Preparation and glass-like polymer resin based on epoxide containing dynamic bond

Abstract

Formulations intended to be cured for the production of glass-like polymer resins of the epoxy type. The first component comprises one or more epoxy components, wherein at least one epoxy component comprises at least one aromatic ring, two or more epoxy moieties, and one or more dynamic covalent bonds; wherein at least one epoxy moiety is separated from at least one other epoxy moiety by at least one dynamic covalent bond, and the second component is or comprises one or more curing agents; and wherein at least one of the first component and the second component is a liquid at a temperature of less than or equal to 65 DEG C; and wherein the first component is compatible with the second component as determined by a compatibility test A at a temperature of less than or equal to 65 DEG C; and wherein the formulation cures at a temperature less than or equal to 65 DEG C to form an epoxy-based glass polymer.

Description

Technical Field

[0001] This disclosure relates to a formulation intended for curing to manufacture an epoxy-type vitrified polymer resin, and the use of the formulation in manufacturing one or more epoxy-type vitrified polymer resins. This disclosure also relates to a method for manufacturing said one or more epoxy-type vitrified polymer resins, and an epoxy-type vitrified polymer resin comprising a composition prepared by combining all the formulation components. Background Technology

[0002] Thermosetting resins (or thermosetting materials) possess advantages such as high mechanical strength, high heat resistance, and chemical resistance, allowing them to replace metals in certain applications. They are also lighter than metals. They can be used as matrices in composite materials, as adhesives, and as coatings. For example, they are widely used in the automotive industry and wind turbine engineering. However, a major problem with thermosetting materials is that they are not repairable or recyclable. This leads to end-of-life management issues for industrial thermosetting materials. For example, it is predicted that by 2050, approximately 65 million tons of epoxy-based composite waste from the wind energy sector alone will accumulate.

[0003] To address these challenges associated with end-of-life management, a new family of polymers has emerged. These are vitrifiers, which offer typical thermoset properties, such as chemical resistance and creep resistance, along with good thermal and mechanical properties, combined with reprocessability similar to thermoplastics, including weldability, repairability, and chemical and mechanical recyclability. Vitrifiers are permanent networks of polymer chains linked by dynamic covalent bonds (e.g., carboxylic acid ester bonds), which allow the network to change its topology while maintaining a near-constant number of chemical bonds at temperatures below its degradation temperature.

[0004] In their study, Qin J. et al., entitled "Thermo-healing and recyclable epoxy thermosets based on dynamic phenol-carbamate bonds" (Reactive and Functional Polymers, 2022, 180, 105411), a dynamically reversible epoxy thermosetting material based on phenol-carbamate bonds was obtained. A low relaxation time, as well as a high glass transition temperature and a high storage modulus (E'), were reported. However, this thermosetting material was obtained by heating the components under vacuum at a high temperature (80°C). The need for heating during curing hinders industrial development in the field of composite material manufacturing.

[0005] In a study titled "Hempseed oil-based covalent adaptable epoxy-amine network and its potential use for room temperature curable coatings" (ACS Sustainable Chem. Eng., 2020, 8, 14964-14974) by Zhang S. et al., a room-temperature curable bio-based epoxy glass polymer was designed. The pure hemp seed oil-based network reported a glass transition temperature of 40°C to approximately 50°C and a relaxation time of approximately 1900 seconds. The storage modulus (E') measured at 25°C was below 2000 MPa. Adding DER 331 epoxy resin (bisphenol A diglycidyl ether, DGEBA) allowed for an increase in both the glass transition temperature and storage modulus (E'), but significantly increased the relaxation time, thus impairing recyclability and repairability.

[0006] In a study titled "Insight into the structure-property relationships of intramolecularly-catalyzed epoxy vitrimers" (Materials & Design, 2022, 221, 110924) by Wang H. et al., epoxy glass-like polymers with intramolecularly catalyzed transesterification were prepared by curing ester-containing epoxy resins with diethylenetriamine and monoamines. Curing began at room temperature. Glass-like polymers with high Tg (i.e., 99°C as determined by the tan δ peak using DMTA) and moderate relaxation times of 712 s measured at 180°C were obtained.

[0007] These studies indicate that existing epoxy formulations for preparing glass-like polymers lack the combination of properties required for industrial processing and use in structural applications. In particular, existing glass-like polymers produced from epoxy formulations typically suffer from at least one of the following problems:

[0008] 1) They exhibit low glass transition temperatures (Tg), typically between -30°C and 50°C, as determined by differential scanning calorimetry, which means they cannot be used for load-bearing capacity due to softening and loss of mechanical properties at temperatures associated with structural applications.

[0009] 2) They exhibit a combination of low room temperature stiffness determined by dynamic mechanical analysis (DMA storage modulus, E') or quasi-static mechanical testing (e.g., tensile modulus, flexural modulus, etc.) and rapid reworkability (short relaxation time at temperatures far below degradation temperature) determined by isothermal stress relaxation experiments, which facilitates repair and recycling, but makes them unsuitable for structural (load-bearing) applications.

[0010] 3) They exhibit a combination of high room temperature stiffness determined by dynamic mechanical analysis (DMA storage modulus, E') or quasi-static mechanical tests (e.g., tensile modulus, flexural modulus, etc.) and limited reworkability (high relaxation time even at temperatures close to degradation temperature) determined by isothermal stress relaxation experiments, which makes them usable for structural (load-bearing) applications, but difficult or impossible to repair, recycle or reuse.

[0011] 4) They are derived from formulations that do not meet the requirements of many industrial production processes for formulations that can be treated as liquids and crosslinked at low or ambient temperatures (<65°C) to form glass-like materials.

[0012] This highlights the clear need to develop epoxide-based formulations and glass-like polymers that combine the properties required for industrial processing and use in structural applications. Summary of the Invention

[0013] According to a first aspect, this disclosure relates to formulations comprising at least a first component and a second component, wherein the formulation is intended to be cured for use in the manufacture of epoxy-type glass-like polymers, and the significant feature of the formulation is that:

[0014] - The first component comprises one or more epoxy components, wherein at least one epoxy component comprises at least one aromatic ring, two or more epoxy moieties and one or more dynamic covalent bonds; wherein at least one epoxy moiety is separated from at least one other epoxy moieties by at least one dynamic covalent bond;

[0015] -The second component is or contains one or more curing agents;

[0016] Wherein at least one of the first component and the second component is a liquid at a temperature below or equal to 65°C; and

[0017] Wherein, as determined by compatibility test A at a temperature below or equal to 65°C, the first component is compatible with the second component.

[0018] More particularly, this disclosure relates to formulations comprising at least a first component and a second component, and optionally a third component, said third component being one or more kinetic modifiers, wherein said formulation is intended to be cured for use in the manufacture of epoxy-type glass-like polymers, and said formulation is notable for the following:

[0019] - The first component comprises one or more epoxy components, wherein at least one epoxy component comprises at least one aromatic ring, two or more epoxy moieties and one or more dynamic covalent bonds; wherein at least one epoxy moiety is separated from at least one other epoxy moieties by at least one dynamic covalent bond;

[0020] - The second component is or contains one or more curing agents, said curing agents being selected from compounds containing at least two active hydrogens, said active hydrogens being in the form of at least two aliphatic amine hydrogens and / or at least two aliphatic thiols;

[0021] Wherein at least one of the first component, the second component, and, if present, the third component is a liquid at a temperature below or equal to 65°C; and

[0022] Wherein, as determined by compatibility test A at a temperature below or equal to 65°C, the first component is compatible with the second component and, if present, the third component.

[0023] Furthermore, the formulations disclosed herein allow for the easy generation of high-performance glass-like polymers.

[0024] For example, at least one of the first component, the second component, and, if present, the third component is a liquid at a temperature below or equal to 60°C; preferably below or equal to 55°C, more preferably below or equal to 50°C, even more preferably below or equal to 45°C, most preferably below or equal to 40°C, or below or equal to 35°C, or below or equal to 30°C. For example, at least one of the first component, the second component, and, if present, the third component is a liquid at room temperature, i.e., at a temperature between 15°C and 30°C or between 20°C and 25°C.

[0025] Advantageously, each of the first component, the second component, and, if present, the third component is a liquid at a temperature of 65°C or lower. For example, each of the first component, the second component, and, if present, the third component is a liquid at a temperature of 60°C or lower; preferably 55°C or lower, more preferably 50°C or lower, even more preferably 45°C or lower, most preferably 40°C or lower, or 35°C or lower, or 30°C or lower. For example, each of the first component, the second component, and, if present, the third component is a liquid at room temperature, i.e., at a temperature of 15°C to 30°C or 20°C to 25°C.

[0026] Advantageously, according to ASTM D2196-20, the formulation has a viscosity of less than 10,000 mPa·s, preferably less than 9,500 mPa·s, or less than 9,000 mPa·s at a temperature below or equal to 65°C, as determined by a Brookfield viscometer with a suitable rotor.

[0027] Advantageously, the molar ratio of the amount of epoxy in the first component to the amount of active hydrogen in the second component is between 0.80:1 and 1.20:1, preferably between 0.85:1 and 1.15:1, more preferably between 0.90:1 and 1.10:1, and even more preferably between 0.95:1 and 1.05:1.

[0028] Preferably, the second component comprises two or more thiol moieties and / or one or more amine moieties, and the two or more active hydrogens are hydrogens derived from the two or more thiol moieties and / or one or more amine moieties.

[0029] More preferably, the second component comprises two or more thiol moieties and / or one or more primary amine moieties, and the two or more active hydrogens are hydrogens derived from the two or more thiol moieties and / or one or more primary amine moieties.

[0030] Advantageously, the formulation also comprises one or more kinetic modifiers.

[0031] Preferably, the one or more kinetic modifiers do not contain hydroxyl groups.

[0032] Preferably, the one or more kinetic modifiers are selected from one or more nonnucleophilic amine bases, one or more Lewis acids, one or more Brønsted bases, one or more Brønsted acids, one or more ionic liquids, or any combination thereof.

[0033] Preferably, the content of each of the one or more kinetic modifiers is less than 15 mol.% relative to the dynamic covalent bond molar content and / or less than the solubility limit, or lower, and more preferably less than 10 mol.% relative to the dynamic covalent bond molar content and / or less than the solubility limit.

[0034] Preferably, the content of each of the one or more kinetic modifier components is at least 0.01 mol.% relative to the molar content of the dynamic covalent bond and / or less than the solubility limit, or even lower, and more preferably at least 0.1 mol.% relative to the molar content of the dynamic covalent bond and / or less than the solubility limit.

[0035] For example, the formulation is a homogeneous liquid at a temperature of 65°C or less, preferably 60°C or less, more preferably 55°C or less, even more preferably 50°C or less, most preferably 45°C or less, or 40°C or less, or 35°C or less, or 30°C or less.

[0036] For example, the formulation is a homogeneous liquid at room temperature, i.e., at a temperature of 15°C to 30°C or 20°C to 25°C.

[0037] First component

[0038] Preferably, the first component has the following chemical structure:

[0039]

[0040] Where R contains at least one aromatic ring;

[0041] Wherein X contains at least one dynamic covalent bond;

[0042] Where n, m, and k are integers and n+m+k≥2;

[0043] Where n+k≥1;

[0044] Furthermore, R' is an optional group, which is selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more alicyclic groups, one or more aromatic groups, one or more heterocyclic (C3-C6 alkyl) groups having one or more heteroatoms selected from N, S, O or any combination thereof, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof, and one or more ketone heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof.

[0045] Furthermore, R'' is an optional group, which is or contains one or more selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more alicyclic groups, and one or more heteroatoms selected from N, S, O, or any combination thereof; one or more -CH2- groups are present or absent that connect the optional R'' group to the remainder of the chemical structure and / or the adjacent epoxy moiety; preferably, a -CH2- group that connects the optional R'' group to the remainder of the chemical structure and / or the adjacent epoxy moiety is present.

[0046] Preferably, R comprises one or more aromatic rings, said aromatic rings being functionalized from one or more of the following: one or more linear aliphatic groups, one or more branched aliphatic groups, one or more alicyclic groups, one or more aromatic groups, one or more heterocyclic (C3-C6 alkyl) groups having one or more heteroatoms selected from N, S, O or any combination thereof, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof, and one or more ketone heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof.

[0047] Preferably, X comprises at least one dynamic covalent bond, wherein the one or more dynamic covalent bonds are selected from one or more carboxylic ester bonds, one or more siloxane bonds, one or more silyl ether bonds, one or more disulfide bonds, one or more borate ester bonds, one or more phosphonate ester bonds, one or more phosphate ester bonds, one or more triazine ether bonds, one or more amide bonds, or combinations thereof; and are in any orientation and may or may not contain one or more -CH2- groups that connect the dynamic bond to the remainder of the chemical structure.

[0048] Preferably, X comprises a dynamic covalent bond, which is one or more carboxylic acid ester bonds; the one or more carboxylic acid ester bonds are in any orientation and have or do not have one or more -CH2- groups that connect the one or more carboxylic acid ester bonds to the rest of the chemical structure; more preferably, X comprises a dynamic covalent bond, which is a carboxylic acid ester bond, the carboxylic acid ester bond is in any orientation and has a -CH2- group that connects the carboxylic acid ester bond to the rest of the chemical structure.

[0049] For example, the first component has the following chemical structure

[0050]

[0051] Where R contains at least one aromatic ring;

[0052] Wherein X contains at least one dynamic covalent bond;

[0053] Where m is an integer between 1 and 6.

[0054] Where n is an integer greater than or equal to 0.

[0055] Furthermore, R' is an optional group selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more alicyclic groups, one or more aromatic groups, one or more heterocyclic (C3-C6 alkyl) groups having one or more heteroatoms selected from N, S, O or any combination thereof, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof, and one or more ketone heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof.

[0056] Preferably, R comprises one or more aromatic rings, said aromatic rings being functionalized from one or more of the following: one or more linear aliphatic groups, one or more branched aliphatic groups, one or more alicyclic groups, one or more aromatic groups, one or more heterocyclic (C3-C6 alkyl) groups having one or more heteroatoms selected from N, S, O or any combination thereof, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof, and one or more ketone heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof.

[0057] Preferably, X comprises at least one dynamic covalent bond, wherein the one or more dynamic covalent bonds are selected from one or more carboxylic ester bonds, one or more siloxane bonds, one or more silyl ether bonds, one or more disulfide bonds, one or more borate ester bonds, one or more phosphonate ester bonds, one or more phosphate ester bonds, one or more triazine ether bonds, one or more amide bonds, or combinations thereof; and are in any orientation and may or may not contain one or more -CH2- groups that connect the dynamic bond to the remainder of the chemical structure.

[0058] Preferably, X comprises a dynamic covalent bond, which is one or more carboxylic acid ester bonds; the one or more carboxylic acid ester bonds are in any orientation and have or do not have one or more -CH2- groups that connect the one or more carboxylic acid ester bonds to the rest of the chemical structure; more preferably, X comprises a dynamic covalent bond, which is a carboxylic acid ester bond, the carboxylic acid ester bond is in any orientation and has a -CH2- group that connects the carboxylic acid ester bond to the rest of the chemical structure.

[0059] For example, the first group is selected from

[0060] Or a mixture thereof.

[0061] More preferably, the first component is selected from

[0062] Or a mixture thereof.

[0063] In one implementation scheme, the first component is selected from:

[0064] -The diglycidyl ester family of phthalic acid; and / or

[0065] - The diglycidyl ester family of phthalic acid; wherein the phthalic acid may be substituted or unsubstituted; and / or

[0066] -The triglycidyl ester family of benzotriglycerides; and / or

[0067] -The triglycidyl ester family of benzotricarboxylic acid; wherein benzotricarboxylic acid may or may not be substituted; and / or

[0068] - A family of epoxidized hydroxybenzoic acids containing one glycidyl ether and one glycidyl ester; and / or

[0069] - A family of epoxidized hydroxybenzoic acids containing a glycidyl ether and a glycidyl ester; wherein the hydroxybenzoic acid may be substituted or unsubstituted; and / or

[0070] -A family of diglycidyl ethers of bisphenols containing two phenolic substituents separated by a dynamic bond;

[0071] - A family of diglycidyl ethers comprising two phenolic substituents separated by a dynamic bond; wherein the bisphenol may be substituted or unsubstituted; and / or

[0072] - A family of epoxidized aminobenzoic acids containing two glycidylamines and one glycidyl ester; and / or

[0073] - A family of epoxidized aminobenzoic acids containing two glycidylamines and one glycidyl ester; wherein the aminobenzoic acid can be substituted or unsubstituted.

[0074] Second component

[0075] For example, the second component comprises two or more thiol moieties (e.g., -SH) and / or one or more amine moieties. Preferably, the one or more amine moieties are one or more primary amine moieties (e.g., -NH2) and zero or more secondary amine moieties (e.g., -NH-) or two or more secondary amine moieties, more preferably one or more primary amine moieties (e.g., -NH2).

[0076] For example, the second component is selected from compounds containing at least two aliphatic amine hydrogens and / or at least two aliphatic thiols.

[0077] Preferably, the at least one curing agent is selected from one or more poly(epoxide) oligomers, one or more poly(siloxane) oligomers, one or more poly(diene) oligomers, one or more poly(olefin) oligomers, one or more poly(amide) oligomers, one or more poly(alkylene sulfide) oligomers, one or more poly(alkylene disulfide) oligomers, or any combination thereof, wherein the one or more oligomers are one or more amine-terminated oligomers and / or one or more thiol-terminated oligomers.

[0078] Preferably, the second component, which is or includes the at least one curing agent, is selected from:

[0079]

[0080] Or a mixture thereof.

[0081] According to the second aspect, this disclosure relates to the use of the formulation according to the first aspect for manufacturing one or more epoxy-type glass-like polymer resins.

[0082] According to a third aspect, the present invention relates to a method for manufacturing an epoxy-type glass-like polymer resin, the significant feature of which is that it comprises the following steps:

[0083] a) Provide at least a first component and a second component of the formulation according to the first aspect;

[0084] b) Mix all components together to obtain the formulation; wherein the formulation is a homogeneous liquid at a temperature of 65°C or below;

[0085] c) Curing the formulation to obtain an epoxy-type glass-like polymer resin;

[0086] The curing in step (c) is initiated at a temperature below 65°C.

[0087] More particularly, according to a third aspect, the present invention relates to a method for manufacturing an epoxy-type glass-like polymer resin, the notable feature of which is that it comprises the following steps:

[0088] a) Provide a first component and a second component of the formulation according to the first aspect, and optionally a third component, said third component being one or more kinetic modifiers;

[0089] b) Mix the first component, the second component, and, if present, the third component together to obtain the formulation; wherein the formulation is a homogeneous liquid at a temperature below or equal to 65°C;

[0090] c) Curing the formulation to obtain an epoxy-type glass-like polymer resin;

[0091] The curing in step (c) is initiated at a temperature below 65°C.

[0092] For example, the curing in step (c) is initiated at a temperature below 60°C, preferably below 55°C, more preferably below 50°C, even more preferably below 45°C, most preferably below 40°C, and even most preferably below 35°C.

[0093] For example, the curing in step (c) is initiated at a temperature of 15°C to 65°C, or 15°C to 60°C, or 15°C to 55°C, or 20°C to 50°C.

[0094] For example, the curing in step (c) is initiated at room temperature, i.e. at a temperature of 15°C to 30°C or 20°C to 25°C.

[0095] According to the fourth aspect, this disclosure relates to an epoxy-type glass-like polymer resin containing a composition prepared by combining all the components of the formulation as defined in the first aspect.

[0096] More specifically, according to the fourth aspect, this disclosure relates to an epoxy-type glass-like polymer resin comprising a composition prepared by combining a first component, a second component, and, if present, a third component of a formulation as defined in the first aspect.

[0097] Advantageously, the resin exhibits a glass transition temperature T of at least 55°C, as determined by differential scanning calorimetry at a heating rate of 5°C / min according to ASTM D3418-21. g Preferably, the glass transition temperature T is at least 60°C, more preferably at least 65°C, even more preferably at least 70°C, most preferably at least 75°C, or at least 80°C, or at least 85°C, or at least 90°C, or at least 100°C, or at least 105°C, or at least 110°C, or at least 115°C, or at least 120°C, or even most preferably at least 125°C, or at least 130°C, or at least 135°C, or at least 140°C. g .

[0098] Advantageously, the resin exhibits a room temperature modulus of elasticity of at least 1,400 MPa; or at least 1,450 MPa, or at least 1,500 MPa, or at least 1,550 MPa, or at least 1,600 MPa, or at least 1,650 MPa, or at least 1,700 MPa, or at least 1,750 MPa, or at least 1,800 MPa, or at least 1,850 MPa, or at least 1,900 MPa, or at least 1,950 MPa, or at least 2,000 MPa, or at least 2,050 MPa, or at least 2,100 MPa, or at least 2,150 MPa, or at least 2,200 MPa, or at least 2,250 MPa, or at least 2,300 MPa, or at least 2,350 MPa. MPa; preferably at least 2,390 MPa, or at least 2,400 MPa, more preferably at least 2,450 MPa, even more preferably at least 2,500 MPa, most preferably at least 2,550 MPa, even most preferably at least 2,600 MPa, or at least 2,650 MPa, or at least 2,700 MPa, or at least 2,750 MPa, or at least 2,800 MPa, or at least 2,850 MPa, or at least 2,900 MPa, or at least 2,950 MPa, or at least 3,000 MPa, or at least 3,050 MPa, or at least 3,100 MPa, determined by measuring the storage modulus (E') through calibrated dynamic mechanical thermal analysis performed at a heating rate of 5°C / min, according to ASTM D4065-20.

[0099] Advantageously, the resin exhibits a relaxation time τ37% of up to 2,000 seconds, determined at 37% residual stress on the relaxation modulus curve measured by torsional rheology of torsion bar specimens tested at 180°C and 5% constant strain; preferably, up to 1,950 s, or up to 1,900 s, or up to 1,850 s, or up to 1,800 s, or up to 1,750 s; more preferably up to 1,700 s. 00s, or at most 1,650s; or at most 1,600s, or at most 1,550s, or at most 1,500s, or at most 1,450s, or at most 1,400s, or at most 1,350s, or at most 1,300s; or at most 1,250s, or at most 1,200s, or at most 1,150s, more preferably at most 1,100s, even more preferably at most 1,050s; or at most 1,000s. The relaxation time τ37 is up to 950 s, up to 900 s, up to 850 s, up to 800 s, up to 750 s, up to 700 s, up to 650 s, up to 600 s, or up to 550 s, with the optimal relaxation time being up to 500 s, up to 450 s, up to 425 s, or up to 400 s, or even up to 375 s. Attached Figure Description

[0100] Figure 1: Representative tanδ, storage modulus and loss modulus of compound E(a) as a function of temperature; control 1(b) and control 2(b).

[0101] Figure 2: Representative stress-strain curves of compound E(a) at 22°C; control 1(b) and control 2(b).

[0102] Figure 3: Representative normalized stress-relaxation plots of compound E(a) at 1% strain at various temperatures; linear regression of the logarithm of relaxation time [ln(τ)] of compound E(b) relative to the reciprocal of temperature (1 / T); normalized stress-relaxation plots of control 1(c) and control 2(d) at 180°C and 1% strain. Detailed Implementation

[0103] The following definitions are given for this disclosure:

[0104] As used herein, the terms “comprising,” “comprises,” and “comprisedof” are synonymous with “including,” “includes,” “containing,” and “contains,” and are inclusive or open-ended, not excluding additional, unlisted members, elements, or method steps. The terms “comprising,” “comprises,” and “comprised of” also include the term “composed of.”

[0105] A description of a numerical range by endpoints includes all integers and, where appropriate, fractions contained within that range (e.g., when referring to, for example, the quantity of elements, 1 to 5 may include 1, 2, 3, 4, 5, and when referring to, for example, a measure, it may also include 1.5, 2, 2.75, and 3.80). The enumeration of endpoints also includes the listed endpoint values ​​themselves (e.g., 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range described herein is intended to include all subranges contained therein.

[0106] The term "dynamic covalent bond" should be understood in the context of glass-like polymers. Glass-like polymers are permanent chemical networks with dynamic covalent bonds, which allow the network to change its topology while maintaining a near-constant number of chemical bonds in the system at all temperatures below degradation. Dynamic covalent bonds are reversible and can rapidly reach thermodynamic equilibrium in response to stimuli. Further information can be found in Section 2.1 of the paper by Van Zee NJ et al., entitled "Vitrimers: Permanently crosslinked polymers with dynamic network topology" (Progress in Polymer Science, 2020, 104, 101233).

[0107] In one or more embodiments, specific features, structures, characteristics, or implementation methods may be combined in any suitable manner as will be apparent to those skilled in the art from this disclosure.

[0108] This disclosure relates to a formulation comprising at least a first component and a second component, wherein the formulation is intended to be cured for use in the manufacture of an epoxy-type glass-like polymer resin, the significant feature of which is that the first component comprises one or more epoxy components, wherein at least one epoxy component comprises at least one aromatic ring, two or more epoxy moieties and one or more dynamic covalent bonds; wherein at least one epoxy moieties are separated from at least one other epoxy moieties by at least one dynamic covalent bond; and the second component is or comprises one or more curing agents; and wherein at least one of the first component and the second component is a liquid at a temperature below or equal to 65°C; and wherein the first component is compatible with the second component as determined by compatibility test A at a temperature below or equal to 65°C.

[0109] More particularly, this disclosure relates to formulations comprising at least a first component and a second component, and optionally a third component, said third component being one or more kinetic modifiers, wherein said formulation is intended to be cured for use in the manufacture of epoxy-type glass-like polymers, and said formulation is notable for the following:

[0110] - The first component comprises one or more epoxy components, wherein at least one epoxy component comprises at least one aromatic ring, two or more epoxy moieties and one or more dynamic covalent bonds; wherein at least one epoxy moiety is separated from at least one other epoxy moieties by at least one dynamic covalent bond;

[0111] - The second component is or contains one or more curing agents, said curing agents being selected from compounds containing at least two active hydrogens, said active hydrogens being in the form of at least two aliphatic amine hydrogens and / or at least two aliphatic thiols;

[0112] Wherein at least one of the first component, the second component, and, if present, the third component is a liquid at a temperature below or equal to 65°C; and

[0113] Wherein, as determined by compatibility test A at a temperature below or equal to 65°C, the first component is compatible with the second component and, if present, the third component.

[0114] For example, at least one of the first component, the second component, and, if present, the third component is a liquid at a temperature below or equal to 60°C; preferably below or equal to 55°C, more preferably below or equal to 50°C, even more preferably below or equal to 45°C, most preferably below or equal to 40°C, or below or equal to 35°C, or below or equal to 30°C. For example, at least one of the first component, the second component, and, if present, the third component is a liquid at room temperature, i.e., at a temperature between 15°C and 30°C or between 20°C and 25°C.

[0115] Advantageously, each of the first component, the second component, and, if present, the third component is a liquid at a temperature of 65°C or lower. For example, each of the first component, the second component, and, if present, the third component is a liquid at a temperature of 60°C or lower; preferably, at 55°C or lower, more preferably at 50°C or lower, even more preferably at 45°C or lower, most preferably at 40°C or lower, or at 35°C or lower, or at 30°C or lower. For example, each of the first component, the second component, and, if present, the third component is a liquid at room temperature, i.e., at a temperature of 15°C to 30°C or 20°C to 25°C.

[0116] The formulations disclosed herein are specifically provided to produce easily processable epoxy compositions containing dynamic covalent bonds and forming robust and high-performance networks. In practice, the fact that at least one of the first and second components, preferably all, has a low melting point (i.e., below 65°C) facilitates their processing. For example, according to ASTM D2196-20, the viscosity of the formulation at a temperature below or equal to 65°C, as measured by a Brookfield viscometer with a suitable rotor, is less than 10,000 mPa·s, preferably less than 9,500 mPa·s, or less than 9,000 mPa·s. For example, as measured by a Brookfield viscometer with a suitable rotor according to ASTM D2196-20, the formulation has a viscosity at a temperature below or equal to 65°C in the range between 1 mPa·s and 10,000 mPa·s, preferably between 10 mPa·s and 9,500 mPa·s, or in the range between 100 mPa·s and 9,000 mPa·s. Low viscosity allows industrial composite materials to be processed in a way that enables conventional techniques, such as resin transfer molding (RTM), injection molding, pultrusion, or filament winding, to be implemented without problems.

[0117] For example, the formulation is a homogeneous liquid at a temperature of 65°C or less, preferably 60°C or less, more preferably 55°C or less, even more preferably 50°C or less, most preferably 45°C or less, or 40°C or less, or 35°C or less, or 30°C or less.

[0118] For example, the formulation is a homogeneous liquid at room temperature, i.e., at a temperature of 15°C to 30°C or 20°C to 25°C.

[0119] Therefore, this formulation can be used to manufacture one or more epoxy-type glass-like polymer resins. Advantageously, this formulation allows the manufacture of glass-like polymer materials without providing a significant amount of energy for curing. Thus, the manufacture of glass-like polymers can be initiated at temperatures below 65°C, or below 60°C, preferably below 55°C, more preferably below 50°C, even more preferably below 45°C, most preferably below 40°C, and even most preferably below 35°C.

[0120] Advantageously, the molar ratio of the amount of epoxy in the first component to the amount of active hydrogen in the second component is between 0.80:1 and 1.20:1, preferably between 0.85:1 and 1.15:1, more preferably between 0.90:1 and 1.10:1, and even more preferably between 0.95:1 and 1.05:1.

[0121] Preferably, the second component comprises two or more thiol moieties and / or one or more amine moieties, and the two or more active hydrogens are hydrogens derived from the two or more thiol moieties and / or one or more amine moieties. More preferably, the second component comprises one or more thiol moieties and / or one or more primary amine moieties, and the two or more active hydrogens are hydrogens derived from the two or more thiol moieties and / or the one or more primary amine moieties.

[0122] Advantageously, the formulation further comprises one or more kinetic modifiers. A kinetic modifier is defined herein as a compound capable of altering reaction kinetics. The reaction can be a network formation and / or bond exchange reaction. Therefore, the kinetic modifier can be a catalyst or a retarder for a given reaction. Those skilled in the art will select one or more kinetic modifiers depending on the reaction to be modulated.

[0123] Preferably, the one or more kinetic modifiers are free of hydroxyl groups. Preferably, the one or more kinetic modifiers are selected from one or more non-nucleophilic amine bases, one or more Lewis acids, one or more Brønsted bases, one or more Brønsted acids, one or more ionic liquids, or any combination thereof.

[0124] For example, the one or more nonnucleophilic amine bases are selected from triazabicyclodecene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (mTBD), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), one or more N-substituted imidazoles, or any mixture thereof.

[0125] For example, the one or more Lewis acids are selected from one or more of metal carboxylates, metal acetylacetonates, metal mercaptoacetates, metal thiopropionates, or any mixture thereof. Preferably, the one or more Lewis acids are selected from one or more of alkali metal carboxylates, alkali metal acetylacetonates, alkali metal mercaptoacetates, alkali metal thiopropionates, or any mixture thereof.

[0126] Examples of Brønsted bases are metal alkoxides.

[0127] Examples of Brønsted acids are sulfuric acid, organic sulfonic acid, hydrogen halide, carboxylic acid, halocarboxylic acid, boric acid, or any mixture thereof.

[0128] Examples of ionic liquids are quaternary ammonium salts, quaternary phosphonium salts, quaternary imidazolium salts, or any mixture thereof.

[0129] Preferably, the content of each of the one or more kinetic modifiers is less than 15 mol.% relative to the dynamic covalent bond molar content and / or less than the solubility limit, whichever is lower, and more preferably less than 10 mol.% relative to the dynamic covalent bond molar content and / or less than the solubility limit.

[0130] Preferably, the content of each of the one or more kinetic modifiers is at least 0.01 mol.% relative to the molar content of the dynamic covalent bond and / or less than the solubility limit, whichever is lower, and more preferably at least 0.1 mol.% relative to the molar content of the dynamic covalent bond and / or less than the solubility limit.

[0131] To properly determine the molar content of dynamic covalent bonds, the epoxy equivalent number of the first component can be considered. The epoxy equivalent number gives the average molecular weight per epoxy group and must be multiplied by the total number of epoxy groups. This gives the molecular weight of the first component recalculated from the epoxy content. Then, taking into account the number of dynamic covalent bonds in the first component, the molar content of dynamic covalent bonds can be determined.

[0132] First component

[0133] Preferably, the first component has the following chemical structure:

[0134]

[0135] Where R contains at least one aromatic ring;

[0136] Wherein X contains at least one dynamic covalent bond;

[0137] Where n, m, and k are integers and n+m+k≥2;

[0138] Where n+k≥1;

[0139] Wherein R' is an optional group, R' is selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more alicyclic groups, one or more aromatic groups, one or more heterocyclic (C3-C6 alkyl) groups having one or more heteroatoms selected from N, S, O or any combination thereof, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof, and one or more ketone heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof.

[0140] Furthermore, R'' is an optional group selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more alicyclic groups, and one or more heteroatoms selected from N, S, O, or any combination thereof; one or more -CH2- groups are present or absent that connect the optional R'' group to the remainder of the chemical structure and / or the adjacent epoxy moiety; preferably, a -CH2- group that connects the optional R'' group to the remainder of the chemical structure and / or the adjacent epoxy moiety is present.

[0141] Since n+m+k≥2, this means that the total number of epoxy functional groups is at least 2.

[0142] Since n+k≥1, this means that the total number of dynamic bonds is at least 1.

[0143] For example, R'' may be or may contain a heteroatom selected from N. More preferably, R'' may be or may contain .

[0144] Preferably, R comprises one or more aromatic rings, said aromatic rings being functionalized from one or more of the following: one or more linear aliphatic groups, one or more branched aliphatic groups, one or more alicyclic groups, one or more aromatic groups, one or more heterocyclic (C3-C6 alkyl) groups having one or more heteroatoms selected from N, S, O or any combination thereof, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof, and one or more ketone heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof.

[0145] Preferably, X comprises at least one dynamic covalent bond, wherein the one or more covalent bonds are selected from one or more carboxylic ester bonds, one or more siloxane bonds, one or more silyl ether bonds, one or more disulfide bonds, one or more borate ester bonds, one or more phosphonate ester bonds, one or more phosphate ester bonds, one or more triazine ether bonds, one or more amide bonds, or combinations thereof; and are in any orientation and may or may not contain one or more -CH2- groups that connect the dynamic bond to the remainder of the chemical structure.

[0146] Preferably, X comprises or is a carboxylic ester bond; the carboxylic ester bond is in any orientation and may or may not contain one or more -CH2- groups that connect the carboxylic ester bond to the rest of the chemical structure; more preferably, X comprises or is a dynamic covalent bond, the dynamic covalent bond being a carboxylic ester bond, the carboxylic ester bond being in any orientation and containing a -CH2- group that connects the carboxylic ester bond to the rest of the chemical structure.

[0147] Preferably, the first component comprises one or more epoxy components, wherein at least one epoxy component comprises at least one aromatic ring, two epoxy moieties and one or more dynamic covalent bonds; wherein at least one epoxy moiety is separated from at least one other epoxy moieties by at least one dynamic covalent bond.

[0148] For example, the first component has the following chemical structure

[0149]

[0150] Where R contains at least one aromatic ring;

[0151] Wherein X contains at least one dynamic covalent bond;

[0152] Where m is an integer between 1 and 6.

[0153] Where n is an integer greater than or equal to 0.

[0154] Furthermore, R' is an optional group selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more alicyclic groups, one or more aromatic groups, one or more heterocyclic (C3-C6 alkyl) groups having one or more heteroatoms selected from N, S, O or any combination thereof, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof, and one or more ketone heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof.

[0155] The fact that the dynamic covalent bond (X) is directly attached to the aromatic ring (R) accelerates bond exchange and thus improves processability.

[0156] Preferably, R comprises one or more aromatic rings, said aromatic rings being functionalized from one or more of the following: one or more linear aliphatic groups, one or more branched aliphatic groups, one or more alicyclic groups, one or more aromatic groups, one or more heterocyclic (C3-C6 alkyl) groups having one or more heteroatoms selected from N, S, O or any combination thereof, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof, and one or more ketone heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof.

[0157] Preferably, X comprises at least one dynamic covalent bond, wherein the one or more covalent bonds are selected from one or more carboxylic ester bonds, one or more siloxane bonds, one or more silyl ether bonds, one or more disulfide bonds, one or more borate ester bonds, one or more phosphonate ester bonds, one or more phosphate ester bonds, one or more triazine ether bonds, one or more amide bonds, or combinations thereof; and are in any orientation and may or may not contain one or more -CH2- groups that connect the dynamic bond to the remainder of the chemical structure.

[0158] Preferably, X comprises or is a carboxylic ester bond; the carboxylic ester bond is in any orientation and may or may not contain one or more -CH2- groups that connect the carboxylic ester bond to the rest of the chemical structure; more preferably, X comprises or is a dynamic covalent bond, the dynamic covalent bond being a carboxylic ester bond, the carboxylic ester bond being in any orientation and containing a -CH2- group that connects the carboxylic ester bond to the rest of the chemical structure.

[0159] The first component can preferably be selected from:

[0160]

[0161] Or a mixture thereof.

[0162] More preferably, the first component can be selected from

[0163]

[0164] Or a mixture thereof.

[0165] In one or more embodiments, the first component is selected from the diglycidyl ester family of phthalic acid. For example, the first component is selected from the diglycidyl ester family of phthalic acid; wherein the phthalic acid may be substituted or unsubstituted.

[0166] In one or more embodiments, the first component is selected from the triglycidyl ester family of benzoic acid. For example, the first component is selected from the triglycidyl ester family of benzoic acid; wherein the benzoic acid may be substituted or unsubstituted.

[0167] In one or more embodiments, the first component is selected from the family of epoxidized hydroxybenzoic acids containing a glycidyl ether and a glycidyl ester. For example, the first component is selected from the family of epoxidized hydroxybenzoic acids containing a glycidyl ether and a glycidyl ester; wherein the hydroxybenzoic acid may be substituted or unsubstituted.

[0168] In one or more embodiments, the first component is selected from the family of diglycidyl ethers of bisphenols containing two phenolic substituents separated by a dynamic bond. For example, the first component is selected from the family of diglycidyl ethers of bisphenols containing two phenolic substituents separated by a dynamic bond; wherein the bisphenol may be substituted or unsubstituted.

[0169] In one or more embodiments, the first component is selected from the family of epoxidized aminobenzoic acids containing two glycidylamines and one glycidyl ester. For example, the first component is selected from the family of epoxidized aminobenzoic acids containing two glycidylamines and one glycidyl ester; wherein the aminobenzoic acid may be substituted or unsubstituted.

[0170] Second component

[0171] For example, the second component comprises two or more thiol moieties (e.g., -SH) and / or one or more amine moieties; preferably, the second component comprises one or more amine moieties. Preferably, the one or more amine moieties are one or more primary amine moieties (e.g., -NH2) and zero or more secondary amine moieties (e.g., -NH-) or two or more secondary amine moieties, more preferably one or more primary amine moieties (e.g., -NH2).

[0172] For example, the second component is selected from compounds containing at least two aliphatic amine hydrogens and / or at least two aliphatic thiols.

[0173] Preferably, the at least one curing agent is selected from one or more poly(epoxide) oligomers, one or more poly(siloxane) oligomers, one or more poly(diene) oligomers, one or more poly(olefin) oligomers, one or more poly(amide) oligomers, one or more poly(alkylene sulfide) oligomers, one or more poly(alkylene disulfide) oligomers, or any combination thereof, wherein the one or more oligomers are one or more amine-terminated oligomers and / or one or more thiol-terminated oligomers.

[0174] The second component, which may be selected as or include at least one curing agent, can be chosen from...

[0175]

[0176] Or a mixture thereof.

[0177] Preferably, the second component, which is or includes at least one curing agent, can be selected from...

[0178]

[0179] Or a mixture thereof.

[0180] More preferably, the second component, which is or includes at least one curing agent, may be selected from:

[0181]

[0182] Or a mixture thereof.

[0183] Even more preferably, the second component, which is or includes at least one curing agent, may be selected from:

[0184]

[0185] Or a mixture thereof.

[0186] Most preferably, the second component, which is or includes at least one curing agent, can be selected from:

[0187] Or a mixture thereof.

[0188] A method for manufacturing an epoxy-type glass-like polymer resin is also disclosed, comprising the following steps:

[0189] a) Provide at least a first component and a second component of the formulation according to the first aspect;

[0190] b) Mix all components together to obtain the formulation; wherein the formulation is a homogeneous liquid at a temperature of 65°C or below;

[0191] c) Curing the formulation to obtain an epoxy-type glass-like polymer resin;

[0192] The curing in step (c) is initiated at a temperature below 65°C, or below 60°C, preferably below 55°C, more preferably below 50°C, even more preferably below 45°C, most preferably below 40°C, and even most preferably below 35°C.

[0193] A method for manufacturing an epoxy-type glass-like polymer resin is also disclosed, comprising the following steps:

[0194] a) Provides a first and second component of the formulation according to the first aspect, and an optional third component, said third component being one or more kinetic modifiers;

[0195] b) Mix the first component, the second component, and, if present, the third component together to obtain the formulation; wherein the formulation is a homogeneous liquid at a temperature below or equal to 65°C;

[0196] c) Curing the formulation to obtain an epoxy-type glass-like polymer resin;

[0197] The curing in step (c) is initiated at a temperature below 65°C, or below 60°C, preferably below 55°C, more preferably below 50°C, even more preferably below 45°C, most preferably below 40°C, and even most preferably below 35°C.

[0198] For example, the curing in step (c) is initiated at a temperature of 15°C to 65°C, or 15°C to 60°C, or 15°C to 55°C, or 20°C to 50°C.

[0199] For example, the curing in step (c) is initiated at room temperature, i.e. at a temperature of 15°C to 30°C or 20°C to 25°C.

[0200] For example, this method is a solvent-free method.

[0201] Subsequently, an epoxy-type glass-like polymer resin containing a composition prepared by combining all the components of the formulation is obtained.

[0202] The glass-like polymers disclosed herein advantageously exhibit a glass transition temperature Tg of at least 55°C, determined by differential scanning calorimetry at a heating rate of 5°C / min according to ASTM D3418-21; preferably, at least 60°C, more preferably at least 65°C, even more preferably at least 70°C, most preferably at least 75°C, or at least 80°C, or at least 85°C, or at least 90°C, or at least 100°C, or at least 105°C, or at least 110°C, or at least 115°C, or at least 120°C, or even most preferably at least 125°C, or at least 130°C, or at least 135°C, or at least 140°C.

[0203] The glass-like polymers of this disclosure advantageously exhibit a room temperature elastic modulus of at least 1,400 MPa, as determined by storage modulus (E') measurements via dynamic mechanothermal analysis calibrated according to ASTM D4065-20 at a heating rate of 5°C / min; or at least 1,450 MPa, or at least 1,500 MPa, or at least 1,550 MPa, or at least 1,600 MPa, or at least 1,650 MPa, or at least 1,700 MPa, or at least 1,750 MPa, or at least 1,800 MPa, or at least 1,850 MPa, or at least 1,900 MPa, or at least 1,950 MPa, or at least 2,000 MPa, or at least 2,050 MPa, or at least 2,100 MPa, or at least 2,150 MPa, or at least 2,200 MPa, or at least 2,250 MPa, or at least 2,300 MPa. The room temperature modulus of elasticity is at least 2,350 MPa, preferably at least 2,390 MPa, or at least 2,400 MPa, more preferably at least 2,450 MPa, even more preferably at least 2,500 MPa, most preferably at least 2,550 MPa, even most preferably at least 2,600 MPa, or at least 2,650 MPa, or at least 2,700 MPa, or at least 2,750 MPa, or at least 2,800 MPa, or at least 2,850 MPa, or at least 2,900 MPa, or at least 2,950 MPa, or at least 3,000 MPa, or at least 3,050 MPa, or at least 3,100 MPa.

[0204] The glass-like polymer of this disclosure advantageously exhibits a relaxation time τ37% of up to 2,000 seconds (two thousand), determined at 37% residual stress on the relaxation modulus curve measured by torsional rheology of torsion bar specimens tested at 180°C and 5% constant strain; preferably, up to 1,950 s, or up to 1,900 s, or up to 1,850 s, or up to 1,800 s, or up to 1,750 s; more preferably up to 1, 700s, or at most 1,650s; or at most 1,600s, or at most 1,550s, or at most 1,500s, or at most 1,450s, or at most 1,400s, or at most 1,350s, or at most 1,300s; or at most 1,250s, or at most 1,200s, or at most 1,150s, more preferably at most 1,100s, even more preferably at most 1,050s; or at most 1,000s, or at most 950s The relaxation time τ37 is at most 900 s, or at most 850 s, or at most 800 s, or at most 750 s, or at most 700 s, or at most 650 s, or at most 600 s, or at most 550 s, with the optimal relaxation time being at most 500 s, or at most 450 s, or at most 425 s, or at most 400 s, or even the optimal relaxation time being at most 375 s.

[0205] The glass-like polymers disclosed herein advantageously exhibit onset weight loss temperatures Tonset as determined by thermogravimetric analysis according to ASTM E2550-17, at most 275°C, preferably at most 250°C, more preferably at most 245°C, even more preferably at most 240°C, most preferably at most 235°C, even most preferably at most 230°C, or at most 225°C, or at most 220°C, or at most 215°C, or at most 210°C. 起始 .

[0206] Test and measurement methods

[0207] Compatibility Test A

[0208] In itself, the compatibility test A measures the compatibility between the first and second components, which includes the following methods:

[0209] 1) Provide 5 g of the first component, the weight of which is expressed as dry weight;

[0210] 2) Provide the amount of the second component necessary to achieve a molar ratio of the amount of epoxy in the first component to the amount of active hydrogen in the second component of 0.80:1 to 1.20:1, preferably 0.85:1 to 1.15:1, more preferably 0.90:1 to 1.10:1, and even more preferably 0.95:1 to 1.05:1;

[0211] 3) To liquefy at least one component by heating it to a temperature above its melting point but below 65°C;

[0212] 4) Add the second component provided in the second step to the first component provided in the first step;

[0213] 5) Mix the first and second components in a planetary centrifugal mixer or equivalent at 800 rpm for 30 seconds and at 2,000 rpm for 2 minutes to achieve effective mixing and degassing, while maintaining the mixture at the temperature provided in step 3.

[0214] 6) Place the mixture obtained in the previous step into a 15 mL centrifuge tube and centrifuge at 3,000 rpm for 2 minutes to obtain a centrifuged mixture, while maintaining the mixture at the temperature provided in the third step;

[0215] 7) Visually observe the number of layers and / or phases present in the centrifuged mixture obtained in the previous step, while maintaining the mixture at the temperature provided in the third step.

[0216] If one or more solid particles and / or more than one liquid layer are visible in the centrifuged mixture, visual observation performed in the final step indicates a lack of compatibility.

[0217] Visual observation of a single liquid layer without particles indicates the compatibility of the first and second components at the proportions discussed.

[0218] Differential scanning calorimetry (DSC)

[0219] Differential scanning calorimetry (DSC) was performed according to ASTM D3418-21. Samples were hermetically sealed in an Al disk in air and analyzed by DSC on a DSC 300 Caliris Select differential calorimeter (NETZSCH) from -50°C to 210°C. Each sample underwent two heating-cooling cycles at a heating rate of 5°C / min under a N2 atmosphere. The glass transition temperature (Tg) was determined by the heating profile during the second heating cycle.

[0220] Thermogravimetric analysis (TGA)

[0221] Thermogravimetric analysis (TGA) of polymer samples was performed according to ASTM E2550-17. TGA was conducted in air on a TGA2 STARe system (Mettler Toledo) at a heating rate of 5°C / min. The initial weight loss temperature (T0.5) was determined according to the above standard at 0.5 wt%. 起始Then round to the nearest 5°C. The 5% weight loss temperature (T) is determined according to the above standard at 5 wt%. 5% Then round it to the nearest 5°C.

[0222] Dynamic mechanical thermal analysis (DMTA)

[0223] Dynamic mechanical-thermal analysis was performed according to ASTM D4065-20. Measurements were taken on strips (typically length × width × thickness = 25 × 5.5 × 1.5 mm) using a DMA GABO Eplexor (Netzsch) operating in tensile mode (static strain: 2%, dynamic strain: 0.5%, contact force: 0.80 N). Experiments were conducted in air from -30 to 190°C at a heating rate of 5°C / min at a frequency of 1 Hz. This setup provided the storage and loss moduli (E' and E''). The damping parameter, or loss factor (tanδ), was defined as the ratio tanδ = E'' / E'.

[0224] Using an Anton Paar Physica MCR 302 rheometer equipped with a CTD 450 temperature control unit, in a rectangular torsion mode with bar geometry, Rheological measurement The glass-like polymer resin sample, in strip form (typically length × width × thickness = 25 × 5.5 × 1.5 mm), was directly loaded into the clamping system. All measurements were performed in air at 180°C. The sample was allowed to equilibrate at the specified temperature for 5 minutes, and then a constant strain (1%) was applied. The relaxation time (s) was defined as the time it takes for the relaxation modulus to reach a value equal to 37% (1 / e) of the modulus 1 s after the start of the measurement [Capelot, M., Unterlass, MM, Tournilhac, F. & Leibler, L. Catalytic control of the vitrimerglass transition. ACS Macro Lett. 1, 789–792 (2012).]. The test was repeated at least twice to ensure good reproducibility of the results.

[0225] Mechanical properties of glass-like polymer resin samples , i.e. σ t - Tensile strength (kPa), E t Tensile modulus (MPa) and elongation (%) were measured at room temperature using an Instron 5967 universal testing machine (Norwood, MA, USA) equipped with a 1 kN force sensor, according to ISO 527 standard. Measurements were performed on dog-bone specimens at a crosshead speed of 2 mm / min, according to ISO 527-1BA. At least five specimens were tested for each reference.

[0226] Example

[0227] A better understanding of the implementation of this disclosure will be gained by reviewing the following examples.

[0228] First, all formulation components were placed in a 25 mL polypropylene (PP) cup and then mixed and degassed at 800 rpm for 30 seconds using a planetary centrifuge (Hauschild speed mixer DAC 600.2 VAC-P), followed by mixing and degassed at 2,000 rpm for 120 seconds. The mixture was left to cure under ambient conditions for 12 hours. Post-curing was then performed using the following ramp heating program: 1 hour at 60°C, 1 hour at 90°C, 1 hour at 120°C, 1 hour at 130°C, and 1 hour at 140°C. The glass-like polymer was then demolded and immediately post-cured again at 180°C for 2 hours. After post-curing, the resulting sample was allowed to cool naturally to room temperature.

[0229] The following components have been used:

[0230] bis(2,3-epoxypropyl) phthalate (CAS: 7195-45-1) is commercially available at Nagase ChemTex.

[0231] Cyclohexane-1,3-dimethyldimethylamine (CAS: 2579-20-6) is commercially available from BLD Pharmatech. Bis(3-aminopropyl)methylamine (CAS: 105-83-9) is commercially available from TCI Chemicals.

[0232] Bis(3-aminopropyl)amine (CAS: 56-18-8) is commercially available from TCI Chemicals.

[0233] m-Phenylenediamine (CAS: 1477-55-0) is commercially available at Sigma-Aldrich.

[0234] p-Phenylenediamine (CAS: 539-48-0) is commercially available from Sigma-Aldrich.

[0235] 4,4'-Diaminodicyclohexylmethane (CAS: 1761-71-3) is commercially available from TCI Chemicals.

[0236] Cyclohexane-1,2-dicarboxylic acid bis(2,3-epoxypropyl) ester (CAS: 5493-45-8) is commercially available from TCI Chemicals.

[0237] 1,2-Bis(ethylene oxide-2-ylmethoxy)benzene (CAS: 2851-82-3) is available commercially from BLD Pharmatech.

[0238] Example 1

[0239] The following synthesis of epoxy-type glass-like polymer resin (compound A) was carried out.

[0240] Compound A was prepared according to a standard procedure from bis(2,3-epoxypropyl) phthalate (8.07 g) and bis(3-aminopropyl)methylamine (1.93 g), maintaining a molar ratio of epoxy groups to active amine hydrogens of 1:1. The mixture was brought to room temperature to produce a liquid formulation, which was then allowed to solidify.

[0241] T g (DSC, 5°C / min) = 61°C; T 起始 (TGA, 5°C / min) = 220°C; E'(DMTA, 5°C / min) = 1000MPa; τ 37% (180°C, 1% strain) = 561s.

[0242] Determination of the dynamic covalent bond molar content in 8.07 g bis(2,3-epoxypropyl) phthalate

[0243] The weight of bis(2,3-epoxypropyl) phthalate was calculated using the manufacturer's provided epoxy equivalent weight (EEW) of 152. This EEW refers to an average molecular weight of 152 g / mol per epoxy group. Due to the presence of two epoxy moieties, the recalculated average molecular weight is 304 g / mol. Therefore, the amount of dynamic covalent bonds, i.e., the amount of the two carboxylic acid ester bonds present in the compound, is (8.07 / 304). 2 = 0.053 mol.

[0244] Example 2

[0245] The following synthesis (compound B) of an epoxy-type glass-like polymer resin was carried out.

[0246] Compound B was prepared according to a standard procedure from bis(2,3-epoxypropyl) phthalate (8.53 g) and bis(3-aminopropyl)amine (1.47 g), maintaining a molar ratio of epoxy groups to active amine hydrogens of 1:1. The mixture was brought to room temperature to produce a liquid formulation, which was then allowed to solidify.

[0247] T g (DSC, 5°C / min) = 83°C; T 起始 (TGA, 5°C / min) = 220°C; E'(DMTA, 5°C / min) = 3400MPa; τ 37% (180°C, 1% strain) = 290s.

[0248] Example 3

[0249] The following synthesis (compound C) of an epoxy-type glass-like polymer resin was carried out.

[0250] Compound C was prepared from bis(2,3-epoxypropyl) phthalate (8.17 g) and m-phenylenediamine (1.83 g) according to a standard procedure, maintaining a molar ratio of epoxy groups to active amine hydrogens of 1:1. The mixture was brought to room temperature to produce a liquid formulation, which was then allowed to solidify.

[0251] T g (DSC, 5°C / min) = 106°C; T 起始 (TGA, 5°C / min) = 220°C; E'(DMTA, 5°C / min) = 2700MPa; τ 37% (180°C, 1% strain) = 500s.

[0252] Example 4

[0253] The following synthesis (compound D) of an epoxy-type glass-like polymer resin was carried out.

[0254] Compound D was prepared according to a standard procedure from bis(2,3-epoxypropyl) phthalate (8.17 g) and p-phenylenediamine (1.83 g), maintaining a molar ratio of epoxy groups to active amine hydrogens of 1:1. The mixture was brought to room temperature to produce a liquid formulation, which was then allowed to solidify.

[0255] T g (DSC, 5°C / min) = 104°C; T 起始 (TGA, 5°C / min) = 235°C; E'(DMTA, 5°C / min) = 3100MPa; τ 37% (180°C, 1% strain) = 1050s.

[0256] Example 5

[0257] The following synthesis (compound E) of an epoxy-type glass-like polymer resin was carried out.

[0258] Compound E was prepared according to a standard procedure from bis(2,3-epoxypropyl) phthalate (7.43 g) and 4,4'-diaminodicyclohexylmethane (2.57 g), maintaining a molar ratio of epoxy groups to active amine hydrogens of 1:1. The mixture was brought to room temperature to produce a liquid formulation, which was then allowed to solidify.

[0259] T g (DSC, 5°C / min) = 134°C; T 起始(TGA, 5°C / min) = 230°C; E'(DMTA, 5°C / min) = 2700MPa; τ 37% (180°C, 1% strain) = 1000s.

[0260] Example 6

[0261] The following synthesis (compound F) of an epoxy-type glass-like polymer resin was carried out.

[0262] Compound F was prepared according to a standard procedure from bis(2,3-epoxypropyl) phthalate (8.07 g) and cyclohexane-1,3-dimethyldimethylamine (1.93 g), maintaining a molar ratio of epoxy groups to active amine hydrogens of 1:1. The mixture was brought to room temperature to produce a liquid formulation, which was then allowed to solidify.

[0263] T g (DSC, 5°C / min) = 114°C; T 起始 (TGA, 5°C / min) = 220°C; E'(DMTA, 5°C / min) = 2500MPa; τ 37% (180°C, 1% strain) = 312s.

[0264] Comparative Example 1

[0265] The following synthesis of an epoxy-type glass-like polymer resin was carried out (Comparative Example 1).

[0266] Comparative sample was prepared according to a standard procedure from bis(2,3-epoxypropyl) cyclohexane-1,2-dicarboxylate (7.30 g) and 4,4'-diaminodicyclohexylmethane (2.70 g), maintaining a molar ratio of epoxy groups to active amine hydrogens of 1:1. The mixture was brought to room temperature to produce a liquid formulation, which was then allowed to cure.

[0267] T g (DSC, 5°C / min) = 110°C; T 起始 (TGA, 5°C / min) = 240°C; E'(DMTA, 5°C / min) = 2600MPa; τ 37% (180°C, 1% strain) = 2530s.

[0268] Comparative Example 2

[0269] The following synthesis of an epoxy-type glass-like polymer resin was carried out (Comparative Example 2).

[0270] Comparative example samples were prepared according to a standard procedure from 1,2-bis(ethylene oxide-2-ylmethoxy)benzene (6.79 g) and 4,4'-diaminodicyclohexylmethane (3.21 g), maintaining a molar ratio of epoxy groups to active amine hydrogens of 1:1. The mixtures were mixed at room temperature to produce a liquid formulation, which was then allowed to cure.

[0271] T g (DSC, 5°C / min) = 110°C; T 起始 (TGA, 5°C / min) = 258°C; E'(DMTA, 5°C / min) = 1700 MPa; no relaxation was observed at 180°C and 1% strain.

[0272] In addition to the ability to generate these materials from liquid formulations at low ambient temperatures (typically below 65°C in all the foregoing embodiments, at RT), this disclosure has thus demonstrated that it provides epoxy-type glass-like polymers exhibiting high performance.

[0273] Table 1. Comparative examples of the properties of epoxy-based glass-like polymers and epoxy-based glass-like polymers.

[0274]

[0275] a Measured using DSC at a heating rate of 5°C / min; b The loss was measured in air using a TGA at a heating rate of 5°C / min, resulting in a loss of 0.5% by weight. c The 5% weight loss was measured in air using a TGA at a heating rate of 5°C / min. d Storage modulus (E') at 25°C was measured using DMTA at a heating rate of 5°C / min; e The residual stress was determined on the relaxation modulus curve at 37% by torsional rheology at 180°C and a fixed strain of 1%. f No relaxation was observed.

[0276] Table 1 describes the properties of Examples 1-6 (compound AF) and two comparative examples: Glass-like polymer comparative example 1 and non-glass-like polymer conventional thermosetting comparative example 2.

[0277] All compounds have elevated glass transition temperatures (61–134°C), which enables the disclosed glass-like polymers to have a wider range of application temperatures.

[0278] Since the storage modulus (E') of compounds B to F is higher than that of the comparative examples (both the glass-like polymer and the conventional non-glass-like polymer), this means that compounds B to F are more rigid and more resistant to elastic deformation (see Figure 1). Further evidence of the excellent mechanical properties of compounds A to E is provided by quasi-static tensile testing (Figure 2). Here, although similar tensile properties were observed in both the glass-like polymer E and the glass-like polymer comparative example 1, the modulus of these systems is significantly greater than that of the conventional non-glass-like polymer comparative example 2.

[0279] Finally, glass-like polymers A through F all exhibited faster stress relaxation than glass-like polymer Comparative Example 1, while non-glass-like polymer Comparative Example 2 did not experience significant stress relaxation in any case, consistent with the lack of dynamic bonds in its structure (Figure 3). In all cases, the presence of aromatic ester groups in the epoxides incorporated into the first component of the formulation significantly contributed to the thermal, dynamic, and quasi-static mechanical and rheological properties of the compounds.

[0280] Therefore, compared with Comparative Examples 1 and 2, it has been demonstrated that all compounds according to this disclosure have similar levels of mechanical properties, as well as similar or higher glass transition temperatures and shorter stress relaxation times.

Claims

1. A formulation comprising at least a first component and a second component and optionally a third component, said third component being one or more kinetic modifiers, wherein said formulation is intended to be cured to produce an epoxy-type glass-like polymer resin, said formulation being characterized in that: The first component comprises one or more epoxy components, wherein at least one epoxy component comprises at least one aromatic ring, two or more epoxy moieties and one or more dynamic covalent bonds; At least one epoxy moiety is separated from at least one other epoxy moiety by at least one dynamic covalent bond; The second component is or contains one or more curing agents, said curing agents being selected from compounds containing at least two active hydrogens, said active hydrogens being in the form of at least two aliphatic amine hydrogens and / or at least two aliphatic thiols; Wherein at least one of the first component, the second component, and the third component, if present, is a liquid at a temperature of 65°C or below; and Wherein, as determined by compatibility test A at a temperature below or equal to 65°C, the first component is compatible with the second component and, if present, the third component.

2. The formulation according to claim 1, characterized in that... Each of the first component, the second component, and, if present, the third component, is a liquid at a temperature of 65°C or below.

3. The formulation according to claim 1 or 2, characterized in that, The formulation has a viscosity of less than 10,000 mPa·s at a temperature below or equal to 65°C, as determined by a Brookfield viscometer with a suitable rotor according to ASTM D2196-20.

4. The formulation according to any one of claims 1 to 3, characterized in that, The molar ratio of the amount of epoxy in the first component to the amount of active hydrogen in the second component is between 0.80:1 and 1.20:

1.

5. The formulation according to any one of claims 1 to 4, characterized in that... The one or more kinetic modifiers do not contain hydroxyl groups.

6. The formulation according to any one of claims 1 to 5, characterized in that... The one or more kinetic modifiers are selected from one or more nonnucleophilic amine bases, one or more Lewis acids, one or more Brønsted bases, one or more Brønsted acids, one or more ionic liquids, or any combination thereof.

7. The formulation according to any one of claims 1 to 6, characterized in that... The content of each of the one or more kinetic modifiers is less than 15 mol% relative to the molar content of dynamic covalent bonds.

8. The formulation according to any one of claims 1 to 7, characterized in that... The first component has the following chemical structure Where R contains at least one aromatic ring; Wherein X contains at least one dynamic covalent bond; Where n, m, and k are integers and n+m+k≥2; Where n+k≥1; Furthermore, R' is an optional group, which is selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more alicyclic groups, one or more aromatic groups, one or more heterocyclic (C3-C6 alkyl) groups having one or more heteroatoms selected from N, S, O or any combination thereof, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof, and one or more ketone heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof. And R'' is an optional group, which is selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more alicyclic groups, one or more heteroatoms selected from N, S, O or any combination thereof; with or without one or more -CH2- groups connecting the optional R'' group to the rest of the chemical structure and / or the adjacent epoxy moiety.

9. The formulation according to claim 8, characterized in that, R comprises one or more aromatic rings, said aromatic rings being functionalized from one or more of the following: one or more linear aliphatic groups, one or more branched aliphatic groups, one or more alicyclic groups, one or more aromatic groups, one or more heterocyclic (C3-C6 alkyl) groups having one or more heteroatoms selected from N, S, O or any combination thereof, one or more ortho-substituted phenyl groups, one or more meta-substituted phenyl groups, one or more para-substituted phenyl groups, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof, and one or more ketone heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof.

10. The formulation according to claim 8 or 9, characterized in that... X comprises at least one dynamic covalent bond, wherein the one or more dynamic covalent bonds are selected from one or more carboxylic acid ester bonds, one or more siloxane bonds, one or more silyl ether bonds, one or more disulfide bonds, one or more borate ester bonds, one or more phosphonate ester bonds, one or more phosphate ester bonds, one or more triazine ether bonds, one or more amide bonds, or combinations thereof; And it is in any orientation and has or does not have one or more -CH2- groups that connect the dynamic bond to the rest of the chemical structure.

11. The formulation according to claim 10, characterized in that, X comprises a dynamic covalent bond, which is a carboxylic acid ester bond, the carboxylic acid ester bond being in any orientation and having or not having one or more -CH2- groups that connect the carboxylic acid ester bond to the rest of the chemical structure; preferably, X comprises a dynamic covalent bond, which is a carboxylic acid ester bond, the carboxylic acid ester bond being in any orientation and having a -CH2- group that connects the carboxylic acid ester bond to the rest of the chemical structure.

12. The formulation according to any one of claims 1 to 11, characterized in that... The first component is selected from Or a mixture thereof.

13. The formulation according to any one of claims 1 to 12, characterized in that... The first component is selected from the diglycidyl ester family of phthalic acid.

14. The formulation according to any one of claims 1 to 13, characterized in that... The first component is selected from the triglycidyl ester family of benzotriglycerides.

15. The formulation according to any one of claims 1 to 14, characterized in that... The first component is selected from the epoxidized hydroxybenzoic acid family, which contains a glycidyl ether and a glycidyl ester.

16. The formulation according to any one of claims 1 to 15, characterized in that, The first component is selected from the diglycidyl ether family of bisphenols containing two phenolic substituents separated by dynamic bonds.

17. The formulation according to any one of claims 1 to 16, characterized in that... The epoxidized aminobenzoic acid family contains two glycidylamines and one glycidyl ester.

18. The formulation according to any one of claims 1 to 17, characterized in that... The at least one curing agent is selected from one or more oligomers of poly(epoxide), one or more oligomers of poly(siloxane), one or more oligomers of poly(diene), one or more oligomers of poly(olefin), one or more oligomers of poly(amide), one or more oligomers of poly(alkylene sulfide), one or more oligomers of poly(alkylene disulfide), or any combination thereof, wherein the one or more oligomers are one or more amine-terminated oligomers and / or one or more thiol-terminated oligomers.

19. The formulation according to any one of claims 1 to 18, characterized in that, The second component is or contains at least one curing agent selected from the following: Or a mixture thereof.

20. A method for manufacturing an epoxy-type glass-like polymer resin, characterized in that it comprises the following steps: a) Providing a first component and a second component of the formulation according to any one of claims 1 to 19, and optionally a third component, said third component being one or more kinetic modifiers; b) Mix the first component, the second component, and, if present, the third component together to obtain the formulation; wherein the formulation is a homogeneous liquid at a temperature below or equal to 65°C; c) Curing the formulation to obtain an epoxy-type glass-like polymer resin; The curing in step (c) is initiated at a temperature below 65°C.

21. An epoxy-type glass-like polymer resin comprising a composition prepared by combining a first component, a second component, and, if present, a third component of a formulation as defined in any one of claims 1 to 19.

22. The epoxy-type glass-like polymer resin according to claim 21, characterized in that, The resin exhibits a glass transition temperature T of at least 60°C, as determined by differential scanning calorimetry at a heating rate of 5°C / min according to ASTM D3418-21. g .

23. The epoxy-type glass-like polymer resin according to claim 21 or 22, characterized in that, The resin exhibits a glass transition temperature T of at least 85°C, as determined by differential scanning calorimetry at a heating rate of 5°C / min according to ASTM D3418-21. g .

24. The epoxy-type glass-like polymer resin according to any one of claims 21 to 23, characterized in that, The resin exhibits a room temperature elastic modulus E' of at least 1,500 MPa, which is determined by a storage modulus (E') measurement performed by a calibrated dynamic mechanical-thermal analysis according to ASTM D4065-20 at a heating rate of 5°C / min.

25. The epoxy-type glass-like polymer resin according to any one of claims 21 to 24, characterized in that, The resin exhibits a room temperature elastic modulus E' of at least 2,000 MPa, which is determined by a storage modulus (E') measurement performed by a calibrated dynamic mechanical-thermal analysis according to ASTM D4065-20 at a heating rate of 5°C / min.

26. The epoxy-type glass-like polymer resin according to any one of claims 21 to 25, characterized in that, The resin exhibits a relaxation time τ37% of up to 2,000 seconds, which is determined at 37% residual stress on the relaxation modulus curve using torsional rheology measurements of torsion bar specimens tested at 180°C and 5% fixed strain.

27. The epoxy-type glass-like polymer resin according to any one of claims 21 to 26, characterized in that, The resin exhibits a relaxation time τ37% of up to 1000 seconds, which is determined at 37% residual stress on the relaxation modulus curve using torsional rheology measurements of torsion bar specimens tested at 180°C and 5% fixed strain.

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