Epoxy resin

Abstract

To provide: epoxide-containing compounds comprising three benzene units linked by bridging groups; curable epoxy resin formulations comprising the epoxide-containing compounds; and composite materials comprising the formulations.SOLUTION: A curable epoxy resin formulation comprises an epoxide-containing compound of the formula 1 or 2 in the figure, and a curing agent. An impregnated fiber reinforced material comprises fibers impregnated with a curable epoxy resin formulation.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 62 / 366,443, filed July 25, 2016, and to Australian Provisional Application No. 2016904019, filed October 4, 2016, the contents of which are incorporated herein by reference.

[0002] Disclosed herein are epoxide-containing compounds having three benzene units joined by a bridging atom, the preparation of curable epoxy resin formulations containing the epoxide compounds, and the possibility of incorporating the compounds into composites. [Background technology]

[0003] For fiber-reinforced composites, the efficiency of load transfer at the microscale between the fiber and the surrounding matrix has a direct and continuous impact on the overall mechanical performance of the composite. The region of the matrix that is substantially affected by the presence of the fiber is sometimes called the "interphase" region, which is the interfacial region of the matrix immediately surrounding the fiber. In composites, this interphase experiences high shear strain due to the imbalance between the elastic modulus of the fiber and that of the matrix surrounding the fiber.

[0004] Although various resin matrix formulations have been developed to maximize the deformability of polymer resins, high-performance formulations are still limited by limited fluid resistance and less-than-desirable pre-impregnated composite (prepreg) handling properties (e.g., poor tack and / or prepreg handling life). These issues can be partially addressed by modifying the chemistry of the bulk polymer resin that forms the matrix. However, these modifications require the development of specific monomers or additives, which can increase manufacturing costs. Furthermore, while these specific formulations and additives can improve the fluid resistance of the matrix resin, other properties of the composite may be compromised.

[0005] Epoxies can be deformed by elongation and / or strain. Materials that respond primarily to strain deformation, rather than elongation deformation, tend to exhibit higher strength and improved properties than materials based on elongation deformation. Therefore, the present inventors have conducted extensive research and development to identify alternative classes of epoxy resins that exhibit enhanced strain deformation, while also exhibiting suitable matrix modulus, glass transition temperature (Tg), and environmental resistance.

[0006] Epoxy resins are versatile materials that can be combined with fibers to produce a wide variety of composites, including many prepreg compositions.

[0007] For composites containing epoxy resin and fibers, the fiber angle affects the distribution of strain versus elongational deformation. Therefore, the angle of the incorporated fibers is selected to absorb mechanical energy and create an environment for strain deformation rather than elongational deformation. As the angle approaches parallel to the primary load direction, the deformation mode decreases in the form of elongational deformation and increases in the form of strain deformation. By finding the optimal fiber angle, the load carried by the fibers in these composites can be increased.

[0008] While extensional deformation properties are generally similar for different epoxies, intermolecular strain geometry within the epoxy component means that the strain deformation properties can differ significantly for different epoxy resins.

[0009] Since strain deformation is generally favorable, identifying materials with optimal strain properties while balancing them with material properties such as Tg and stiffness is a challenge.

[0010] Therefore, there is a need to develop and identify alternative types of epoxy resins that exhibit enhanced strain capabilities while maintaining high performance, where strain epoxy resins can be combined with fibers to produce composites that absorb mechanical energy and dissipate this energy as heat, thereby preventing the possibility of extensional failure and increasing the load carried by the fibers.

[0011] Any discussion of documents, works, materials, devices, articles or the like which is included in this specification should not be taken as an admission that any or all of such matter forms part of the state of the art or was general common knowledge in the field pertaining to the present disclosure by virtue of its existence prior to the priority date of each claim of this application. Summary of the Invention

[0012] In one aspect, disclosed herein is a compound of Formula 1 or Formula 2, TIFF0007772508000001.tif26170TIFF0007772508000002.tif32170In the formula, X 1 are each the same and are selected from O and C(O); X 2 are each the same and are selected from C(O), R 1 are hydrogen, and R 2 are each selected from an epoxide group, or R 2are hydrogen, and R 1 are each selected from epoxide groups.

[0013] In one example, the epoxide group is TIFF0007772508000003.tif19170 and Selected from TIFF0007772508000004.tif32170.

[0014] In another example, (a)X 1 When is O, the epoxide group is TIFF0007772508000005.tif20170, (b)X 1 When is C(O), the epoxide group is TIFF0007772508000006.tif32170, and (c)X 2 When is C(O), (i)R 2 is H and R 1 but, TIFF0007772508000007.tif20170 or TIFF0007772508000008.tif32170, or (ii)R 1 is H and R 2 but, The file is TIFF0007772508000009.tif31170.

[0015] In another aspect, disclosed herein is a curable epoxy resin formulation comprising an epoxide-containing compound as defined herein and a curing agent.

[0016] In another aspect, disclosed herein is a curable epoxy resin formulation comprising an epoxy resin and a curing agent; The epoxy resin may be a compound of formula 3: Contains TIFF0007772508000010.tif27170, During the ceremony, X are each the same and are selected from O, CH2, and C(O); R are each the same and are an epoxide group; and The curing agent is a compound of Formula 4: Contains diamine hardener TIFF0007772508000011.tif26170, wherein each Y is the same and is selected from O, CH2, and C(O).

[0017] In one example, the epoxide group is TIFF0007772508000012.tif20170 and Selected from TIFF0007772508000013.tif31170.

[0018] In another example, each R is the same and is from the group consisting of: TIFF0007772508000014.tif19170 and TIFF0007772508000015.tif33170; and optionally, R is TIFF0007772508000016.tif19170 and when X is CH2, the CH2 groups are meta to each other.

[0019] In another aspect, disclosed herein is an impregnated fiber reinforced material comprising fibers impregnated with a curable epoxy resin formulation as defined herein.

[0020] In another aspect, disclosed herein is a composite comprising a fibrous material within a matrix of cured epoxy resin, wherein the cured epoxy resin is formed from a curable epoxy resin formulation as defined herein.

[0021] In one embodiment, disclosed herein is a method of forming an impregnated fiber reinforced material, the method comprising the steps of: a) (i) a curable epoxy resin formulation as defined herein, and (ii) textile materials; and b) (i) combining the resin formulation of step (a) with the fibrous material of step (a) and (ii) subjecting the material to an elevated temperature to cure the material, thereby forming an impregnated fibrous reinforced material. It includes:

[0022] In another aspect, disclosed herein is the use of a compound as defined herein as a curable epoxy resin or in the preparation of a curable epoxy resin formulation.

[0023] In another aspect, disclosed herein is a method for preparing a compound of formula 8, the method comprising the steps of: i) reacting a compound of formula 5 with a compound of formula 6 in the presence of a catalyst to form a compound of formula 7, wherein P is a protecting group, M is a metal, and LG is a leaving group: ii) further reacting the compound of formula 7 with an acid catalyst to form a compound of formula 8: It contains TIFF0007772508000018.tif26170.

[0024] In another aspect, disclosed herein is a method for preparing a compound of formula 10, comprising reacting a compound of formula 8 with a halogenated epoxy compound of formula 9 to form a compound of formula 10: TIFF0007772508000019.tif67170A method for preparing the compound of formula 10.

[0025] In one example, the compound of formula 8 is prepared by a method according to the above embodiment in paragraph

[0023] . It will be appreciated that various examples of the present disclosure may be utilized, some of which are described below with reference to the following drawings: [Brief explanation of the drawings]

[0026] [Figure 1] 1H (image a) and 13C (image b) nuclear magnetic resonance spectra for N,N,N,N-tetraglycidyl 1,4-bis(4-aminophenoxy)benzene (144-TGAPB). [Figure 2] High-performance liquid chromatogram showing resolution times for components in the synthesis of N,N,N,N-tetraglycidyl 1,4-bis(4-aminophenoxy)benzene (144-TGAPB). [Figure 3] 1H (image a) and 13C (image b) nuclear magnetic resonance spectra for N,N,N,N-tetraglycidyl 1,3-bis(4-aminophenoxy)benzene (134-TGAPB). [Figure 4] High-performance liquid chromatogram showing resolution times for components in the synthesis of N,N,N,N-tetraglycidyl 1,3-bis(4-aminophenoxy)benzene (134-TGAPB). [Figure 5] 1H (image a) and 13C (image b) nuclear magnetic resonance spectra for N,N,N,N-tetraglycidyl 1,3-bis(3-aminophenoxy)benzene (133-TGAPB). [Figure 6] High-performance liquid chromatogram showing resolution times for components in the synthesis of N,N,N,N-tetraglycidyl 1,3-bis(3-aminophenoxy)benzene (133-TGAPB). [Figure 7] 1H (image a) and 13C (image b) nuclear magnetic resonance spectra for 1,3-bis(3-glycidyloxyphenoxy)benzene. [Figure 8] High-performance liquid chromatogram showing resolution times for components in the synthesis of 1,3-bis(3-glycidyloxyphenoxy)benzene. [Figure 9] 1H (image a) and 13C (image b) nuclear magnetic resonance spectra for 1,4-bis(4-glycidyloxyphenoxy)benzene. [Figure 10]High-performance liquid chromatogram showing resolution times for components in the synthesis of 1,4-bis(4-glycidyloxyphenoxy)benzene. [Figure 11] Differential scanning chromatogram for purified 1,4-bis(4-glycidyloxyphenoxy)benzene. [Figure 12] High-performance liquid chromatograms showing the resolution times for isomeric products produced during the synthesis of bis(4-hydroxyphenoxy)-m-xylene, where a) indicates phenol, b) indicates the 4,4 isomer, c) indicates the 2,4 isomer, d) indicates the 2,2 isomer, and e) indicates oligomers. [Figure 13] H Nuclear Magnetic Resonance spectrum for bis-hydroxyphenyl-m-xylene, where a) represents two OH groups, b) represents twelve aromatic C—H groups, c) represents four aliphatic C—H groups, and d) represents dimethyl sulfoxide (DMSO). [Figure 14] High-performance liquid chromatograms showing the resolution times for isomeric products produced during the synthesis of bis(4-hydroxyphenoxy)-p-xylene, where a) indicates phenol, b) indicates the 4,4 isomer, c) indicates the 2,4 isomer, d) indicates the 2,2 isomer, and e) indicates oligomers. [Figure 15] H Nuclear Magnetic Resonance spectrum for bis-hydroxyphenyl-p-xylene, where a) represents two OH groups, b) represents twelve aromatic C—H groups, c) represents four aliphatic C—H groups, and d) represents dimethyl sulfoxide (DMSO). [Figure 16] Plot of the respective concentrations of different isomeric, phenolic, and oligomeric species during the synthesis of bis-hydroxyphenyl-p-xylene. [Figure 17]Dynamic mechanical thermal analysis (DMTA) spectra of diglycidyl ether of bisphenol A (BisA), diglycidyl ether of bisphenol F (BisF), and 1,4-bis(4-glycidyl ether phenoxy)benzene (144BGOPB) networks cured with a) 1,3-bis(3-aminobenzoyl)benzene (133BABB), b) 1,3-bis(4-aminobenzoyl)benzene (134BABB), and c) 1,4-bis(4-aminobenzoyl)benzene (144BABB). [Figure 18] a) Flexural modulus, b) strength, and c) fracture displacement for BisA, BisF, and 144BGOPB networks cured with 133BABB, 134BABB, and 144BABB. [Figure 19] Methyl ethyl ketone (MEK) penetration as a function of time for 133, 134, and 144BABB networks cured with a) BisA, b) BisF, and c) 144BGOPB. [Figure 20] DMTA tan delta traces showing the change in Tg for various epoxy resins after curing with a) 44DDS and b) MDA. Curing was done at 150°C for 12 hours and post-cured at 177°C for 3 hours. [Figure 21] DMTA spectra of BGOPpX / 44DDS cured networks after curing at various post-cure temperatures. [Figure 22] 44 Modulus plot of post-cured systems incorporating DDS and MDA curatives. [Figure 23] 44 Plots of a) yield strain and b) yield stress for systems post-cured with both DDS and MDA hardeners. [Figure 24] 44 Plot of solvent penetration as a function of time using MEK at room temperature for networks cured with DDS and MDA hardeners. [Figure 25] Comparison of tan δ spectra of 144-BGOPB and 133-BGOPB epoxy resins with BisF cured with 44DDS and 33DDS. [Figure 26]Compressive strength is shown directly versus strain for 144-BGOPB and 133-BGOPB cured networks compared to BisF cured with 44DDS and 33DDS. DETAILED DESCRIPTION OF THE INVENTION

[0027] In the present disclosure, we have developed a curable epoxy resin formulation containing a compound having three aromatic rings linked together by ether, carbonyl, or methylene groups and end capped with two or four epoxide groups. The aromatic structure provides strength, while the ether, carbonyl, or methylene bridging groups allow any mechanical energy to be dissipated for rotational motion and improve the strain capacity of the cured epoxy resin. Furthermore, the epoxy groups incorporated into the compounds defined herein allow for crosslinking within the polymer network.

[0028] The curable epoxy resins and formulations thereof described herein have been developed for the possible manufacture of composites. One objective of this disclosure is to develop curable epoxy resin formulations with improved strain properties to improve composite performance.

[0029] The compounds, composites, methods and uses defined herein are described in more detail hereinafter.

[0030] For the definitions provided herein, the defined terms and phrases include the meanings given unless specifically stated otherwise or implied from the context. Unless expressly stated otherwise or clear from the context, the following terms and phrases do not exclude the meanings that these terms or phrases have as used by one of ordinary skill in the art. These definitions are provided merely to aid in illustrating particular examples and are not intended to limit the claims, which are limited only by the scope of the claims. Further, unless otherwise required by context, singular terms shall include the plural and plural terms shall include the singular.

[0031] Throughout this specification, various aspects and elements of the invention may be presented in ranges. These ranges are included for convenience and should not be construed as inflexible limitations on the scope of the disclosure. Accordingly, unless otherwise indicated, descriptions of ranges should be construed as including all possible subranges specifically disclosed, as well as individual numerical values ​​within that range. For example, descriptions of a range of 1 to 5 should be construed as including specifically disclosed subranges, such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 5, 3 to 5, etc., as well as individual numerical values ​​and fractions (except where required to be integers) within the stated range, such as 1, 2, 3, 4, 5, 5.5, and 6. This is true regardless of the broadness of the disclosed range. Where specific values ​​are required, these values ​​are provided herein. term

[0032] Throughout this specification the word "comprise" or its variations "comprises" or "comprising" should be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of other elements, integers or steps, or groups of elements, integers or steps.

[0033] Throughout this specification, the term "consisting essentially of" is intended to exclude elements that materially affect the properties of the claimed composition, but may include elements that do not materially affect the properties. Epoxide-containing compounds

[0034] Disclosed herein are compounds of formula 1: TIFF0007772508000020.tif28170In formula, X 1 are each the same and are selected from O, CH2, and C(O); R 1 are hydrogen, and R 2 are each selected from an epoxide group, or R 2 are hydrogen, and R 1 are each selected from epoxide groups.

[0035] Also disclosed herein is a compound of Formula 2: TIFF0007772508000021.tif31170In formula, X 2 are each the same and are selected from O, CH2, and C(O); R 1 are hydrogen, and R 2 are each selected from an epoxide group, or R 2 are hydrogen, and R 1 are each selected from epoxide groups.

[0036] Also disclosed herein is a compound of formula 1a: TIFF0007772508000022.tif26170 formula, X 1 are each the same and are selected from O, CH2, and C(O); R 2 are each selected from epoxide groups.

[0037] Also disclosed herein is a compound of formula 1b: TIFF0007772508000023.tif27170In formula, X 1 are each the same and are selected from O, CH2, and C(O); R 1 are each selected from epoxide groups.

[0038] Also disclosed herein is a compound of formula 2a: TIFF0007772508000024.tif30170In formula, X 2 are each the same and are selected from O, CH2, and C(O); R 1 are each selected from epoxide groups.

[0039] Also disclosed herein is a compound of formula 2b: TIFF0007772508000025.tif22170 formula, X 2 are each the same and are selected from O, CH2, and C(O); R 2 are each selected from epoxide groups. Substituent X 1 , X 2 , R 1 and R 2

[0040] In the compound of any of formulas 1, 1a or 1b, X 1 can be O, CH2 or C(O).

[0041] In one example, X 1 is O. In another example, X 1 is C(O). In another example, X 1 is CH2.

[0042] In the compound of any of formulas 2, 2a or 2b, X 2 can be O, CH2 or C(O).

[0043] In one example, X2 is O. In another example, X 2 is C(O). In another example, X 2 is CH2.

[0044] In another example, X 1 are each the same and selected from O and C(O); X 2 are the same and are selected from C(O).

[0045] In the compound of any of formulas 1, 1b, 2 or 2a, R 1 can be hydrogen or an epoxide group.

[0046] In the compound of any of formulas 1, 1a, 2 or 2b, R 2 can be hydrogen or an epoxide group.

[0047] In one example, R 1 are hydrogen, and R 2 are each selected from epoxide groups.

[0048] In one example, R 2 are hydrogen, and R 1 are each selected from epoxide groups. Epoxide group

[0049] For compounds of formula 1, 1a or 1b, the epoxide group can be selected from the following: TIFF0007772508000026.tif18170 and TIFF0007772508000027.tif32170

[0050] For compounds of formula 2, 2a or 2b, the epoxide group can be selected from: TIFF0007772508000028.tif21170 and TIFF0007772508000029.tif33170

[0051] In one example, R 1 but, The file is TIFF0007772508000030.tif21170.

[0052] In another example, R 1 but, The file is TIFF0007772508000031.tif32170.

[0053] In one example, R 2 but, The file is TIFF0007772508000032.tif20170.

[0054] In yet another example, R 2 but, The file is TIFF0007772508000033.tif32170.

[0055] In one example, X 1 When is O, the epoxide group is TIFF0007772508000034.tif19170. In another example, X 1 When is O, the epoxide group is The file is TIFF0007772508000035.tif31170.

[0056] In one example, X 2 When is O, the epoxide group is TIFF0007772508000036.tif20170. In another example, X 2 When is O, the epoxide group is The file is TIFF0007772508000037.tif32170.

[0057] In one example, X 1 is CH2, the epoxide group is TIFF0007772508000038.tif20170. In another example, X 1 is CH2, the epoxide group is The file is TIFF0007772508000039.tif32170.

[0058] In one example, X 2 is CH2, the epoxide group is TIFF0007772508000040.tif20170. In another example, X 2 is CH2, the epoxide group is The file is TIFF0007772508000041.tif33170.

[0059] In one example, X 1 When is C(O), the epoxide group is TIFF0007772508000042.tif20170. In another example, X 1 When is C(O), the epoxide group is The file is TIFF0007772508000043.tif32170.

[0060] In one example, X 2 When is C(O), the epoxide group is TIFF0007772508000044.tif18170. In another example, X 2 When is C(O), the epoxide group is The file is TIFF0007772508000045.tif32170.

[0061] In one example, the compound of Formula 1 or Formula 2 can be selected from any of the following: TIFF0007772508000046.tif35170 or TIFF0007772508000047.tif34170 or TIFF0007772508000048.tif27170 or TIFF0007772508000049.tif27170

[0062] In one example, the compound of Formula 1 or Formula 2 can be selected from any of the following: TIFF0007772508000050.tif37170 or TIFF0007772508000051.tif37170 or TIFF0007772508000052.tif29170 or TIFF0007772508000053.tif35170

[0063] In one example, the compound of Formula 1 or Formula 2 can be selected from any of the following: TIFF0007772508000054.tif57170 or TIFF0007772508000055.tif57170 or TIFF0007772508000056.tif40170 or TIFF0007772508000057.tif40170

[0064] In one example, the compound of Formula 1 or Formula 2 can be selected from any of the following: TIFF0007772508000058.tif57170 or TIFF0007772508000059.tif58170 or TIFF0007772508000060.tif40170 or TIFF0007772508000061.tif47170

[0065] In one example, the compound of Formula 1 or Formula 2 can be selected from any of the following: TIFF0007772508000062.tif34170 or TIFF0007772508000063.tif34170 or TIFF0007772508000064.tif28170 or TIFF0007772508000065.tif28170

[0066] In one example, the compound of Formula 1 or Formula 2 can be selected from any of the following: TIFF0007772508000066.tif56170 or TIFF0007772508000067.tif58170 or TIFF0007772508000068.tif39170 or TIFF0007772508000069.tif41170Curable epoxy resin preparation

[0067] Disclosed herein are curable epoxy resin formulations comprising compounds of formula 1, 1a, 1b, 2, 2a, or 2b, or mixtures thereof.

[0068] Disclosed herein are curable epoxy resin formulations comprising a compound of Formula 1, 1a, 1b, 2, 2a, or 2b, or mixtures thereof, and a curing agent.

[0069] Also disclosed herein are curable epoxy resin formulations consisting of, or consisting essentially of, any of the compounds of formula 1, 1a, 1b, 2, 2a, or 2b, or mixtures thereof, and a curing agent.

[0070] In one example, a curable epoxy resin formulation includes a compound of Formula 1.

[0071] In one example, a curable epoxy resin formulation includes a compound of Formula 2.

[0072] Disclosed herein is a curable epoxy resin formulation comprising an epoxy resin and a curing agent, wherein the epoxy resin is a compound of formula 3: Contains TIFF0007772508000070.tif26170, During the ceremony, X are each the same and are selected from O, CH2, and C(O); Each R is the same and is an epoxide group.

[0073] Disclosed herein is a curable epoxy resin formulation consisting essentially of an epoxy resin and a curing agent, wherein the epoxy resin is a compound of formula 3: Contains TIFF0007772508000071.tif25170, During the ceremony, X are each the same and are selected from O, CH2, and C(O); Each R is the same and is an epoxide group.

[0074] Disclosed herein is a curable epoxy resin formulation comprising an epoxy resin and a curing agent, wherein the epoxy resin is a compound of formula 3: TIFF0007772508000072.tif26170, During the ceremony, X are each the same and are selected from O, CH2, and C(O); R are each the same and are an epoxide group; and The curing agent is a diamine curing agent of formula 4: Contains TIFF0007772508000073.tif26170, wherein each Y is the same and is selected from O, CH2, and C(O).

[0075] Disclosed herein is a curable epoxy resin formulation consisting of, or consisting essentially of, an epoxy resin and a curing agent, wherein the epoxy resin is a compound of formula 3: Contains TIFF0007772508000074.tif25170, During the ceremony, X are each the same and are selected from O, CH2, and C(O); R are each the same and are an epoxide group; and The curing agent is a diamine curing agent of formula 4: Contains TIFF0007772508000075.tif27170, wherein each Y is the same and is selected from O, CH2, and C(O).

[0076] In Formula 3, the two substituents X may be attached to the central benzene ring at ortho, meta, or para positions relative to each other. In one example, the two substituents X are at the 1- and 2-positions on the central benzene ring (ortho substitution). In another example, the two substituents X are at the 1- and 3-positions on the central benzene ring (meta substitution). In yet another example, the two substituents X are at the 1- and 4-positions on the central benzene ring (para substitution).

[0077] wherein the compound of formula 3 is a compound of formula 3a: TIFF0007772508000076.tif26170, During the ceremony, X are each the same and are selected from O, CH2, and C(O); Each R is the same and is an epoxide group.

[0078] wherein the compound of formula 3 is a compound of formula 3a-i: TIFF0007772508000077.tif27170, During the ceremony, X are each the same and are selected from O, CH2, and C(O); Each R is the same and is an epoxide group.

[0079] wherein the compound of formula 3 is a compound of formula 3a-ii: TIFF0007772508000078.tif24170, During the ceremony, X are each the same and are selected from O, CH2, and C(O); Each R is the same and is an epoxide group.

[0080] wherein the compound of formula 3 is a compound of formula 3b: TIFF0007772508000079.tif25170, During the ceremony, X are each the same and are selected from O, CH2, and C(O); Each R is the same and is an epoxide group.

[0081] wherein the compound of formula 3 is a compound of formula 3b-i: TIFF0007772508000080.tif31170, During the ceremony, X are each the same and are selected from O, CH2, and C(O); Each R is the same and is an epoxide group.

[0082] wherein the compound of formula 3 is a compound of formula 3b-ii: TIFF0007772508000081.tif21170, During the ceremony, X are each the same and are selected from O, CH2, and C(O); Each R is the same and is an epoxide group.

[0083] In any of the examples of the curable epoxy resin formulations described above, the epoxy resin may consist of or consist essentially of compounds of Formula 3, or in any of the examples described herein, may optionally include a curing agent.

[0084] In another example of any of the curable epoxy resin formulations above, or any examples thereof described herein, the curing agent present in the curable epoxy resin formulation may consist of or consist essentially of a diamine curing agent of Formula 4.

[0085] The compound of formula 3 may be selected from the compounds of formula 1 as defined herein. Alternatively, the compound of formula 3 may be selected from the compounds of formula 1a or formula 1b as defined herein.

[0086] The compound of formula 3 may be selected from the compounds of formula 2 as defined herein. Alternatively, the compound of formula 3 may be selected from the compounds of formula 2a or formula 2b as defined herein.

[0087] The compound of formula 3 may be selected from compounds of formula 3a as defined herein. Alternatively, the compound of formula 3 may be selected from compounds of formula 3a-i or formula 3a-ii as defined herein.

[0088] The compound of formula 3 may be selected from compounds of formula 3b as defined herein. Alternatively, the compound of formula 3 may be selected from compounds of formula 3b-i or formula 3b-ii as defined herein. Substituents R and X

[0089] For compounds of formula 3, X can be O, CH2, or C(O).

[0090] In one example, X is O. In another example, X is C(O). In yet another example, X is CH.

[0091] In compounds of Formula 3, each R can be an epoxide group selected from the following: TIFF0007772508000082.tif19170 and TIFF0007772508000083.tif31170

[0092] In one example, the substituent R in the compound of formula 3 is The file is TIFF0007772508000084.tif19170.

[0093] In one example, the substituent R in the compound of formula 3 is The file is TIFF0007772508000085.tif32170.

[0094] In one example, when X is O, the substituent R is TIFF0007772508000086.tif20170. In another example, when X is O, the substituent R is The file is TIFF0007772508000087.tif31170.

[0095] In one example, when X is CH2, the substituent R is TIFF0007772508000088.tif19170. In another example, when X is CH2, the substituent R is The file is TIFF0007772508000089.tif31170.

[0096] In one example, when X is C(O), the substituent R is TIFF0007772508000090.tif19170. In another example, when X is C(O), the substituent R is The file is TIFF0007772508000091.tif31170.

[0097] In one example, the compound of formula 3 can be selected from any of the following: TIFF0007772508000092.tif33170 or TIFF0007772508000093.tif34170 or TIFF0007772508000094.tif27170 or TIFF0007772508000095.tif27170

[0098] In one example, the compound of formula 3 can be selected from any of the following: TIFF0007772508000096.tif36170 or TIFF0007772508000097.tif37170 or TIFF0007772508000098.tif28170 or TIFF0007772508000099.tif37170

[0099] In one example, the compound of formula 3 can be selected from any of the following: TIFF0007772508000100.tif57170 or TIFF0007772508000101.tif57170 or TIFF0007772508000102.tif40170 or TIFF0007772508000103.tif40170

[0100] In one example, the compound of formula 3 can be selected from any of the following: TIFF0007772508000104.tif57170 or TIFF0007772508000105.tif57170 or TIFF0007772508000106.tif39170 or TIFF0007772508000107.tif47170

[0101] In one example, the compound of formula 3 can be selected from any of the following: TIFF0007772508000108.tif34170 or TIFF0007772508000109.tif34170 or TIFF0007772508000110.tif27170 or TIFF0007772508000111.tif27170

[0102] In one example, the compound of formula 3 can be selected from any of the following: TIFF0007772508000112.tif57170 or TIFF0007772508000113.tif57170 or TIFF0007772508000114.tif39170 or TIFF0007772508000115.tif40170 Hardener

[0103] Curing agents such as amines, imidazoles, anhydrides, phenols, and mercaptans are known to those skilled in the art and can be used in the compositions described herein.

[0104] Here, the ratio of the curing agent to the compound of Formula 1, Formula 2, or Formula 3 can vary from a balanced stoichiometry of about 1.0:1.0 to a stoichiometry of about 0.6:1.0. For example, the ratio of the curing agent to the compound of Formula 1, Formula 2, or Formula 3 can be about 1.0:1.0, about 0.95:1.0, about 0.90:1.0, about 0.85:1.0, about 0.75:1.0, about 0.70:1.0, about 0.65:1.0, or about 0.6:1.0. In one example, the ratio is 0.7:1.0.

[0105] For the curable epoxy resin formulations disclosed herein, the curing agent can be an amine.

[0106] In one example, the curing agent is an aliphatic amine, a cycloaliphatic amine, or an aromatic amine. Examples of possible amine curing agents include, but are not limited to, N-aminoethylpiperazine, menthanediamine, isophoronediamine, m-xylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, 3,3'-sulfonyldianiline, 4,4'-sulfonyldianiline, 4,4'-methylenedianiline, 4,4'-oxydianiline, 4,4'-methylenebis(2-ethylaniline), 3,3'-( (2,2-dimethylpropane-1,3-diyl)bis(oxy))dianiline, 4,4'-(1,4-phenylenebis-(propane-2,2-diyl))dianiline, 3-(4-(4-aminobenzyl)-benzyl)aniline, 4,4'-(1,4-phenylenebis(propane-2,2-diyl))bis(2,6-dimethylaniline), 4,4'-(1,4-phenylenebis(oxy))-dianiline, 3,3'-((propane-2,2-diylbis-(4,1phenylene) 4,4'-(1,4-phenylenedi-sulfonyl)dianiline, 4,4'-(pentane-1,5-diylbis-(oxy))dianiline, 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))dianiline, 4,4'-(1,3- Phenylenebis-(propane-2,2-diyl))bis(2,6-diisopropylaniline), 4,4'-(1,3-phenylenebis-(propane-2,2-diyl))dianiline, 4,4'-((sulfonylbis(4,1-phenylene))bis(oxy))dianiline, 4,4'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))dianiline, 4,4'-disulfanediyldianiline, and 4,4'-disulfanediyldianiline.

[0107] In one example, the curing agent is an amine, where the ratio of the amine to the compound of Formula 1, Formula 2, or Formula 3 can vary from a balanced stoichiometry of about 1.0:1.0 to a stoichiometry of about 0.6:1.0. For example, the ratio of the amine curing agent to the compound of Formula 1, Formula 2, or Formula 3 can be about 1.0:1.0, about 0.95:1.0, about 0.90:1.0, about 0.85:1.0, about 0.75:1.0, about 0.70:1.0, about 0.65:1.0, or about 0.6:1.0. In one example, the ratio is 0.7:1.0.

[0108] The curing agent is a diamine curing agent of formula 4: TIFF0007772508000116.tif26170, wherein each Y is the same and is selected from O, CH2, and C(O).

[0109] In Formula 4, the two substituents Y may be attached to the central benzene ring at ortho, meta, or para positions relative to each other. In one example, the two substituents Y are at the 1- and 2-positions on the central benzene ring (ortho substitution). In another example, the two substituents Y are at the 1- and 3-positions on the central benzene ring (meta substitution). In yet another example, the two substituents Y are at the 1- and 4-positions on the central benzene ring (para substitution).

[0110] The curing agent is a diamine curing agent of formula 4a: TIFF0007772508000117.tif26170, wherein each Y is the same and is selected from O, CH2, and C(O).

[0111] The curing agent is a diamine curing agent of formula 4b: TIFF0007772508000118.tif27170, wherein each Y is the same and is selected from O, CH2, and C(O).

[0112] The curing agent is a diamine curing agent of formula 4c: TIFF0007772508000119.tif31170, wherein each Y is the same and is selected from O, CH2, and C(O).

[0113] The curing agent is a diamine curing agent of formula 4d: TIFF0007772508000120.tif21170, wherein each Y is the same and is selected from O, CH2, and C(O).

[0114] For compounds of formula 4, 4a, 4b, 4c, or 4d, Y can be O, CH2, or C(O).

[0115] In one example, Y is O. In another example, Y is C(O). In another example, Y is CH.

[0116] In one example, the compound of formula 4 can be selected from any of the following: TIFF0007772508000121.tif30170 or TIFF0007772508000122.tif32170 or TIFF0007772508000123.tif39170 or TIFF0007772508000124.tif32170 or TIFF0007772508000125.tif39170 or TIFF0007772508000126.tif39170

[0117] In one example, the compound of formula 4 can be selected from any of the following: TIFF0007772508000127.tif22170 or TIFF0007772508000128.tif23170 or TIFF0007772508000129.tif24170 or TIFF0007772508000130.tif23170 or TIFF0007772508000131.tif24170 or TIFF0007772508000132.tif24170

[0118] In one example, the compound of formula 4 can be selected from any of the following: TIFF0007772508000133.tif23170 or TIFF0007772508000134.tif23170 or TIFF0007772508000135.tif23170 or TIFF0007772508000136.tif22170 or TIFF0007772508000137.tif23170 or TIFF0007772508000138.tif24168

[0119] Here, the ratio of the curing agent of Formula 4 to the compound of Formula 1, Formula 2, or Formula 3 can vary from a balanced stoichiometry of about 1.0:1.0 to a stoichiometry of about 0.6:1.0. For example, the ratio of the curing agent of Formula 4 to the compound of Formula 1, Formula 2, or Formula 3 can be about 1.0:1.0, about 0.95:1.0, about 0.90:1.0, about 0.85:1.0, about 0.75:1.0, about 0.70:1.0, about 0.65:1.0, or about 0.6:1.0. In one example, the ratio is 0.7:1.0.

[0120] The curable epoxy resin formulations described herein can further include one or more additives or one or more additional epoxy resins, each known to those skilled in the art. These include diglycidyl ether of bisphenol A, F epoxy resin, triglycidyl p-aminophenol epoxy resin, and tetraglycidylamine epoxy resin. For example, the curable epoxy resin formulation can further include 4,4'-methylenediphenolol (bisphenol F). Bisphenol F can be added as a liquid carrier for producing prepreg materials.

[0121] Examples of additives include, but are not limited to: functional additives that can be added to curable epoxy resin formulations to impart properties that affect the mechanical, rheological, electrical, optical, chemical, flame retardant, and / or thermal properties of the cured or uncured epoxy resin formulation. Examples of additives include, but are not limited to, flame retardants, ultraviolet (UV) stabilizers, and inorganic fillers.

[0122] Additives such as rheology modifiers, fillers, heat or UV stabilizers, flame retardants, lubricants, surfactants, etc. a) film formers, such as esters of dicarboxylic acids (e.g., Lusolvan FBH, BASF), and glycol ethers (e.g., Dowanol, Dow), and b) surfactants, such as fatty acid derivatives (e.g. Bermadol SPS 2543, Akzo), and quaternary ammonium salts may include:

[0123] In one example, the curable epoxy resin formulation is additive-free. composite material

[0124] Disclosed herein are impregnated fiber reinforced materials comprising fibers impregnated with the curable epoxy resin formulations defined herein.

[0125] The fiber reinforcement material may include, but is not limited to, fibers selected from fibers composed of glass, carbon, or aramid (aromatic polyamide).

[0126] In one example, the impregnated fiber reinforcement material comprises any of the compounds of formula 1, 1a, 1b, 2, 2a or 2b, or mixtures thereof, and a curing agent.

[0127] In one example, the impregnated fiber reinforcement material includes a compound of Formula 3 and a curative, for example, the curative is any of Formulas 4, 4a, 4b, 4c, or 4d, or a mixture thereof.

[0128] Also disclosed herein are composites comprising a fibrous material within a matrix of cured epoxy resin, wherein the cured epoxy resin is formed from a curable epoxy resin formulation as defined herein.

[0129] In one example, the composite comprises any of the compounds of formula 1, 1a, 1b, 2, 2a or 2b, or mixtures thereof, and a curing agent.

[0130] In one example, the composite comprises a compound of formula 3 and a curing agent of any of formulas 4, 4a, 4b, 4c or 4d, or a mixture thereof.

[0131] Also disclosed herein is a method of forming an impregnated fiber reinforced material, the method comprising the steps of: a) (i) a curable epoxy resin formulation as defined herein, and (ii) textile materials; and b) (i) combining the resin formulation of step (a) with the fibrous material of step (a) and (ii) subjecting the material to an elevated temperature to cure the material, thereby forming an impregnated fibrous reinforced material. It includes:

[0132] The fibrous materials can include fibers composed of glass fibers, carbon, and aramid (aromatic polyamide) fibers.

[0133] Further disclosed herein is the use of any of the compounds of Formula 1, 1a, 1b, 2, 2a, 2b, or mixtures thereof as a curable epoxy resin or in the preparation of a curable epoxy resin formulation, which can be used to prepare impregnated fiber-reinforced materials or composites thereof.

[0134] Also disclosed herein is a method for preparing a compound of Formula 8, the method comprising the steps of: i) reacting a compound of formula 5 with a compound of formula 6 in the presence of a catalyst to form a compound of formula 7, wherein P is a protecting group, M is a metal, and LG is a leaving group: ii) further reacting the compound of formula 7 with an acid catalyst to form a compound of formula 8: It contains TIFF0007772508000140.tif27170.

[0135] Also disclosed herein is a method for preparing a compound of formula 10, comprising reacting a dihydroxy compound of formula 8 with a halogenated epoxy compound of formula 9, to form a compound of formula 10: TIFF0007772508000141.tif65170A method for preparing the compound of formula 10.

[0136] For Formula 9, the alkyl group is C 1~3 For example, the compound of formula 9 can be epichlorohydrin.

[0137] Protecting groups (which may be temporary or permanent) are known to those skilled in the art, and methods for introducing and removing protecting groups are described in standard texts, such as Protective Groups in Organic Synthesis, T.W. Greene and P. Wutz, John Wiley and Sons, 2nd Edition (1991), the contents of which are incorporated by reference. In formulas 5 and 7, the hydroxy group can be protected, for example, with groups such as acetyl, benzoyl, benzyl, methoxymethyl ether, methoxytrityl, methylthiomethyl ether, pivaloyl, tetrahydropyranyl, tetrahydrofuran, trityl, silyl ether (including trimethylsilyl, tert-butyldimethylsilyl, triisopropylsilyloxymethyl, and triisopropylsilyl ether), alkyl ether (e.g., methyl ether), and ethoxyethyl ether protecting groups. For example, the protecting group "P" for formulas 5 and 7 can be an alkyl group, such as a methyl group.

[0138] Examples of metals "M" include, but are not limited to, potassium or sodium.

[0139] The term "leaving group" or "LG," as will be understood by those skilled in the art, refers to a fragment of a molecule that is displaced when a stable species takes the leaving group along with the bonding electrons. Leaving groups are used in organic chemistry to facilitate covalent bonding between two molecules. The term "leaving group" or "LG" includes, but is not limited to, halo groups (e.g., iodo, bromo, and chloro), or sulfonate ester groups, such as mesylate, tosylate, osylate, nosylate, or besylate. [Example]

[0140] raw materials Certain chemicals referred to in this specification (including the examples below) can be obtained from the sources set forth in Table 1. TIFF0007772508000142.tif110170Device

[0141] Nuclear Magnetic Resonance (NMR) Spectroscopy

[0142] NMR experiments were performed using a Bruker Avance 400 NMR spectrometer (400.13 MHz) 1 H frequency) and a 5 mm triple-resonance broadband probe (BB / 2 H- 1 H / 19 F), or a 5mm inverse broadband probe ( 1 H / 2 H-BB). Solutions for NMR analysis were prepared by dissolving the material in 0.6 ml of deuterated chloroform (CDCl). NMR experiments were performed with the sample maintained at 25 ± 0.1 °C. 1 Chemical shifts for the H experiment are referenced to the residual solvent signal (CHCl3, δ 7.24 ppm), 13Chemical shifts for C are referenced to the solvent signal (CDCl3, δ 77.23 ppm).

[0143] High-performance liquid chromatography (HPLC)

[0144] High-performance liquid chromatography was performed using a Waters 2695 Separation Module and a Waters 2996 Photodiode Array (PDA) or 2414 infrared (IR) detector. The column was an Alltima C18 150 x 4.6 mm reversed-phase column. A flow rate of 1.00 mL / min was used, and the mobile phase was changed from 55% acetonitrile (CAN / 45% HO) to 65% acetonitrile (CAN) / 35% HO.

[0145] Electrospray ionization (ESI) mass spectrometry (MS)

[0146] Mass spectral analysis was performed on a Thermo Scientific Q Exactive mass spectrometer equipped with a HESI-II ion source. Positive and / or negative ion electrospray mass spectra were recorded with the appropriate mass range set to 140,000 mass resolution. The probe was used with a solvent flow rate of 0.3 ml / min. The nitrogen nebulizing / desolvation gas used for evaporation was heated to 350°C in these experiments. The sheath gas flow rate was set to 35 and the auxiliary gas flow rate was set to 25 (both arbitrary units). The spray voltage was 3.0 kV and the capillary temperature was 300°C.

[0147] Differential Scanning Calorimetry (DSC)

[0148] Differential scanning calorimetry (DSC) was performed using a Mettler DSC821 eDSC was performed in dynamic mode using approximately 5-10 g samples. The samples were placed in sealed alumina crucibles and transferred to a furnace under a nitrogen blanket. Both cured and uncured samples were heated from 50°C to 300°C at a rate of 10°C / min to identify the best cure temperature, gain an initial understanding of reactivity, identify the glass transition temperature of the network, and obtain a rough understanding of the extent of cure. Abbreviation

[0149] Table 2 provides a list of abbreviations used herein. TIFF0007772508000143.tif104170 Example 1: Synthesis of N,N,N,N-tetraglycidyl 1,4-bis-(4-aminophenoxy)benzene (144-TGAPB) TIFF0007772508000144.tif67170

[0150] The materials used in the synthesis of 144-TGAPB are as follows: 1,4-bis(4-aminophenoxy)benzene (TPE-Q) 5.84g (2.00x10 -2 moles); Epichlorohydrin (27.75g, 3.00×10 -1 moles) Dichloroethane (50ml) Lanthanum nitrate hexahydrate (55 mg) NaOH (4.00 g, 1.00 × 10 -1 moles), and Isopropanol (30 ml).

[0151] TPE-Q, epichlorohydrin, dichloroethane, and lanthanum nitrate (dissolved in 2 ml of isopropanol) were placed in a 250 ml three-neck round-bottom flask. The mixture was refluxed in an oil bath for 90 minutes (oil bath temperature approximately 100°C, reaction flask temperature approximately 87°C). After 980 minutes, the oil bath temperature was reduced to approximately 80°C, and the reaction flask temperature was reduced to approximately 70-75°C.

[0152] The NaOH was ground to a coarse powder and suspended in isopropanol. This suspension was slowly added (by spoon) to the TPE-Q / epichlorohydrin solution in small portions over 30 minutes. After addition was complete, the mixture was stirred at 70-75°C for an additional 15 minutes and then allowed to cool to room temperature.

[0153] The salt was filtered, and the solvent and excess epichlorohydrin were removed by rotary evaporation (oil pump) at about 50°C for 1-2 hours. The residue was then suspended in methanol (50 ml). The solid product was filtered, then resuspended in methanol (50 ml) and filtered again. The white solid product was dried overnight in a vacuum oven at about 70°C. The yield was 9.70 g (94%). This product was purified by NMR ( 1 H and 13 C) (Figure 1, images a) and b) respectively), high performance liquid chromatography (HPLC) (Figure 2), mass spectrometry (MS), differential scanning calorimetry (DSC), and thin layer chromatography (TLC).

[0154] TLC (silica plate, solvent: 2% v / v MeOH in DCM)-R f The value is approximately 0.8.

[0155] MS(ESI) m / z 516.

[0156] HPLC: HPLC column: Altima C18, mobile phase: 55% acetonitrile / water; single peak at retention time (RT) of 17.267 min; 95.7% (Figure 2). Example 2: Synthesis of N,N,N,N-tetraglycidyl 1,3-bis-(4-aminophenoxy)benzene (134-TGAPB) TIFF0007772508000145.tif47170

[0157] The materials used in the synthesis of 134-TGAPB are as follows: 1,3-bis(4-aminophenoxy)benzene (TPE-R) 5.84g (2.00x10 -2moles); Epichlorohydrin (27.75g, 3.00×10 -1 moles) Dichloroethane (50ml) Lanthanum nitrate hexahydrate (55 mg) NaOH (4.0 g, 1.00 × 10 -1 moles), and Isopropanol (30 ml).

[0158] TPE-R, epichlorohydrin, dichloroethane, and lanthanum nitrate (dissolved in 2 ml of isopropanol) were placed in a 250 ml three-neck round-bottom flask. The mixture was refluxed in an oil bath for 90 minutes (oil bath temperature approximately 100°C, reaction flask temperature approximately 87°C). After 90 minutes, the oil bath temperature was reduced to approximately 80°C, and the reaction flask temperature was reduced to approximately 70-75°C.

[0159] NaOH was ground to a coarse powder and suspended in isopropanol. This suspension was slowly added (using a spoon) to the TPE-R / epichlorohydrin solution in small portions over 30 minutes. After the addition was complete, the mixture was stirred at 70-75°C for an additional 15 minutes. The solution was then allowed to cool to room temperature. The salt was filtered, and the solvent and excess epichlorohydrin were removed by rotary evaporation (oil pump) at approximately 50°C for 1-2 hours. The residue was dissolved in dichloromethane (50 ml), washed with water (50 ml), and dried over Na2SO4 (anhydrous). The Na2SO4 was then filtered off (through Celite), and the dichloromethane was removed. The product was a dark oil, yielding 9.90 g (96%). The oily product was characterized by NMR ( 1 H and 13 C, Figure 3, images a) and b) respectively, analyzed by HPLC (Figure 4), MS and TLC.

[0160] TLC (silica plate, solvent: 2% v / v MeOH in DCM), R f The value is approximately 0.7.

[0161] MS(ESI) m / z 516.

[0162] HPLC: HPLC column: Altima C18, mobile phase: 55% acetonitrile / water; single peak at RT of 18.73 min; 92.4% (Figure 4). Example 3: Synthesis of N,N,N,N-tetraglycidyl 1,3-bis-(3-aminophenoxy)benzene (133-TGAPB) TIFF0007772508000146.tif45170

[0163] The materials used for the synthesis of 133-TGAPB are as follows: 1,3-bis(3-aminophenoxy)benzene (133-APB) 5.84g (2.00x10 -2 moles); Epichlorohydrin (27.75g, 3.00×10 -1 moles) Dichloroethane (50ml) Lanthanum nitrate hexahydrate (55 mg) NaOH (4.0 g, 1.00 × 10 -1 moles), and Isopropanol (30 ml).

[0164] 133-APB, epichlorohydrin, dichloroethane, and lanthanum nitrate (dissolved in 2 mL of isopropanol) were placed in a 250 mL three-neck round-bottom flask. The mixture was refluxed in an oil bath for 90 minutes (oil bath temperature approximately 100°C, reaction flask temperature approximately 87°C). After 90 minutes, the oil bath temperature was reduced to approximately 80°C, and the reaction flask temperature was reduced to approximately 70-75°C.

[0165] NaOH was crushed to a coarse powder and then suspended in isopropanol. This suspension was slowly added in small portions (using a spoon) to the 133-APB / epichlorohydrin solution over 30 minutes. After the addition was complete, the mixture was stirred at 70-75°C for an additional 15 minutes and then allowed to cool to room temperature. The salt was filtered, and the solvent and excess epichlorohydrin were removed by rotary evaporation (oil pump) at approximately 50°C for 1-2 hours. The residue was dissolved in dichloromethane (50 ml), washed with water (50 ml), and dried over Na2SO4 (anhydrous). The Na2SO4 was filtered off (through Celite), and the dichloromethane was removed. The product was a yellow oil, and the yield was 9.90 g (96%). The oily product was characterized by NMR ( 1 H and 13 C, Figure 5, images a) and b) respectively, analyzed by HPLC (Figure 6), MS and TLC.

[0166] TLC (silica plate, solvent: 2% v / v MeOH in DCM), R f The value is approximately 0.85.

[0167] MS(ESI) m / z 516.

[0168] HPLC: HPLC column: Altima C18, mobile phase: 55% acetonitrile / water; single peak at RT of 18.56 min; 90.2% (Figure 6). Example 4: Synthesis of 1,3-bis-(3-glycidyloxyphenoxy)benzene (133-BGOPB) TIFF0007772508000147.tif35170Step 1: Synthesis of 1,3-bis-(3-methoxyphenoxy)benzene

[0169] This synthesis is a modification of the method published by L. Wang et al., Synthesis Communication, 30(2), 227-234, 2000, the contents of which are incorporated herein by reference. TIFF0007772508000148.tif40170

[0170] 3-Methoxyphenol (62.05g, 5.00×0 -1 mol) in KOH (30.85 g, 5.50 × 10 -1 A mixture of copper(II) chloride (1.25 g, 1.25 × 10 mol) dissolved in ethanol / toluene (75 ml / 150 ml) was added. The mixture was stirred and refluxed under a nitrogen atmosphere until the solid was completely dissolved. The solvent was removed first by distillation and then using a rotary evaporator. Copper(II) chloride (1.25 g, 1.25 × 10 mol) was added to the mixture. The mixture was stirred and refluxed under a nitrogen atmosphere until the solid was completely dissolved. The solvent was removed first by distillation and then using a rotary evaporator. -2 mol) and 1,3-dibromobenzene (59 g, 2.50 × 10 -1 (mol) was added to the residue and then stirred at 170-180°C for 16 hours. The next day, the reaction flask was warmed to approximately 50°C, and then ethanol (200 ml) and water (200 ml) were added to the mixture. The product was extracted with CHCl (250 ml × 2), washed separately with 5% aqueous NaOH solution (250 ml × 2), and finally with water (250 ml × 2). After drying over NaSO, the CHCl solvent was removed to give 46.9 g (58.2% yield) of a dark oil. NMR analysis confirmed this to be the expected product, which was ready for the next step. Step 2: Synthesis of 1,3-bis-(3-hydroxyphenoxy)benzene (133-BGOPB) TIFF0007772508000149.tif22170

[0171] 1,3-bis(3-methoxyphenoxy)benzene (46.89 g, 1.46 × 10 -1 A mixture of 1000 mol), glacial acetic acid (460 ml), and HBr (300 ml) was refluxed for 5 hours, after which the reaction mixture was allowed to cool to room temperature. The reaction mixture was then poured into water (5 L), and the product was extracted with 2 L of ether (500 ml x 4). The combined ether solution was then washed with water (750 ml x 2), dried over Na2SO4, and filtered. The ether was removed under vacuum, and the resulting product was a dark oil (40.0 g) (93% yield). NMR analysis confirmed the identity of the product, which was used in the next step. Step 3: Synthesis of 1,3-bis-(3-glycidyloxyphenoxy)benzene (133-BGOPB) TIFF0007772508000150.tif27170

[0172] The synthesis of epoxy resin was carried out using 1,3-bis(3-hydroxyphenoxy)benzene, epichlorohydrin (125.58 g, 1.36 mol), and isopropanol (57 g, 9.50 × 10 -1 The reaction was completed by mixing the two halves of the HCl solution together and heating at 70°C with stirring. The epoxy ring was closed by adding 100 ml of 15% (w / v) aqueous NaOH solution to the stirred solution in two stages. First, 8-9 ml was added dropwise over 5 minutes, and then the remaining 90 ml was added slowly over 10 minutes. After this time, the mixture was heated at 70-75°C for an additional 30 minutes and then allowed to cool to room temperature. The organic phase (lower phase containing the product) was separated from the aqueous phase (upper phase) and washed with water (250 ml x 2). The organic solution was then diluted with CHCl (200 ml), dried over NaSO, and filtered. The solvent was removed under vacuum, and the product was obtained as a dark oil. The product was purified by passing through a short SiO column using CHCl as the solvent. The pure product was obtained as a yellow oil (40 g, 72.6% yield). The epoxy equivalent weight of 133-BGOPB was found to be 239 mol / g.

[0173] The proton and carbon NMR spectra are shown in Figure 7, images a) and b), respectively. These spectra demonstrate that the product is clean and free of impurities. Each peak can be successfully assigned to the corresponding hydrogen or carbon atom, as shown in the inset. The integrals of the hydrogen peaks are in good agreement with those expected for the 133BGOPB molecule. This synthesis is clean and does not contain any readily detectable impurities. In addition, the HPLC chromatogram in Figure 8 shows the resolved components of 133BGOPB, providing clear evidence that this molecule is a pure, single-component epoxy resin. A 150 x 4.6 mm Altima C18 column was used for HPLC analysis. The mobile phase was run at a flow rate of 1.0 ml min -1 The solvent was 65% acetonitrile / water. Example 5: Synthesis of 1,4-bis-(4-glycidyloxyphenoxy)benzene (144-BGOPB) Step 1: Synthesis of 1,4-bis-(4-acetophenoxy)benzene

[0174] This synthesis utilizes a modification of the method published in GW Yeager et al., Synthesis, 1991, 63-68, the contents of which are incorporated herein by reference. TIFF0007772508000151.tif33170

[0175] Anhydrous K2CO3 (64.27g, 4.65×10 -1 mol) to 1,4-dihydroxybenzene (25.6 g, 2.33 × 10 -1 mol), 4-fluoroacetophenone (64.17 g, 4.65 × 10 -1The resulting mixture was refluxed overnight under nitrogen. The following day, the mixture was allowed to cool to room temperature and slowly poured into water (2.0 L). The product precipitated as a solid and was isolated from the solution by filtration. The product was suspended in water (2 x 1 L) and dried in a vacuum oven at 50-70 °C for 24 hours. The yield was 74 g (92%). NMR analysis confirmed this was the expected product and it was ready for the next step. Step 2: Synthesis of 1,4-bis-(4-acetoxyphenoxy)benzene TIFF0007772508000152.tif31170

[0176] 1,4-bis(4-acetophenoxy)benzene (69.2 g, 2.00 × 10 -1 A mixture of 1,2,3-trimethylsilyl methylpropional (107.5 g), m-chloroperoxybenzoic acid (107.5 g), and CHCl (500 mL) was stirred under reflux for 5 hours. The reaction mixture was then allowed to cool to room temperature, and the solid was filtered and washed with CHCl (200 mL). The combined organic phase was washed with saturated NaHSO (2 x 250 mL), then saturated NaHSO (2 x 250 mL), and finally with water (2 x 500 mL). The organic phase was dried over anhydrous NaSO, filtered, and the organic solvent was removed by rotary evaporation. The product formed as a yellow solid. The solid product was dried in a vacuum oven at 50 °C overnight. The yield was 64 g (84.6%). The product was confirmed by NMR and used in the next step. Step 3: Synthesis of 1,4-bis-(4-hydroxyphenoxy)benzene TIFF0007772508000153.tif25170

[0177] 1,4-bis(4-acetatophenoxy)benzene (63.75 g, 1.69 × 10 -1To a stirred solution of 100 mol of HCl in MeOH (700 ml) was added 0.5 M KOH / MeOH (85 ml) and heated to reflux for 1 hour. The solvent was then removed by rotary evaporation. The residue was suspended in water (800 ml) and acidified with concentrated HCl. The solid product was isolated from the solution by filtration, washed twice with water, and then dried in a vacuum oven at 70°C overnight. The yield was 46.5 g (93.8%). The product was confirmed by NMR and was ready for the next step. Step 4: Synthesis of 1,4-bis-(4-glycidyloxyphenoxy)benzene (144-BGOPB) TIFF0007772508000154.tif47170

[0178] 1,4-bis(4-hydroxyphenoxy)benzene (46.5g, 1.58×0 -1 mol), epichlorohydrin (146.4 g, 1.58 × 10 -1 mol) and isopropanol (66.4 g, 1.11 mol) were dissolved together in a round-bottom flask and heated with stirring at 70 °C. Following this, 115 mL of 15% (w / v) NaOH solution was added to the stirred solution in two stages. First, 10 mL was added dropwise over 5 minutes, and then the remaining 105 mL was added slowly over 10 minutes. After this time, the mixture was held at 70-75 °C for an additional 30 minutes and then allowed to cool to room temperature with continued stirring. The solid in the reaction flask was filtered and washed with water (250 mL x 2), then suspended in methanol (300 mL x 2), filtered again, and dried in a vacuum oven at 50 °C overnight. The product was again dissolved in CHCl (300 mL), and the very fine insoluble solid was filtered off. The CHCl was then removed by rotary evaporation. The yield was 52.0 g (81%). 1 H and 13 C NMR again provided evidence of a clean, expected product, and DSC showed a sharp melting point at approximately 133° C. The epoxy equivalent mass of 144-BGOPB was determined to be 226 mol / g.

[0179] The proton and carbon NMR spectra are shown in Figure 9, images a) and b), respectively. These spectra show that the product is clean and free of impurities. Each peak can be successfully assigned to the corresponding hydrogen or carbon atom, as shown in the inset.

[0180] The HPLC chromatogram (Figure 10) also shows that a pure, single-component epoxy resin was formed; however, in this example, the increase in oligomer formation for this synthetic procedure is not as great as that for 133 BGOPB, which is indicated by several very small peaks at longer elution times. For HPLC analysis, a 150 x 4.6 mm Altima C18 column was used. The mobile phase was eluted at a flow rate of 1.0 ml min. -1 The solvent was 65% acetonitrile / water.

[0181] Since the 144BGOPB synthesized here was a solid (indicative of a pure compound), the melting point was determined by DC as shown in Figure 11 and was found to be 131 °C, which is significantly higher than the melting point for typical epoxy resins.

[0182] 1,3-Bis(4-glycidyloxyphenoxy)benzene (134 BGOPB) can be synthesized using the same method as 44 BGOPB. Example 6: Synthesis of meta-substituted hydroxy precursors to epoxy resins Step 1: Preparation of ZnCl / SiO catalyst

[0183] Preparation of this catalyst is crucial to ensure adequate reaction conversion and selectivity. Silica gel-supported zinc chloride was prepared by impregnating silica gel (Wakogel C-200, 31.7 g) with a solution of anhydrous zinc chloride (5.0 g) in anhydrous methanol (80 ml). The mixture was stirred at room temperature for 0.5 hours, and then the methanol was removed by rotary evaporation. The resulting solid was dried under vacuum (15 mmHg) at 150°C for 12 hours. Step 2: Laboratory-scale synthesis of bis(4-hydroxyphenyl) m-xylene (BHPmX)

[0184] Phenol (403.30 g, 4.29 mol) and dichloro-m-xylene (75 g, 4.29 × 10 -1 ZnCl / SiO (58.7 g, 8.57 × 10 mol) was placed in a three-necked round-bottom flask (3 L). Dichloroethane (1.35 L) was added to the flask, and the reaction mixture was stirred in a water bath at approximately 10 °C under nitrogen. -2 mol) was slowly added to the reaction mixture and stirred at about 10°C for 2 hours. During the latter step, the temperature inside the flask was about 5°C at the beginning. After adding ZnCl / SiO to the mixture, the temperature slowly rose to about 10°C. Ice was slowly added to the water bath to maintain the temperature at 10°C.

[0185] After 2 hours, the ZnCl2 / SiO2 was filtered and washed with dichloromethane (100 ml). The solvent was then removed using a rotary evaporator (first under vacuum, then using an oil-sealed rotary vacuum pump). During this process, some of the excess phenol was removed by the solvent. The remaining oil (product and a large amount of excess phenol) was washed with 500 ml of hot water (65-70°C). This washing process was repeated 10 times. Hot water was used to effectively remove the phenol (8 g phenol / 100 ml water at room temperature). The oil became viscous as more phenol was removed from the product.

[0186] Following washing, the oil was then redissolved in dichloromethane, dried over Na2SO4 (anhydrous), and filtered. The dichloromethane was removed and the product was identified by NMR, TLC, and GC / MS analysis. Yields were typically 75-80%.

[0187] It was very difficult to detect <10% phenol in the product by NMR. TLC is the quickest way to confirm the presence of phenol in the product (silica / CH2Cl2 as solvent, phenol is R fThe chromatographic analysis of phenolic compounds (values ​​are approximately 0.4-0.45) does not allow for the determination of the percentage of phenol present in the product. GC / MS can be used to confirm the percentage of phenol and the percentage of the three isomers, but it cannot detect the higher-boiling oligomers. HPLC is probably the best method for determining the percentage of phenol, the three isomers, and the oligomers present in the product. If HPLC indicates that there is more than 5% phenol in the product (calculated by peak area %), the product should be washed again with water. Example 7: Synthesis of para-substituted hydroxy precursors to epoxy resins Step 1: Preparation of ZnCl / SiO catalyst

[0188] This catalyst was prepared in the same manner as in Example 6, step 1. Step 2: Large-scale synthesis of bis(4-hydroxyphenyl)-p-xylene (BHPpX)

[0189] Phenol (21.50 kg, 228.57 mol) and dichloro-p-xylene (4.00 kg, 22.86 mol) were placed in a 100 L reactor. Dichloromethane (50 L) was added to the reaction mixture, and the reactor was slowly heated to 40 °C while stirring. Once the temperature in the reactor reached 25-30 °C, ZnCl2 / SiO2 (3.13 kg, 4.57 mol) was slowly added to the stirred reaction mixture and gently refluxed at 35-40 °C for 3 hours. HCl released from the reaction required passing sodium hydroxide solution. At the 4.0 kg scale, it was calculated that a maximum of 1170 L of HCl gas could be produced.

[0190] After 3 hours, the heater was turned off, and the volume of the solution in the reactor was reduced by vacuum to approximately 60 L (current volume was approximately 70 L). The ZnCl2 / SiO2 was filtered and washed with 2–3 L of dichloromethane (DCM). The dichloromethane solution was stored in buckets (five 20 L buckets) at room temperature overnight. The product precipitated from the DCM solution as a fine white solid, which was filtered the next day (the filtrate should be saved, as additional product can be recovered from this later). The white solid product was washed with warm water (40–50 °C) until the pH of the washing solution was neutral. The white solid product was then washed with DCM until the washing solution was colorless (two or three washes may be necessary). Finally, the white solid product was dried in air at room temperature over the weekend. The yield was approximately 1.8–2.0 kg.

[0191] The second crop was recovered by the following method. DCM was removed from the filtrate. The remaining oil (product and excess phenol) was washed with warm (50-60°C) water (40 L). The washing process was repeated until the remaining oil became a semi-solid or viscous paste (seven washes with 40 L of water may be required). This viscous paste was then suspended in DCM (8-10 L) overnight. The product formed as a fine white solid, which was filtered and washed with DCM until the washing solution was colorless. The second crop was pink in color if the DCM washing was insufficient. The white solid product was dried overnight at room temperature in a vacuum box. The yield was approximately 1.0-1.2 kg. The first and second crops were characterized by NMR and HPLC, and the combined yield varied between 42 and 48%. Example 8: Isomeric Composition of Bis-hydroxyphenyl-m-xylene (BHPmX) and Bis-hydroxyphenyl-p-xylene (BHPpX)

[0192] Due to the ortho- and para-directivity of the phenolic group and the double substitution of the phenol, a range of isomeric forms with various substitution patterns would be expected. This was indeed found to be the case, as shown in the typical HLPC chromatogram in Figure 12, where three primary peaks are clearly evident. Beyond these peaks, there is some evidence of the phenolic starting material and higher molecular weight oligomeric species. Considering the standard geometry, these isomers are predicted to consist of 4,4-, 2,4-, and 2,2-substituted isomers (1:4:4 in composition, respectively). This is clearly not what was observed when these isomers were present in a 16:43:19 ratio. This relative composition is commonly found to be present when meta-hydroxy compounds are synthesized multiple times. The variation from the expected composition can be explained by steric constraints favoring para-substitution over the more difficult ortho-substitution. As a result, the relative concentrations of the 4,4- and 2,4-isomers increase at the expense of the 2,2-isomer. This is clearly observed in the HPLC chromatogram shown in Figure 12. The HPLC trace also shows that the synthesis of meta-hydroxy compounds contains significant levels of higher molecular weight oligomers. 1 The 1 H-NMR spectrum indicates that this compound was synthesized with a high level of purity.

[0193] The HPLC trace for the para-substituted hydroxy compound is shown in Figure 14, where it is observed that very little of the 2,2 isomer is present. Here, the difference between the meta-substituted and para-substituted xylene syntheses relates to the difference in solubility of the more rigid para-substitution on the central phenyl ring compared to the more twisted meta-substituted hydroxy compound. The para-substituted version is less soluble than the meta-substituted version and more easily precipitates out of solution during synthesis. While this makes isolation easier, the drawback is that the 2,2 isomer remains in solution and is effectively lost during purification. This explains the presence of only two isomers and the much lower yield than the meta synthesis. Conversely, the benefit of the lack of solubility is the much lower level of oligomer concentration, since oligomers are also found to remain in solution. The NMR spectrum in Figure 15 also demonstrates that the para-substituted compound was synthesized with a high level of purity. Overview of hydroxy and epoxy resin synthesis.

[0194] Here, we have synthesized and characterized the isomeric composition of a novel epoxy resin made from three benzene groups linked via methylene bonds. The methylene bonds are understood to provide deformation mobility, while the aromatic rings provide thermal stability and resistance to solvent intrusion. The structural difference between bishydroxy and epoxy resins arises from the central xylene group being meta- or para-substituted. While this does not affect the reaction mechanism for forming the molecule, the kinked backbone of the meta compound versus the rigid, linear backbone of the para compound has a significant impact on the overall product formed. Some of the key experimental aspects of the synthesis that distinguish it from other methods are as follows: BHPmX 1. After the reaction, filter off the catalyst and evaporate the DCM completely. 2. The oily product is washed successively with water to remove phenol. This is an advantage as it aids the washing steps in removing phenol. 3. The final product is an oil containing three isomers, high molecular weight oligomers, with a yield of approximately 75% in the laboratory. BHPpX 1. After the reaction, the catalyst is filtered off and the DCM volume is reduced until the product crystallizes out of solution. 2. The product is filtered to yield a white solid having three isomers, however the third isomer, the 2,2 substituted isomer, is present only in very low concentration. 3. The final product was obtained in a yield of about 50%, and only a small amount of high molecular weight oligomers was observed. Example 9: Scale-up of bis(hydroxyphenyl)-p-xylene (BHPpX) synthesis

[0195] 26 kg of para-hydroxy compounds were synthesized in the CSIRO experimental plant over three separate periods. The first period was a 1 kg trial for condition optimization; the second period produced 16.2 kg; and the third period produced approximately 10 kg. However, during scale-up, due to the design constraints of the experimental plant, only 2–4 kg of product was produced in each case. Each batch was prepared and characterized by HPLC to determine the isomer composition. Figure 16 shows a plot of the concentrations of various isomers (including the phenol starting reactant and oligomeric species). During scale-up synthesis, it was typical to obtain a second crop from the filtrate, as the product was more miscible than the first product that precipitated. As expected, these products are characterized in that their isomer composition is affected by the high levels of oligomers and the increased concentration of 2,2-substituted isomers. This is significant in that the 2,2 substituted isomer is indeed synthesized, but is simply more soluble in the solvent and does not precipitate in the first instance. Example 10: Curing and Characterization of Carbonyl-Linked Aromatic Amines, 1,3-Bis(3-aminobenzoyl)benzene (133BABB), 1,3-Bis(4-aminobenzoyl)benzene (134BABB), and 1,4-Bis(4-aminobenzoyl)benzene (144BABB) Resin manufacturing

[0196] A series of epoxy / amine formulations were blended in 1:1 epoxide to amine stoichiometry, mixed and degassed on a rotary evaporator using a water bath at a temperature of 110°C.

[0197] The epoxy resins used were: Glycidyl ether of bisphenol A (BisA) Glycidyl ether of bisphenol F (BisF), and 1,4 bis(4-glycidyl ether phenoxy)benzene (144BGOPB), TIFF0007772508000155.tif46170TIFF0007772508000156.tif46170TIFF0007772508000157.tif32170

[0198] The amines used were based on compounds of formula 4': TIFF0007772508000158.tif34170

[0199] Specifically, the following amines were tested: 1,3-bis(3-aminobenzoyl)benzene (133BABB) 1,3-bis(4-aminobenzoyl)benzene (134BABB), and ·1,4-bis(4-aminobenzoyl)benzene (144BABB).

[0200] Due to the potential for reaction and lack of miscibility in some preparations, mixing was generally stopped as soon as it was apparent that the amine was completely dissolved in the epoxy resin and no air bubbles were present.

[0201] The resin was then poured into preheated silicone molds for flex testing and dynamic mechanical thermal analysis. These molds were preheated at 110°C for a minimum of 1 hour. The epoxy resin was then cured in an air circulating oven, typically at 177°C for 10 hours, with a post-cure at 210°C.

[0202] Table 3 shows exemplary BABB-based resins that were prepared. In each case, the cure profile was 177°C for 10 hours, then 210°C for 2 hours. TIFF0007772508000159.tif122170 Identification

[0203] Dynamic mechanical thermal analysis (DMTA) spectra are shown in Figure 17 and show fairly typical behavior for high-performance epoxy networks. The tan δ spectra appear particularly sharply symmetric, likely attributable to their extreme homogeneity and lack of significant chemical defects. The 133BABB product produced networks with the lowest Tg values, at 140-170°C (tan δmax), while networks cured with 144BABB had the highest, at approximately 160-200°C. The Tg values ​​for networks cured with 134BABB were very similar to those of 144BABB, suggesting that the Tg values ​​are primarily determined by the substitution pattern of the outer aromatic rings. BisA resins exhibited the highest Tg values, followed by 144BGBOP and BisF, which yielded similar Tg values ​​regardless of the amine.

[0204] The flexural properties of the cured networks are compared to each other in Figure 18. In this case, these results were also compared to BisA and BisF resins cured with 4,4-diaminodiphenyl sulfone (44DDS). As shown, the compressive modulus and compressive strength for the BABB-cured networks are at least equivalent to those of the BisA and BisF resins, and indeed, show superior toughening when cured with 133BABB amine. This is somewhat surprising, since meta-substituted networks generally have lower glass transition temperatures. The rupture displacement also suggests increased ductility, so curing various epoxy resins with BABB amine produced networks with improved strength, stiffness, and ductility—properties that are not usually improved simultaneously.

[0205] Figure 19 shows the results obtained for the mass gain during immersion of cured epoxy resin networks in methyl ethyl ketone (MEK). The results show overall resistance to MEK uptake by networks cured with BABB. 133 Networks cured with BABB provide very good chemical resistance. Greater resistance to MEK intrusion is achieved using BiSF, followed by 144 BGBOP, and then BisA. Example 11: Curing and Characterization of Methylene-Bonded Aromatic Epoxy Resins, Bisamines, 1,3-Bis(3-aminobenzoyl)benzene (133BABB), 1,3-Bis(4-aminobenzoyl)benzene (134BABB), and 1,4-Bis(4-aminobenzoyl)benzene (144BABB) Resin manufacturing

[0206] In this preparation, diglycidyl ethers of bisphenol F (BisF), bis[(glycidyl ether)phenyl)]-m-xylene (BGOPmX), bis[(glycidyl ether)phenyl)]-p-xylene (BGOPpX), and diglycidyl ether biphenyl (BGOBP) were used: TIFF0007772508000160.tif100170

[0207] The amine curing agents used to cure the epoxy resin were 4,4-diaminodiphenyl sulfone (44DDS) and methylenedianiline (MDA). TIFF0007772508000161.tif55170Sample production

[0208] The epoxy resins were conditioned at 100°C for approximately 0.5 hours and then mixed together under vacuum on a rotary evaporator at approximately 120°C. They were then placed in a vacuum oven set at approximately 95°C and -100 kPa for 1 hour to minimize dissolved gas levels. The curing agent was then added to the epoxy resin to achieve an overall 1:1 epoxide:amino stoichiometry, and mixing continued on the rotary evaporator until the curing agent was dissolved within the epoxy resin. This continued for approximately 1-2 hours, depending on the reactivity of the formulation. During this time, Teflon-coated molds were preheated at 120-150°C for 4 hours. Upon completion of mixing, the resin samples were poured into the Teflon molds and cured in an air-circulating oven. Due to the relatively high reactivity of the MDA system, they were cured at 150°C for 12 hours, followed by a 3-hour post-cure at 177°C. On the other hand, the relatively less reactive 4,4DDS system was cured at 177°C for 12 hours followed by a post-cure at 205°C for 3 hours.

[0209] To achieve uniform cure and a homogeneous network, careful attention had to be paid to ensuring that the curing agent was completely dissolved within the epoxy resin before curing. This was true even when higher temperatures were required to dissolve the amine. If this was not done properly, a non-uniform network with very poor properties resulted. Additionally, because BGOBP epoxy resin is a solid at room temperature, it was necessary to blend it with 30 mol% BiSF epoxy to improve processability.

[0210] A list of the samples produced in this program, along with their cure profiles and post-cure specifications, is shown in Table 4. TIFF0007772508000162.tif124170 Identification

[0211] DMTA analysis is shown in Figure 20, showing that for the 44DDS and MDA cured systems, the T values ​​follow a trend with BGOPmX having the lowest T, followed by BGOPpX, BisF, and finally the BGOBP blend formulation, which has the highest T despite containing 30 mol% BisF epoxy resin. The tan δ traces are observed to be highly symmetrical and homogeneous, which is indicative of a simple curing mechanism for both the MDA and 4,4DDS-based systems. However, it should be noted that for the 44DDS-cured system, the epoxy resin does indeed exhibit a smaller peak at higher temperatures above T, which worsens at higher cure temperatures and increases with continued post-cure. The peaks in the tan δ spectra are shown in Table 5 for the 44DDS and MDA systems, confirming that the T values ​​are close to those previously determined. TIFF0007772508000163.tif130170 Table 5: Tg values ​​after curing measured from tan delta spectra for the cured system of 44DDS and MDA in Example 11

[0212] Figure 21 shows the effect of various post-curing temperatures on the DMTA spectra. As can be seen, although there is some additional reaction in the rubbery region at higher temperatures, there is only a minimal effect on the Tg of the network. The consistency of the Tg values ​​suggests that the cure mechanism is very robust and stable.

[0213] The compressive properties measured for each of the networks are shown in Figures 22 and 23. The modulus results in Figure 22 reveal that BGOPmX yields the highest modulus, followed by the BGOPpX network and then the BisF network. The rigid-rod biphenyl polymer network has the lowest modulus of all. These results indicate that the modulus in glassy polymers is controlled by short-range motion and free volume, and by packing density rather than crosslink density.

[0214] In the case of BGOPmX, the meta-substitution results in a backbone structure that tends to provide better packing, reduced free volume, and therefore higher modulus. BGOPpX para-substituted networks are more rigid polymer networks and, as a result, have somewhat lower modulus. Biphenyl-based networks, as one might expect, have even poorer packing density due to their rigid structure, resulting in increased free volume, lower density, and significantly lower modulus. In contrast, yield strain and yield stress are more controlled by longer-range factors (e.g., crosslink density); as a result, these parameters are significantly lower for BGOPpX and BGOPmX epoxy resins compared to BisF and rigid-rod biphenyl network networks.

[0215] Samples similar to those used for compression measurements were placed in MEK and Skydrol (Solutia Inc.) at room temperature for approximately 45 days, and weight uptake was measured at appropriate time intervals. Figures 24a and 24b show the results obtained for systems cured with 44DDS and MDA, respectively, demonstrating that biphenyl and BGOPmX resins cured with 44DDS exhibit reduced levels of absorbed MEK compared to the commercially available BisF / 44DDS system. These results are similar for the corresponding MDA networks, although in this example the BGOPmX network is slightly superior to, rather than slightly inferior to, BisF. However, the key finding from this study is that BGOPmX possesses much higher levels of MEK uptake compared to BisF, regardless of the amine used. This can be explained by the predicted larger free volume (which itself stems from the higher rigidity and linearity of the para-substituted network) resulting from reduced packing efficiency. Example 12: Comparison of the cure and characterization of 1,4-bis(4-glycidyloxyphenoxy)benzene (144BGOPB) and 1,3-bis(3-glycidyloxyphenoxy)benzene (133BGOPB) cured with 44 diaminodiphenyl sulfone (44DDS) with the cure and characterization of the diglycidyl ether of bisphenol A (BisA) and the diglycidyl ether of bisphenol F (BisF) cured with 44 diaminodiphenyl sulfone (44DDS). Sample preparation

[0216] Epoxy resins 144-BGOPB and 133-BGOPB were placed in round-bottom flasks in water baths at approximately 140°C (133-BGOPB) and 145°C (144-BGOPB), respectively, and degassed on a rotary evaporator for 5 minutes. Then, 4,4-diaminodiphenyl sulfone (44DDS) (or 3,3-diaminodiphenyl sulfone (33DDS)) was slowly added over approximately 10 minutes, and mixing was continued until the resin became clear and free of air bubbles. This composition ensured that the epoxy amine resins were always blended at a 1:1 stoichiometric ratio. These resins were then poured into Teflon-coated molds preheated to 150°C and cured in an air circulatory system. The formulations and their curing profiles are listed in Table 6. TIFF0007772508000164.tif79170TIFF0007772508000165.tif174170Identification

[0217] Figure 25 shows a selection of tan δ traces for the 133 and 144BGOPB systems after 12 hours of curing at 177°C, compared to BisF (a widely used aerospace epoxy resin) cured under the same conditions with 33DDS and 44DDS. As can be seen, the 144BGOPB polymer network has a Tg that is only about 10°C lower than the BisF / 44DDS network. In contrast, however, the polymer network cured with 133BGOPB / 44DDS is somewhat lower, below the 43°C level.

[0218] Figure 26 shows a raw plot of compressive stress versus compressive strain illustrating the differences in mechanical properties of the 133 and 144BGOPB systems, particularly in relation to the degree of yield and stiffness. Full results are presented in Table 7. An important point to note is that, compared to each other, 144BGOPB has a lower modulus (1239 MPa), followed by the BisF / 4,4DDS system (1612 MPa). Despite this, the yield strain for the 144BGOPB network (a key indicator of the network's ability to act as a strain resin) is significantly higher than the other resins. Otherwise, 144BGOPB has a lower yield stress, although it tends not to show a significant trend with stress. The stress-rupture and strain-rupture times appear similar. TIFF0007772508000166.tif116170

[0219] Those skilled in the art will appreciate that numerous changes and modifications can be made to the above examples without departing from the general breadth and scope of the present disclosure, and therefore, these examples are to be considered in all respects as illustrative and not restrictive.

Claims

1. A curable epoxy resin formulation comprising an epoxy resin and a curing agent, The epoxy resin is a compound of Formula 1 or Formula 2, During the ceremony, X 1 are each the same and are O; X 2 are each the same and are C(O); each R 1 is hydrogen and each R 2 is an epoxide group, or each R 2 is hydrogen and each R 1 is an epoxide group; (a) When X 1 is O, the epoxide group is and a compound of Formula 1 or Formula 2, The curing agent may be a compound of Formula 4: [wherein Y is the same as each other, and O, CH ２ and C(O)].

1. A curable epoxy resin formulation comprising a diamine curing agent of formula:

2. The compound of formula 4 may be a compound of formula 4a: wherein Y is as defined in claim 1.

2. The curable epoxy resin formulation of claim 1, wherein the curable epoxy resin formulation is selected from the group consisting of:

3. The compound of formula 4 may be a compound of formula 4b: wherein Y is as defined in claim 1.

2. The curable epoxy resin formulation of claim 1, wherein the curable epoxy resin formulation is selected from the group consisting of:

4. The compound of formula 4 may be a compound of formula 4c: wherein Y is as defined in claim 1.

2. The curable epoxy resin formulation of claim 1, wherein the curable epoxy resin formulation is selected from the group consisting of:

5. The compound of formula 4 may be a compound of formula 4d: wherein Y is as defined in claim 1.

2. The curable epoxy resin formulation of claim 1, wherein the curable epoxy resin formulation is selected from the group consisting of:

6. 6. The curable epoxy resin formulation of claim 1, further comprising one or more additives.

7. 6. An impregnated fiber-reinforced material comprising fibers impregnated with the curable epoxy resin formulation of any one of claims 1 to 5.

8. 6. A composite comprising a fibrous material within a matrix of cured epoxy resin, wherein the cured epoxy resin is formed from a curable epoxy resin formulation according to any one of claims 1 to 5.

9. The following steps: a) (i) a curable epoxy resin formulation according to any one of claims 1 to 5, and (ii) textile materials; and b) combining the resin formulation of step (a) with (i) the fibrous material of step (a) and (ii) subjecting the material to an elevated temperature to cure the material, thereby forming an impregnated fibrous reinforced material.

1. A method of forming an impregnated fiber reinforced material, comprising:

10. 6. Use of a curable epoxy resin formulation according to any one of claims 1 to 5 in the production of an impregnated fibre-reinforced material or a composite thereof.

11. reacting a compound of formula 8 with a halogenated epoxy compound of formula 9 to form a compound of formula 10: A method for preparing a compound of formula 10, comprising:

12. The compound of formula 8 can be prepared by the following steps: i) reacting a compound of formula 5 with a compound of formula 6 in the presence of a catalyst to form a compound of formula 7, wherein P is a protecting group, M is a metal, and LG is a leaving group: ii) further reacting the compound of formula 7 with an acid catalyst to form a compound of formula 8: The method of claim 11 , wherein the compound is produced by a process comprising:

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