature equal to or greater than about 300°C. For example, when cured, the polyfunctional cyanate ester may have a glass transition temperature equal to or greater than about 310°C, such as equal to or greater than about 320°C, such as equal to or greater than about 330°C, such as equal to or greater than about 340°C, such as equal to or greater than about 350°C, such as equal to or greater than about 360°C, such as equal to or greater than about 370°C, such as equal to or greater than about 380°C. For example, when cured, the polyfunctional cyanate ester may have a glass transition temperature of about 500° C. or less, such as about 490° C. or less, such as about 480° C. or less, such as about 470° C. or less, such as about 460° C. or less, such as about 450° C. or less, such as about 440° C. or less, such as about 430° C. or less, such as about 420° C. or less, such as about 410° C. or less, such as about 400° C. or less. For example, when cured, the polyfunctional cyanate ester may have a glass transition temperature in the range of about 300° C. to about 500° C., or about 350° C. to about 450° C., or about 380° C. to about 420° C., or about 380° C. to about 400° C. This refers to the glass transition temperature of the polyfunctional cyanate ester when cured alone (i.e., without the other components in the ternary resin blend).

[0074] The glass transition temperature can be measured, for example, by dynamic mechanical analysis (DMA) according to ASTM D4065-12 or D5279-13.

[0075] The polyfunctional cyanate ester may, for example, be one of the polyfunctional cyanate esters disclosed in “Chemistry and Technology of Cyanate Ester Resins” (Edited by I Hamerton), Blackie Academic and Professional: Glasgow, 1994, pp. 34-43, the contents of which are incorporated herein by reference.

[0076] The polyfunctional cyanate ester may be, for example, a phenolic cyanate ester.

[0077] A phenolic resin is a polymer derived from a phenolic derivative and formaldehyde, wherein the phenolic units are linked by methylene and / or ethylene groups in the ortho and / or para positions. The phenolic derivative may, for example, be phenol or methylphenol. The ratio of formaldehyde to phenolic derivative may, for example, be less than one. The phenolic resin may, for example, contain from about 10 to about 20 phenolic units.

[0078] Novolac cyanates are phenolic resins in which one or more hydrogen atoms of one or more phenolic OH groups have been replaced by cyanide (-C≡N) groups. For example, a novolac cyanate may be a phenolic resin in which the hydrogen atoms of two or more phenolic OH groups have been replaced by cyanide (-C≡N) groups. For example, a novolac cyanate may be a phenolic resin in which all hydrogen atoms of the phenolic OH groups have been replaced by cyanide (-C≡N) groups.

[0079] The polyfunctional cyanate may be, for example, an oligomer of the following formula (II):

[0080]

[0081] Where n is 1, 2, or 3.

[0082] The polyfunctional cyanate of formula (II) may, for example, have a molecular weight ranging from about 300 g / mol to about 500 g / mol, such as from about 350 g / mol to about 450 g / mol, such as from about 360 to about 400 g / mol.

[0083] The polyfunctional cyanate esters may be supplied, for example, by Lonza Group Ltd as PT-30 material, or as supplied by Huntsman Advanced Materials XU-371 is a material based on cyanate ester of phenolic resin.

[0084] Asymmetric bisphenol-derived cyanate esters

[0085] As used herein, the term "cyanate ester" refers to a molecule in which the hydrogen atom of a phenolic OH group has been replaced with a cyanide (-C≡N) group.

[0086] As used herein, the term "bisphenol" refers to a molecule having two hydroxyphenyl groups. A bisphenol may be, for example, diphenylmethane having one hydroxyl group on each benzene ring.

[0087] "Bisphenol-derived cyanate" is a bisphenol in which the hydrogen atom of each hydroxyl group on the phenyl ring has been replaced by a cyanide (-C≡N) group. "Asymmetric bisphenol-derived cyanate" is a bisphenol-derived cyanate that does not possess any reflection symmetry.

[0088] Any suitable asymmetric bisphenol derived cyanate ester may be used. For example, the asymmetric bisphenol derived cyanate ester may be an asymmetric bisphenol derived cyanate ester having a bridging unit that disrupts the crystallinity of the monomer, making it a liquid or a solid having a melting point below 100°C.

[0089] The unsymmetrical bisphenol-derived cyanate ester may, for example, be one of the unsymmetrical bisphenol-derived cyanate esters disclosed in “Chemistry and Technology of Cyanate Ester Resins” (Editor: I. Hamerton), Blackie Academic and Professional: Glasgow, 1994, pp. 34-44, the contents of which are incorporated herein by reference. For example, the asymmetric bisphenol-derived cyanate ester can be selected from bisphenol E dicyanate, p-cumylphenyl cyanate (see Table 2.7 of the "Chemistry and Technology of Cyanate Ester Resins" cited above), the siloxanes in Table 2.9 of the "Chemistry and Technology of Cyanate Ester Resins" cited above, diallyl bisphenol A dicyanate and its diallyl analogs (see Table 2.9 of the "Chemistry and Technology of Cyanate Ester Resins" cited above), the fluoropolymers in Table 2.13 of the "Chemistry and Technology of Cyanate Ester Resins" cited above, and the monofunctional cyanate esters in Table 2.15 of the "Chemistry and Technology of Cyanate Ester Resins" cited above).

[0090] The unsymmetrical bisphenol-derived cyanate esters may, for example, be suitable for use as reactive diluents to enhance the low temperature processability of the polyfunctional cyanate esters described herein.

[0091] The asymmetrical bisphenol-derived cyanate ester may be, for example, a compound of the following formula (III):

[0092]

[0093] where R 9 and R 10 independently selected from hydrogen and C 1-4 Alkyl, and R 9 and R 10 different.

[0094] The asymmetrical bisphenol-derived cyanate ester may be, for example, a compound of the following formula (IIIa):

[0095]

[0096] where R 9 and R 10 independently selected from hydrogen and C1-4 Alkyl, and R 9 and R 10 different.

[0097] For example, R 9 and R 10 One of them may be hydrogen, and R 9 and R 10 The other one can be C 1-4 Alkyl (ie, an alkyl group having between 1 and 4 carbon atoms). For example, R 9 and R 10 One of them may be hydrogen, and R 9 and R 10 The other of R may be methyl or ethyl. 9 and R 10 One of them may be hydrogen, and R 9 and R 10 The other of may be methyl.

[0098] For example, the unsymmetrical bisphenol-derived cyanate ester may be bisphenol E dicyanate having the following structure:

[0099]

[0100] The unsymmetrical bisphenol-derived cyanate esters are available, for example, from Lonza Group Limited as LECy materials, or materials supplied by Huntsman Advanced Materials, are called L-10 is a material based on a low viscosity cyanate ester of bisphenol E.

[0101] Reinforcement materials

[0102] The composition of the first aspect of the present disclosure, the cured resin material of the second aspect of the present disclosure, the composite material of the third aspect of the present disclosure, and the articles of the fourth and fifth aspects of the present disclosure may further comprise a reinforcing material.

[0103] As used herein, a "reinforcement material" is any material that increases any of the mechanical properties of the composition of the first aspect after it has been cured.

[0104] For example, the composition of the first aspect of the present disclosure, the cured resin material of the second aspect of the present disclosure, the composite material of the third aspect of the present disclosure, and the articles of the fourth and fifth aspects of the present disclosure may further comprise nanomaterials.

[0105] As used herein, "nanomaterial" is any material having one or more average dimensions in the range of 1 nm to 100 nm.

[0106] Nanomaterials can be, for example, selected from nanoparticles (e.g., aluminum oxide, silicon dioxide, titanium dioxide, boron nitride, aluminum nitride), metal nanowhiskers, graphene (e.g., sheets, tubes, spheres), graphite, functionalized graphene (e.g., sheets, tubes, spheres), silicon nanotubes, and appropriately functionalized polyhedral oligomeric silsesquioxane (POSS) cages to co-react them with cyanate esters. Functionalized graphene can be, for example, functionalized with oxygen or carboxyl groups. The nanomaterial can be, for example, edge-oxidized graphene oxide.

[0107] The nanomaterial can, for example, be present in the composition of the first aspect in an amount equal to or less than about 5.0 wt %, based on the total dry weight of the composition. For example, the nanomaterial can be present in the composition in an amount equal to or less than about 4.5 wt %, such as equal to or less than about 4.0 wt %, such as equal to or less than about 3.5 wt %, such as equal to or less than about 3.0 wt %, such as equal to or less than about 2.5 wt %, such as equal to or less than about 2.0 wt %, such as equal to or less than about 1.5 wt %, such as equal to or less than about 1.0 wt %, such as equal to or less than about 0.5 wt %.

[0108] The nanomaterial can be present in the composition of the first aspect, for example, in an amount equal to or greater than about 0.01 wt % based on the total dry weight of the composition. For example, the nanomaterial can be present in the composition in an amount equal to or greater than about 0.05 wt %, such as equal to or greater than about 0.1 wt %, based on the total dry weight of the composition.

[0109] For example, the nanomaterial can be present in the composition of the first aspect in an amount ranging from about 0.01 wt% to about 5.0 wt%, such as about 0.05 wt% to about 2.0 wt%, such as about 0.1 wt% to about 1.0 wt%, based on the total dry weight of the composition.

[0110] Ternary resin blend

[0111] The composition according to the first aspect disclosed herein may, for example, comprise a compound of formula (I), a compound of formula (II), and a compound of formula (III). For example, the composition according to the first aspect disclosed herein may, for example, comprise bisphenol C (BPC), a compound of formula (II), and a compound of formula (III). The composition according to the first aspect disclosed herein may, for example, comprise a compound of formula (I), a compound of formula (II), and bisphenol E dicyanate.

[0112] The polyfunctional cyanate, the unsymmetrical bisphenol-derived cyanate and the compound of formula (I) may be present in the composition of the first aspect of the present disclosure in any amount provided that the total amount does not exceed 100 wt % based on the total dry weight of the composition.

[0113] Based on the total dry weight of the composition, the compound of formula (I) can, for example, be present in the composition according to the first aspect disclosed herein in an amount equal to or less than about 10.0 wt %. The total dry weight of the composition refers to the weight of the composition from which any water or other solvents have been removed. For example, based on the total dry weight of the composition, the compound of formula (I) can be present in the composition according to the first aspect in an amount equal to or less than about 9.0 wt %, or equal to or less than about 8.0 wt %, or equal to or less than about 7.0 wt %, or equal to or less than about 6.0 wt %, or equal to or less than about 5.0 wt %.

[0114] The compound of formula (I) can, for example, be present in the composition according to the first aspect disclosed herein in an amount equal to or greater than about 1.0 wt %, based on the total dry weight of the composition. For example, the compound of formula (I) can be present in the composition according to the first aspect in an amount equal to or greater than about 1.5 wt %, or equal to or less than about 2.0 wt %, or equal to or less than about 2.5 wt %, or equal to or less than about 3.0 wt %, or equal to or less than about 3.5 wt %, or equal to or greater than about 4.0 wt %, based on the total dry weight of the composition.

[0115] For example, the compound of formula (I) may be present in the composition according to the first aspect disclosed herein, for example, in an amount ranging from about 1.0 wt % to about 10.0 wt %, for example from about 1.5 wt % to about 7.0 wt %, for example from about 3.0 wt % to about 5.0 wt %, based on the total dry weight of the composition.

[0116] The polyfunctional cyanate ester can, for example, be present in the composition according to the first aspect disclosed herein in an amount equal to or less than about 95.0 wt %, based on the total dry weight of the composition. For example, the polyfunctional cyanate ester can be present in the composition according to the first aspect in an amount equal to or less than about 94.0 wt %, or equal to or less than about 93.0 wt %, or equal to or less than about 92.0 wt %, or equal to or less than about 91.0 wt %, or equal to or less than about 90.0 wt %, or equal to or less than about 89.0 wt %, or equal to or less than about 88.0 wt %, or equal to or less than about 87.0 wt %, or equal to or less than about 86.0 wt %, or equal to or less than about 85.0 wt %.

[0117] The polyfunctional cyanate ester can, for example, be present in the composition according to the first aspect disclosed herein in an amount equal to or greater than about 75.0 wt %, based on the total dry weight of the composition. For example, the polyfunctional cyanate ester can be present in the composition according to the first aspect in an amount equal to or greater than about 76.0 wt %, or equal to or greater than about 77.0 wt %, or equal to or greater than about 78.0 wt %, or equal to or greater than about 79.0 wt %, or equal to or greater than about 80.0 wt %, or equal to or greater than about 81.0 wt %, or equal to or greater than about 82.0 wt %, or equal to or greater than about 83.0 wt %, or equal to or greater than about 84.0 wt %.

[0118] For example, the polyfunctional cyanate ester may be present in the composition according to the disclosed first aspect in an amount ranging from about 75.0 wt % to about 95.0 wt %, such as from about 80.0 wt % to about 90.0 wt %, such as from about 83.0 wt % to about 88.0 wt %, based on the total dry weight of the composition.

[0119] The asymmetric bisphenol-derived cyanate ester can be present in the composition of the first aspect disclosed herein, for example, in an amount equal to or less than about 15.0 wt. %, based on the total dry weight of the composition. For example, the asymmetric bisphenol-derived cyanate ester can be present in the composition of the first aspect in an amount equal to or less than about 14.0 wt. %, or equal to or less than about 13.0 wt. %, or equal to or less than about 12.0 wt. %, or equal to or less than about 11.0 wt. %, based on the total dry weight of the composition.

[0120] The asymmetric bisphenol-derived cyanate ester can be present in the composition of the first aspect disclosed herein, for example, in an amount equal to or greater than about 5.0 wt. %, based on the total dry weight of the composition. For example, the asymmetric bisphenol-derived cyanate ester can be present in the composition of the first aspect in an amount equal to or greater than about 6.0 wt. %, or equal to or greater than about 7.0 wt. %, or equal to or greater than about 8.0 wt. %, or equal to or greater than about 9.0 wt. %, based on the total dry weight of the composition.

[0121] For example, the unsymmetrical bisphenol-derived cyanate ester can be present in the composition of the first aspect in an amount ranging from about 5.0 wt % to about 15.0 wt % or from about 8.0 wt % to about 12.0 wt %, based on the total dry weight of the composition.

[0122] The composition of the first aspect of the present disclosure may, for example, have a bulk viscosity of about 500 cP or less at 20°C. For example, the composition of the first aspect of the present disclosure may have a bulk viscosity of about 450 cP or less or about 400 cP or less at 20°C. The composition of the first aspect of the present disclosure may, for example, have a bulk viscosity of about 200 cP or more at 20°C. For example, the composition of the first aspect of the present disclosure may have a bulk viscosity of about 250 cP or more or about 300 cP or more at 20°C. For example, the composition of the first aspect of the present disclosure may have a bulk viscosity in the range of about 200 cP to about 500 cP, or about 250 cP to about 450 cP, or about 300 cP to about 400 cP at 20°C. The bulk viscosity may be measured by ASTM D4440-15.

[0123] The composition of the first aspect of the present disclosure may, for example, have a dynamic rheology equal to or less than about 500 Pa.s at 30°C. For example, the composition of the first aspect of the present disclosure may have a dynamic rheology equal to or less than about 450 Pa.s, or equal to or less than about 400 Pa.s, or equal to or less than about 350 Pa.s, or equal to or less than about 300 Pa.s at 30°C. The composition of the first aspect of the present disclosure may, for example, have a dynamic rheology equal to or greater than about 10 Pa.s. For example, the composition of the first aspect of the present disclosure may have a dynamic rheology equal to or greater than about 20 Pa.s, or equal to or greater than about 50 Pa.s, or equal to or greater than about 100 Pa.s, or equal to or greater than about 150 Pa.s at 30°C. Dynamic rheology can be measured by ASTM D4440-15.

[0124] Also disclosed herein is a method for preparing a composition according to the first aspect of the present disclosure, the method comprising mixing a polyfunctional cyanate ester, an asymmetric bisphenol-derived cyanate ester, and a compound of formula (I). The components can be mixed in any suitable order. Any suitable mixing technique and / or equipment can be used. One or more components of the composition of the first aspect of the present disclosure can be heated before weighing and / or before mixing with other components to improve their viscosity and workability. For example, before weighing and / or mixing with other components, the polyfunctional cyanate ester and / or the asymmetric bisphenol-derived cyanate ester can be heated to a temperature in the range of, for example, about 60°C to about 120°C, for example, about 80°C to about 100°C, for example, about 90°C.

[0125] Curing resin material

[0126] Also disclosed herein is a cured resin material obtained and / or obtainable by curing the composition according to the first aspect of the present disclosure. Also disclosed herein is a method for preparing the cured resin material, the method comprising curing the composition according to the first aspect of the present disclosure.

[0127] Without wishing to be bound by theory, it is believed that curing the composition comprising a polyfunctional cyanate ester results in crosslinking between cyanate groups to form a network of oxygen-linked triazine rings (cyanurates) and bisphenol ethers. This structure is the result of cyclotrimerization of -OC≡N groups. The presence of reactive groups on other components of the composition of the first aspect of the present disclosure may result in these components also being incorporated into the crosslinked structure of the cured resin material. For example, the -OC≡N groups of the asymmetric bisphenol-derived cyanate ester may crosslink with the -OC≡N groups in the polyfunctional cyanate ester and / or the asymmetric bisphenol-derived cyanate ester, for example to form oxygen-linked triazine rings. For example, the double bonds and / or -OH groups of the compound of formula (I) may crosslink with the -OC≡N groups in the polyfunctional cyanate ester and / or the asymmetric bisphenol-derived cyanate ester. This may, for example, reduce the amount of hydrolyzable residual cyanate and hydroxyl groups present in the cured resin material.

[0128] Curing of the composition of the first aspect of the present disclosure can, for example, result in a degree of cure equal to or greater than about 85.0%. For example, the curing can result in a degree of cure equal to or greater than about 86.0%, such as equal to or greater than about 87.0%, such as equal to or greater than about 88.0%, such as equal to or greater than about 89.0%, such as equal to or greater than about 90.0%, such as equal to or greater than about 91.0%, such as equal to or greater than about 92.0%.

[0129] Curing of the composition of the first aspect of the present disclosure can, for example, result in a degree of cure equal to or less than about 98.0%. For example, curing can result in a degree of cure equal to or less than about 97.0%, such as equal to or less than about 96.0%, such as equal to or less than about 95.0%, such as equal to or less than about 94.0%.

[0130] For example, curing of the composition of the first aspect of the present disclosure can result in a degree of cure ranging from about 85.0% to about 98.0%, or from about 88.0% to about 95.0%, or from about 90.0% to about 94.0%.

[0131] The degree of cure can be measured by differential scanning calorimetry (DSC) running a dynamic scan from room temperature to 400°C at a heating rate of 10 K / min. The degree of cure is calculated using the following formula, where ΔH c is the curing exothermic enthalpy (J / g), and ΔH pc is the heat release enthalpy after curing (J / g).

[0132]

[0133] The composition of the first aspect of the present disclosure may, for example, be prepared and placed into a mold before curing so that the cured resin material has a desired shape.

[0134] The curing of the composition according to the first aspect of the present disclosure may occur at a temperature equal to or greater than about 110° C. For example, the curing of the composition according to the first aspect of the present disclosure may occur at a temperature equal to or greater than about 115° C., such as equal to or greater than about 120° C., such as equal to or greater than about 125° C., such as equal to or greater than about 130° C., such as equal to or greater than about 135° C., such as equal to or greater than about 140° C., such as equal to or greater than about 145° C., such as equal to or greater than about 150° C., such as equal to or greater than about 155° C., such as equal to or greater than about 160° C.

[0135] The curing of the composition according to the first aspect of the present disclosure may occur at a temperature equal to or less than about 300° C. For example, the curing of the composition according to the first aspect of the present disclosure may occur at a temperature equal to or less than about 295° C., such as equal to or less than about 290° C., such as equal to or less than about 285° C., such as equal to or less than about 280° C., such as equal to or less than about 275° C., such as equal to or less than about 270° C., such as equal to or less than about 265° C., such as equal to or less than about 260° C., such as equal to or less than about 255° C., such as equal to or less than about 250° C.

[0136] For example, curing of the composition according to the first aspect of the present disclosure may occur at a temperature in the range of about 110°C to about 300°C, such as about 120°C to about 270°C, such as about 140°C to about 250°C.

[0137] The curing of the composition according to the first aspect of the present disclosure can occur in a plurality of different stages, each of which is carried out at a different temperature and / or for a different length of time. For example, the curing of the composition according to the first aspect of the present disclosure can occur in two or three different stages, each of which is carried out at a different temperature. The temperature of the curing can increase with each subsequent stage.

[0138] For example, curing of the composition may occur in a first stage at a temperature in the range of about 140°C to about 180°C for between about 30 minutes and about 2 hours, a second stage at a temperature in the range of about 180°C to about 200°C for between about 2 hours and about 4 hours, and a third stage at a temperature in the range of about 230°C to about 270°C for between about 30 minutes and about 2 hours.

[0139] The onset of polymerization (cross-linking) of the composition of the first aspect of the present disclosure may, for example, be equal to or less than about 140° C. For example, the onset of polymerization of the composition of the first aspect of the present disclosure may be equal to or less than about 135° C., for example, equal to or less than about 130° C. The onset of polymerization of the composition of the first aspect of the present disclosure may, for example, be equal to or greater than about 120° C., for example, equal to or greater than about 125° C. The onset of polymerization may be measured, for example, by differential scanning calorimetry (DSC), to measure the significant deflection from the baseline, running a dynamic scan from room temperature to 400° C. at a heating rate of 10 K / min (see, for example, http: / / www.tainstruments.com / pdf / literature / TA073.pdf, the contents of which are incorporated herein by reference).

[0140] The curing of the composition of the first aspect of the present disclosure may, for example, occur in the presence of a catalyst. The catalyst may, for example, comprise a carboxylate and / or chelate of a transition metal such as copper, zinc, manganese, cobalt or nickel dissolved in a hydrogen-donating solvent such as an alkylphenol. The curing of the composition of the first aspect of the present disclosure may, for example, occur in the absence of any catalyst.

[0141] The composition of the first aspect of the present disclosure may be degassed, for example, prior to curing. Degassing may be performed at any temperature less than the temperature at which polymerization of the particular composition begins. Degassing may be performed at any temperature and for any time period less than the time period required to initiate curing. For example, degassing may be performed at a temperature in the range of about 60°C to about 120°C for about 15 minutes to about 1 hour.

[0142] The cured resin material may, for example, have a glass transition temperature of about 300° C. or greater. For example, the cured resin material may have a glass transition temperature of about 310° C. or greater, for example, about 320° C. or greater, for example, about 330° C. or greater, for example, about 340° C. or greater, for example, about 350° C. or greater, for example, about 360° C. or greater, for example, about 370° C. or greater, for example, about 380° C. or greater. For example, the cured resin material may have a glass transition temperature of about 500° C. or less, for example, about 490° C. or less, for example, about 480° C. or less, for example, about 470° C. or less, for example, about 460° C. or less, for example, about 450° C. or less, for example, about 440° C. or less, for example, about 430° C. or less, for example, about 420° C. or less, for example, about 410° C. or less, for example, about 400° C. or less. For example, the cured resin material may have a glass transition temperature in the range of about 300°C to about 500°C, or about 350°C to about 450°C, or about 380°C to about 420°C, or about 380°C to about 400°C.

[0143] The glass transition temperature can be measured, for example, by dynamic mechanical analysis (DMA) according to ASTM D4065-12 or D5279-13.

[0144] The temperature at which the cured resin material of the second aspect of the present disclosure loses 5 wt% of its mass may be, for example, equal to or greater than about 400° C. For example, the temperature at which the cured resin material of the second aspect of the present disclosure loses 5 wt% of its mass may be, for example, equal to or greater than about 405° C., such as equal to or greater than about 410° C., such as equal to or greater than about 415° C.

[0145] The temperature at which the cured resin material of the second aspect of the present disclosure loses 5 wt % of its mass may be, for example, equal to or less than about 430°C, such as equal to or less than about 425°C, such as equal to or less than about 420°C.

[0146] For example, the temperature at which the mass of the cured resin material of the second aspect of the present disclosure loses 5 wt % may be, for example, in the range of about 400°C to about 430°C or about 410°C to about 420°C.

[0147] The temperature at which the cured resin material of the second aspect of the present disclosure loses 50% by weight of its mass may be, for example, equal to or greater than about 630° C. For example, the temperature at which the cured resin material of the second aspect of the present disclosure loses 50% by weight of its mass may be, for example, equal to or greater than about 635° C., such as equal to or greater than about 640° C., such as equal to or greater than about 645° C., such as equal to or greater than about 650° C.

[0148] The temperature at which the cured resin material of the second aspect of the present disclosure loses 50 wt% of its mass may be, for example, equal to or less than about 670°C, such as equal to or less than about 665°C, such as equal to or less than about 660°C, such as equal to or less than about 655°C.

[0149] For example, the temperature at which the cured resin material of the second aspect of the present disclosure loses 50 wt% of its mass may be in the range of about 630°C to about 670°C, or about 640°C to about 660°C, or about 645°C to about 655°C.

[0150] The mass loss at a specific temperature (thermal stability) can be determined by thermogravimetric analysis (TGA) under air or nitrogen.

[0151] The cured resin material of the second aspect of the present disclosure may, for example, have a cm-1 value equal to or less than about 0.35% after 4 hours. -3 , for example, equal to or less than about 0.32% cm -3 , for example, equal to or less than about 0.30% cm -3 , for example, equal to or less than about 0.28% cm -3The cured resin material of the second aspect of the present disclosure may, for example, have a moisture uptake of equal to or greater than about 0.10% cm -3 , for example, equal to or greater than about 0.15% cm -3 , for example, equal to or greater than about 0.20% cm -3 , for example, equal to or greater than about 0.25% cm -3 For example, the cured resin material may have a moisture uptake of about 0.10% cm -3 to about 0.35%cm -3 or about 0.20% cm -3 to about 0.30%cm -3 Water intake within the range.

[0152] The cured resin material of the second aspect of the present disclosure may, for example, have a cm-1 value equal to or less than about 0.75% after 25 hours. -3 , for example, equal to or less than about 0.70% cm -3 , for example, equal to or less than about 0.65% cm -3 , for example, equal to or less than about 0.60% cm -3 The cured resin material of the second aspect of the present disclosure may, for example, have a moisture uptake of equal to or greater than about 0.40% cm -3 , for example, equal to or greater than about 0.45% cm -3 , for example, equal to or greater than about 0.50% cm -3 For example, the cured resin material may have a moisture uptake of about 0.40% cm after 25 hours. -3 to about 0.75%cm -3 or about 0.50% cm -3 to about 0.60%cm -3 Water intake within the range.

[0153] The cured resin material of the second aspect of the present disclosure may, for example, have a cm-1 value equal to or less than about 1.70% after 505 hours. -3 , for example, equal to or less than about 1.65% cm -3 , for example, equal to or less than about 1.60% cm -3 , for example, equal to or less than about 1.55% cm -3 , for example, equal to or less than about 1.50% cm -3 , for example, equal to or less than about 1.45% cm -3 , for example, equal to or less than about 1.40% cm -3 , for example, equal to or less than about 1.35% cm -3 The cured resin material of the second aspect of the present disclosure may, for example, have a moisture uptake of equal to or greater than about 1.10% cm-3 , such as equal to or greater than about 1.15% cm -3 , for example, equal to or greater than about 1.20% cm -3 , for example, equal to or greater than about 1.25% cm -3 , for example, equal to or greater than about 1.30% cm -3 For example, the cured resin material may have a moisture uptake of approximately 1.10% cm after 505 hours. -3 to about 1.70%cm -3 or about 1.20% cm -3 to about 1.40%cm -3 or about 1.25% cm -3 to about 1.35%cm -3 Water intake within the range.

[0154] Water uptake can be measured by ASTM D570-98.

[0155] Composite materials

[0156] Also disclosed herein is a composite material comprising a cured resin material according to the second aspect of the present disclosure. As used herein, a "composite material" is a material comprising two or more different materials that remain separate and distinct within the composite material, wherein the two or more different materials have different chemical and / or physical properties such that, when combined, they produce a material having properties that differ from those of the individual components. Thus, one component of the composite material disclosed herein is a cured resin material as disclosed herein.

[0157] Another component of the composite material disclosed herein may be, for example, a reinforcing material as disclosed herein. The reinforcing material may be, for example, a nanomaterial.

[0158] Also disclosed herein is a method for preparing a composite material, the method comprising combining the composition according to the first aspect of the present disclosure with a reinforcing material, and subsequently curing the resulting composition.

[0159] The curing process may be, for example, according to the curing process described herein for curing resin materials.

[0160] The composite material may, for example, have one or more of the properties described herein with respect to the cured resin material, such as glass transition temperature, thermal stability, and / or moisture uptake.

[0161] The composite materials disclosed herein can be formed using any method known to those skilled in the art, such as hot melt prepreg methods, filament winding methods, and resin transfer molding (RTM) methods.

[0162] Products

[0163] Also provided herein are articles comprising the cured resin material of the second aspect of the present disclosure and articles comprising the composite material according to the third aspect of the present disclosure. As used herein, "article" refers to a commercial product or object comprising the cured resin material of the second aspect of the present disclosure and / or the composite material according to the third aspect of the present disclosure. Thus, the article may be in contact with one or more other materials.

[0164] An article may, for example, be a product or object that is a part of a larger product or object.

[0165] The article can be, for example, any article that can benefit from a material having low moisture uptake, high flame and smoke retardancy, and / or high high temperature resistance.

[0166] The article may be, for example, a gas turbine engine component (e.g., a gas turbine shaft, such as a compressor / fan shaft, a gearbox shaft, an auxiliary drive shaft), a generator component, a motor component, a compressor variable blade, a stator blade, a rotor blade, or an airframe structure (e.g., an airframe structure for a high Mach number aircraft). The article may be, for example, a component of a gas turbine engine.

[0167] The article may, for example, be included in an engine.The article may, for example, be included in an aircraft.

[0168] Example

[0169] Example 1 - Water Intake

[0170] PT-30(1) and LECy(2) was purchased from Lonza AG (Visp, Switzerland) and used as received. PT-30 is an oligomeric phenol cyanate (average relative molecular mass 381.39 gmol -1 ). Bisphenol C (4, BPC) and edge-oxidized graphene oxide (5, EOGO) were purchased from Sigma-Aldrich and Garmor Inc, respectively, and used as received. For clarity, each monomer is assigned a number and will be referred to by that number throughout the text. For blends, the notation [1 x :2 y ], where 1 and 2 are the designated monomer numbers, and x and y are their corresponding weight percentages in the blend composition.

[0171] A blend was prepared by weighing 1, 2, 4 and 5 into a 100 ml custom reaction vessel (without lid) in the following weight ratios: 1 85 :2 9.9 :45:5 0.1 (Blend 1) and 1 85 :210 :45 (Blend 2) and stirred at 90°C for 30 minutes using an overhead stirrer (until a homogeneous blend is achieved). The resulting homogeneous blend is poured into the desired mold where it is degassed in a vacuum oven at 90°C for 30 minutes. The resin sample is cured in a convection oven using the following cure cycle: 160°C for 1 hour, 200°C for 3 hours, and 250°C for 1 hour. Due to its viscosity, Before weighing PT-30(1), it was heated to 90°C for 30 minutes. To further assist in the blending of the materials, LECy was also melted at 90°C.

[0172] Comparative compositions were prepared in a similar manner using one or more of PT-30, LECy, and diallylbisphenol A (DBA).

[0173] The water absorption was determined by ASTM D570-98. The cured resin was placed in a round-bottom flask half-filled with deionized water. The temperature of the water was monitored using a thermocouple connected to the turntable insert of the hot plate (to allow the use of more than one round-bottom flask heated simultaneously). After a specified time period, the resin block was removed from the water, dried using a paper towel, and weighed in a mass balance with a readability of up to 0.0001 g.

[0174] The results are shown in Figure 1 and Table 1 below.

[0175] Table 1

[0176]

[0177]

[0178] Example 2 - Dynamic Rheology of Resin Blends

[0179] Various resin blends were prepared as described above in Example 1 (but not cured).

[0180] The dynamic rheological properties of the resin blends were measured by ASTM D4440-15.

[0181] The results are shown in Table 2 below.

[0182] Table 2

[0183] Resin blends Complex viscosity at 30°C (Pa.s) PT-30 296 <![CDATA[PT-30 95 LECy0BPC5]]> 926 <![CDATA[PT-30 90 LECy5BPC5]]> 383 <![CDATA[PT-30 85 LECy 10 BPC5]]> 203 <![CDATA[PT-30 80 LECy 15 BPC5]]> 101 <![CDATA[PT-30 75 LECy 20 BPC5]]> 47 <![CDATA[PT-30 70 LECy 25 BPC5]]> 28

[0184] Example 3 - Onset of Polymerization and Extent of Curing

[0185] Various resin blends were prepared as described above in Example 1 (but without curing).

[0186] The degree of cure was measured by differential scanning calorimetry (DSC) running a dynamic scan from room temperature to 400° C. at a heating rate of 10 K / min. The degree of cure was calculated using the following formula, where ΔH c is the curing exothermic enthalpy (J / g), and ΔH pc is the heat release enthalpy after curing (J / g).

[0187]

[0188] The onset of polymerization was measured by differential scanning calorimetry (DSC) to measure the significant deflection from the baseline, running a dynamic scan from room temperature to 400° C. at a heating rate of 10 K / min.

[0189] The results are shown in Table 3 below.

[0190] Table 3

[0191]

[0192] Example 4 - Thermal Stability

[0193] Various resin blends were prepared as described above in Example 1 (but without curing).

[0194] Thermal stability was determined by thermogravimetric analysis (TGA) under air or nitrogen.

[0195] The results are shown in Tables 4 and 5 below.

[0196] Table 4

[0197]

[0198] Table 5

[0199]

[0200] It should be understood that the present invention is not limited to the above-described embodiments and that various modifications and improvements may be made without departing from the concepts described herein. Unless mutually exclusive, any feature may be used alone or in combination with any other feature, and the present disclosure extends to and includes all combinations and subcombinations of one or more features described herein.

Claims

1. A composition comprising, based on the total dry weight of the composition: (a) 80.0% to 90.0% by weight of a polyfunctional cyanate of formula (II): Where n is 1 to 3; (b) 5.0% to 15.0% by weight of an asymmetrical bisphenol-derived cyanate of formula (III): where R 9 and R 10 Independently selected from H and C 1-4 Alkyl, and R 9 and R 10 different; and (c) 1.5% to 7.0% by weight of a compound of formula (I): in: R1 and R2 are the same or different and are halogen; and R3, R4, R5 and R6 are hydrogen; The limitation is that the total amount of the compound of formula (I), the polyfunctional cyanate ester and the asymmetric bisphenol-derived cyanate ester is equal to or less than 100% by weight.

2. The composition of claim 1, wherein R1 and R2 are the same halogen.

3. The composition of claim 1, wherein R1 and R2 are Cl.

4. The composition of claim 1, wherein the composition further comprises a nanomaterial.

5. The composition of claim 4, wherein the nanomaterial is edge-oxidized graphene oxide.

6. The composition according to claim 4 or 5, wherein the nanomaterial is present in the composition in an amount of 0.01 wt% to 5.0 wt% based on the total dry weight of the composition.

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