Method for preparing epoxy-derived covalent adaptive networks

Abstract

The present invention relates to a process for preparing a composition comprising an epoxy-based covalent adaptive network. The method comprises the steps of: a) contacting a controlled amount of compound A with compound B to obtain a mixture comprising a curing agent. Compound A has a'functional groups of the-C (= O) ORx type and / or-C (= O)-type, where the a 'functional groups are arranged in pairs at a controlled distance from each other. The b'primary amine functions are arranged in pairs and are arranged at a controlled distance from one another, b) contacting the mixture obtained in step a) with at least one compound C having epoxy functions to obtain an epoxy-derived covalent adaptive network, and compositions obtainable by such a process.

Description

Technical Field

[0001] The present invention relates to a method for preparing a composition comprising an epoxy-derivatized covalent adaptive network. In addition, the present invention relates to a composition comprising an epoxy-derivatized covalent adaptive network. Background Art

[0002] Epoxy-based compositions are known in the art. Due to their excellent physical-mechanical properties and excellent corrosion resistance and wear resistance, epoxy-based compositions are widely used, for example, as coatings.

[0003] Most epoxy-based coatings are obtained by using multifunctional amines such as aliphatic amines, polyamides and polyamidoamines as curing agents.

[0004] EP1024159 describes the use of polyamidoamine curing agents for curing epoxy resins. The epoxy curing agent includes a reaction product of a mixture comprising aliphatic monocarboxylic acids, aromatic monocarboxylic acids, aromatic dicarboxylic acids and polyethyleneamine, wherein the equivalent ratio of aliphatic monocarboxylic acids to aromatic monocarboxylic acids is in the range of about 1:0.2 to about 1:1.5, the equivalent ratio of monocarboxylic acids to aromatic dicarboxylic acids is in the range of about 1:0.1 to about 1:0.6, and the ratio of the total number of moles of polyamine to the total equivalent of acid may be in the range of about 0.8:1 to about 1.3:1.

[0005] Although conventionally obtained cross-linked epoxy resins are widely used, they have some disadvantages. For example, they cannot be reshaped or reprocessed into high-value products due to their permanent and irreversible cross-linking. Therefore, conventional epoxy resins cannot be mechanically recycled.

[0006] Recently, the incorporation of exchangeable covalent bonds has brought interesting properties to conventional thermosetting formulations, especially their (re)processing options and recyclability. Such networks containing dynamic covalent bonds are generally referred to as covalent adaptable networks (CANs).

[0007] Although the addition of dynamic covalent bonds in epoxy networks results in materials with interesting properties, the introduction of such dynamic covalent bonds may negatively affect the properties of the materials (e.g., thermal stability and dimensional stability of the materials). Therefore, the addition of dynamic covalent bonds to obtain epoxy networks remains challenging. In addition, achieving thermally induced material flow is usually limited to specific polymer networks composed of specific monomers, monomer ratios, or catalysts, which limits their applications. For example, epoxide monomers have been combined with transesterification (e.g., Leibler and co-workers, Science, 2011, 334(6058) 965-968), transamination (e.g., Du Prez and co-workers, Macromolecules, 2020, 53(7) 2485-2495), disulfide replacement (e.g., Odriozola and co-workers, Mater. Horizons, 2016, 3(3) 241-247), and imine exchange (e.g., Wu and co-workers, Chemical Engineering Journal, 2019, 368 61-70) to obtain epoxy-derived covalent adaptive networks. Summary of the invention

[0008] It is an object of the present invention to provide a curing agent for the preparation of a composition comprising an epoxy-derived covalent adaptive network and a process for the preparation of a composition comprising an epoxy-derived covalent adaptive network which does not exhibit the disadvantages of the compositions known from the prior art.

[0009] Another object of the present invention is to provide a method for preparing a composition comprising epoxy-derived covalent adaptive networks, said composition having good thermal stability (> 200°C) allowing (re)processability at high temperatures (200-300°C).

[0010] Another object of the present invention is to provide a curing agent for preparing a composition comprising an epoxy-derived covalent adaptive network and a method for preparing a composition comprising an epoxy-derived covalent adaptive network, wherein the composition is suitable for processing techniques such as in additive manufacturing, casting, extrusion, injection molding, compression molding, transfer molding, foam molding, thermoforming and rotational molding.

[0011] Another object of the present invention is to provide a method of applying an adhesive or coating comprising an epoxy-derived covalent adaptive network onto a substrate.

[0012] It is an object of the present invention to provide a method for applying an encapsulant comprising an epoxy-derived covalent adaptive network to an electronic component.

[0013] It is yet another object of the present invention to provide compositions comprising epoxy-derived covalent adaptive networks having good recyclability.

[0014] Furthermore, it was an object of the present invention to provide a composition which is suitable as a (structural) adhesive, as a (fusion-bonded) epoxy coating or for use in composite materials, such as fiber-reinforced composite materials.

[0015] According to a first aspect of the present invention, a method for preparing a composition comprising an epoxy-based covalent adaptive network is provided. The method comprises the following steps:

[0016] a) contacting at least one compound A with at least one compound B, thereby obtaining a mixture comprising or consisting of a curing agent,

[0017] wherein the at least one compound A has a' functional groups of the -C(=O)ORx and / or -C(=O)- type, wherein a' is an integer equal to or greater than 2, and wherein Rx of each of the a' functional groups is independently selected from the group consisting of H and C1-C4 alkyl.

[0018] Each of the a' functional groups of -C(=O)ORx type and / or -C(=O)- type belongs to a functional group pair including a first functional group and a second functional group, wherein the number of atoms between the carbonyl group of the first functional group and the carbonyl group of the second functional group is in the range of 2 to 8.

[0019] The at least one compound B has b' primary amine functional groups, wherein b' is an integer equal to or greater than 2, wherein each of the b' primary amine functional groups belongs to a functional group pair including a first primary amine functional group and a second primary amine functional group, whereby the number of atoms between the first primary amine functional group and the second primary amine functional group is at least 5, and each of the b' primary amine functional groups is directly connected to a primary carbon atom.

[0020] During step a), dynamic bonds are formed by reaction of at least a portion of the a' functional groups of the -C(=O)ORx and / or -C(=O)- type with at least a portion of the b' primary amine functional groups.

[0021] b) contacting said mixture obtained in step a) with at least one compound C, thereby obtaining an epoxy-derived covalent adaptive network, wherein said at least one compound C has c' epoxy functional groups, wherein c' is an integer equal to or greater than 2.

[0022] During step b), permanent (non-dynamic) bonds are formed by reaction of at least a portion of the at least c′ epoxy functions with active hydrogen atoms of functional groups capable of reacting with epoxy functions present in the mixture.

[0023] Meet the following requirements:

[0024] - Equal to or greater than ,

[0025] - Ratio is in the range of 0.5 to 1.5, and

[0026] - When x ≥ In the case of is equal to or greater than 0.4, or when x< In the case of Equal to or greater than 0.4.

[0027] in

[0028] n i Is a functional a' i Compound A i The number of millimoles (mmol),

[0029] n j Is a functional b' j Compound B j The number of millimoles (mmol),

[0030] n k Is a functional group c' k Compound C i The number of millimoles (mmol),

[0031] x is the total number of active hydrogen atoms of all functional groups present at the beginning of step b) which are capable of reacting with epoxy functional groups.

[0032] In the case where at least one compound A comprises a functional group pair having a —(C═O)-type functional group as the first and second functional groups, at least one compound A comprises a cyclic carboxylic acid anhydride, wherein the first and second functional groups belong to the carboxylic acid functional group of at least one compound A.

[0033] In a preferred embodiment, the at least one compound A has a' functional groups of the -C(=O)ORx type, wherein each of the a' functional groups of the -C(=O)ORx type belongs to a functional group pair comprising a first functional group and a second functional group.

[0034] For completeness, a' i Compound A i a' number of -C(=O)ORx type and / or -C(=O)- type functional groups of (A1, A2, A3, ...). b' j Compound B j The number of b' primary amine functional groups in (B1, B2, B3, ...). c' k Compound C kThe number of c' epoxy functional groups of (C1, C2, C3, ...).

[0035] For the purpose of the present invention, can be referred to as the combined molar amount of a' functional groups of the -C(=O)ORx type and / or -C(=O)- type of all compounds A at the beginning of step a). In the case where two different compounds A (A1 and A2) are present at the beginning of step a), the combined molar amount of b' primary amine functional groups of all compounds A can be written as

[0036]

[0037] where n i Is a functional a' i Compound A i The number of millimoles (mmol),

[0038] n1 is the number of millimoles (mmol) of compound A1 having functionality a'1,

[0039] n2 is the number of millimoles (mmol) of compound A2 having functionality a'2.

[0040] Similarly, can be referred to as the combined molar amount of b' primary amine functional groups of all compounds B at the beginning of step a). In case two different compounds B (B1 and B2) are present at the beginning of step a), the combined molar amount of b' primary amine functional groups of all compounds B can be written as

[0041]

[0042] where n j Is a functional b' j Compound B j The number of millimoles (mmol),

[0043] n1 is the number of millimoles (mmol) of compound B1 having functionality b'1, and

[0044] n2 is the number of millimoles (mmol) of compound B2 having functionality b'2.

[0045] Similarly, can be referred to as the combined molar amount of c' epoxy functional groups of all compounds C at the beginning of step b). In the case where two different compounds C (C1 and C2) are present at the beginning of step b), the combined molar amount of c' epoxy functional groups of all compounds C can be written as

[0046]

[0047] where n k Is a functional group c' j Compound C j The number of millimoles (mmol),

[0048] n1 is the number of millimoles (mmol) of compound C1 having functionality c'1, and

[0049] n2 is the number of millimoles (mmol) of compound C2 having functionality c'2.

[0050] The total number of active hydrogen atoms of the functional groups which are capable of reacting with the epoxy functional groups is defined as x. The total number of active hydrogen atoms present at the start of step b) is further specified in more detail.

[0051] Although it is generally believed that the addition of dynamic covalent bonds in a network (such as an epoxy network) negatively affects properties such as thermal stability and dimensional stability, it was surprisingly found that by using the starting compounds A, B, C in the amounts specified above, epoxy-based covalent adaptive networks with good thermal and dimensional stability are obtained. In addition, it is important to control the (maximum) number of dynamic bonds relative to the (maximum) number of dynamic and permanent (non-dynamic) bonds.

[0052] Since in step a) a dynamic bond is formed by reaction of a' functional group of the -C(=O)ORx type and / or -C(=O)- type of at least one compound A with b' primary amine functional groups of at least one compound B, and the combined molar amount of b' primary amine functional groups of all compounds B at the beginning of step a) ( ) is equal to or greater than the combined molar amount of a' functional groups of the -C(=O)ORx type and / or -C(=O)- type of all compounds at the beginning of step a) ( ), so the maximum number of dynamic bonds is determined by the number of a' functional groups of -C(=O)ORx type and / or -C(=O)- type.

[0053] Preferably, the combined molar amount of b' primary amine functional groups of all compounds B at the beginning of step a) is ( )) is greater than the combined molar amount of a' functional groups of the -C(=O)ORx type and / or -C(=O)- type of all compounds A at the beginning of step a) ( The combined molar amount of b' primary amine functional groups of at least one compound B at the beginning of step a) ( ) for example, compared to the combined molar amount of a' functional groups of the -C(=O)ORx type and / or -C(=O)- type at the beginning of step a) ( ) is 5%, 10%, 20%, 30% or 50% larger.

[0054] Preferably, all or substantially all of the a' functional groups of the -C(=O)ORx type and / or -C(=O)- type react with b' primary amine functional groups of at least one compound B. In the case where all of the a' functional groups of the -C(=O)ORx type and / or -C(=O)- type react with b' primary amine functional groups of at least one compound B, the combined molar amount of dynamic bonds is equal to (The combined molar amount of a' functional groups of the -C(=O)ORx type and / or -C(=O)- type of all compounds A at the beginning of step a)). Preferably, the combined molar amount of dynamic bonds is At least 80% of At least 85% at least 90 % of at least 95 % of

[0055] Since the combined molar amount of b' primary amine functional groups of the at least one compound B at the beginning of step a) is ( ) is preferably greater than the combined molar amount of a'-C(=O)OR-type and / or -C(=O)-type functional groups of the at least one compound A at the beginning of step a) ( ), after the reaction of a' functional groups with b' primary amine functional groups, preferably an excess of unreacted b' primary amine functional groups remains. Such excess b' primary amine functional groups can, for example, be reacted in step b) of the process according to the invention.

[0056] In step b), permanent bonds are formed by reaction of at least a portion of the c′ epoxy functional groups of the at least one compound C with active hydrogen atoms of functional groups capable of reacting with epoxy functional groups.

[0057] According to the present invention, the ratio In the range of 0.5 to 1.5. More preferably, the ratio In the range of 0.7 to 1.3, for example in the range of 0.8 to 1.2. Most preferably, the ratio In the range of 0.9 to 1.1, and for example, 0.95, 1 or 1.05.

[0058] The maximum number of permanent bonds that can be formed is determined by the total number of c' epoxy functional groups present in the mixture at the beginning of step b) or by the total number of active hydrogen atoms of all functional groups capable of reacting with epoxy functional groups present in the mixture at the beginning of step b), whichever is the largest.

[0059] According to the present invention, when x≥ In the case of Must be equal to or greater than 0.4. In the case of Equal to or greater than 0.4.

[0060] In a preferred embodiment of the present invention, the ratio ,ratio Respectively equal to or greater than 0.5, equal to or greater than 0.6, or equal to or greater than 0.8.

[0061] Optionally, one or more additional compounds may be present in step a) of the method according to the present invention. In a preferred embodiment, at least one compound E is present in step a) of the method. In this case, the mixing step a) includes contacting at least one compound A, at least one compound B and at least one compound E to obtain a mixture containing or consisting of a curing agent. At least one compound E includes e' primary amine functional groups (wherein e' is an integer equal to or greater than 1), and does not include a functional group pair including a first primary amine functional group and a second primary amine functional group, wherein the number of atoms between the first primary amine functional group and the second primary amine functional group is at least 5. Preferably, compound E includes a primary amine functional group with e' being one. In the case where compound E includes a primary amine functional group with e' being more than one, these primary amine functional groups may be the same or may be different.

[0062] It is clear that compound E may contain further functional groups (in addition to the e' primary functional groups). Such further functional groups are referred to as e" further functional groups.

[0063] The main effect of compound E is to influence the viscosity of the mixture obtainable in step a) of the process according to the invention, preferably to reduce the viscosity of the mixture obtainable in step a).

[0064] Preferably, the amount of the at least one compound E is limited to a maximum of 10% by weight of the total amount of the at least one compound B, for example, or to a maximum of 5% by weight of the total amount of the at least one compound B.

[0065] Alternatively or additionally, the active hydrogen atom may include a hydrogen atom of a functional group of at least one additional compound present in the mixture at the start of step b). This additional compound is referred to as at least one compound D having d' as one or more additional functional groups. In the case where compound D has d' as more than one additional functional group, these additional functional groups may be the same or may be different. In a preferred embodiment of the invention, at least one compound D has d' as more than two additional functional groups.

[0066] At least one compound D can function as a crosslinker.

[0067] Preferably, the amount of the at least one compound D is limited to a maximum of 10% by weight of the mixture.

[0068] Active hydrogen atoms of functional groups that can react with epoxy functional groups

[0069] For the purposes of the present invention, any hydrogen atom present which is capable of reacting with an epoxy functional group may be considered an active hydrogen atom.In the context of the present invention, the terms active hydrogen atom and active hydrogen are used interchangeably.

[0070] The functional group capable of reacting with the epoxy functional group preferably includes a functional group selected from the group consisting of a primary amine functional group, a secondary amine functional group, an alcohol functional group, a thiol functional group, and a -C(=O)OH functional group.

[0071] The functional group capable of reacting with the epoxy functional group may contain one or more active hydrogen atoms. Secondary amine functional groups, alcohol functional groups, thiol functional groups and -C(=O)OH functional groups have one active hydrogen atom. Primary amine functional groups have two active hydrogen atoms.

[0072] As mentioned above, the total number of all active hydrogen atoms present at the beginning of step b) (= the sum of all active hydrogen atoms) is referred to as x. The active hydrogen atoms at the beginning of step b) include active hydrogen atoms of compound B and / or active hydrogen atoms of compound E and / or active hydrogen atoms of compound D, etc.

[0073] The active hydrogen atoms at the start of step b) in compound B may include hydrogen atoms of functional groups of at least one compound B, i.e. hydrogen atoms of b' primary amine functional groups that have not yet reacted with a' functional groups of the -C(=O)ORx type and / or -C(=O)- type of at least one compound A, or hydrogen atoms of additional functional groups (except b' primary amine functional groups) of compound B. Such additional functional groups of the at least one compound B are referred to herein as b'' additional functional groups. It is clear that compound B may have one or more b'' additional functional groups. In the case where compound B has more than one b'' additional functional groups, these additional functional groups may be identical or may be different.

[0074] The active hydrogen atoms present at the beginning of step b) of compound E may include hydrogen atoms of e' primary amine functions, i.e. hydrogen atoms of e' primary amine functions which have not yet reacted with a' functional group of the -C(=O)ORx type and / or -C(=O)- type of at least one compound A, or hydrogen atoms of further functional groups (other than the e' primary amine functions) of compound E (referred to as e" further functional groups).

[0075] The active hydrogen atoms present at the start of step b) of compound D may include hydrogen atoms of d' further functional groups.

[0076] It is clear that the at least one compound A may comprise more than one compound A, for example a mixture of compounds An, such as a mixture of compound A1, compound A2 and compound A3.

[0077] Similarly, the at least one compound B may comprise more than one compound B, for example a mixture of compounds Bn, such as a mixture of compound B1, compound B2 and compound B3.

[0078] In case the mixture at the start of step b) further comprises at least one compound D, the at least one compound D may comprise more than one compound D, for example a mixture of compounds Dn, for example a mixture of compound D1, compound D1 and compound D3.

[0079] In case the mixture at the beginning of step a) further comprises at least one compound E, the at least one compound E may comprise more than one compound E, for example a mixture of compounds En, for example a mixture of compound E1, compound E1 and compound E3.

[0080] Compound A

[0081] As described above, at least one compound A has a number of a'-C(=O)ORx type and / or -C(=O)- type functional groups, wherein a' is an integer equal to or greater than 2, such as 2, 3, 4 or 5, and wherein Rx of each functional group is independently selected from the group consisting of H and C1-C4 alkyl. Rx in each of the functional groups preferably includes H, methyl or ethyl.

[0082] In the case where at least one compound A comprises a functional group pair having a —(C═O)-type functional group as the first and second functional groups, at least one compound A comprises a cyclic carboxylic acid anhydride, wherein the first and second functional groups belong to the carboxylic acid functional group of at least one compound A.

[0083] It is clear that the at least one compound A may also contain a combination of a′ functional groups of the —C(═O)ORx type and of the —C(═O)— type.

[0084] Preferred compounds A contain a' functional groups of the type -C(=O)ORx, wherein a' is an integer equal to or greater than 2, such as 2, 3, 4 or 5, wherein Rx of each functional group is independently selected from the group consisting of H and C1-C4 alkyl. Rx in each functional group preferably includes H, methyl or ethyl.

[0085] For compound A, the number of atoms between the carbonyl group of the first functional group and the carbonyl group of the second functional group in the functional group pair of -C(=O)ORx type and / or -C(=O)- type is in the range of 2 to 8. Preferably, the number of atoms between the carbonyl group of the first functional group and the carbonyl group of the second functional group in the functional group pair of -C(=O)ORx type and / or -C(=O)- type is 2, 3 or 4.

[0086] The atom between the carbonyl group of the first functional group and the carbonyl group of the second functional group in the functional group pair of -C(=O)ORx type and / or -C(=O)-type may include a substituted or unsubstituted carbon atom, or a combination of a carbon atom and one or more heteroatoms (e.g., one or more nitrogen atoms and / or one or more oxygen atoms). Preferably, the atom between the carbonyl group of the first functional group and the carbonyl group of the second functional group in the functional group pair of -C(=O)ORx type or -C(=O)-type contains at most one heteroatom, such as an oxygen atom or a nitrogen atom.

[0087] In the case where compound A comprises a cyclic structure and there is more than one linker between the carbonyl group of the first functional group and the carbonyl group of the second functional group in the functional group pair (particularly a functional group pair of the -C(=O)ORx type), at least one of these linkers has 2 to 8 atoms. Preferably, the shortest linker among the multiple linkers between the carbonyl group of the first functional group and the carbonyl group of the second functional group in the functional group pair (particularly a functional group pair of the -C(=O)ORx type) has 2 to 8 atoms, more preferably 2, 3 or 4 atoms, and even more preferably 2, 3 or 4 carbon atoms.

[0088] In the case where the first functional group and the second functional group in the functional group pair comprise a' functional group of the -C(=O)ORx type and there is more than one linker between the carbonyl group of the first functional group of the -C(=O)ORx type and the carbonyl group of the second functional group of the -C(=O)ORx type, the number of atoms of the linker excluding the oxygen atom located between the carbon atom of the a' functional group and the Rx-group is preferably in the range of 2 to 8. More preferably, the number of atoms of the linker excluding the oxygen located between the carbon atom of the a' functional group and the Rx-group is 2, 3 or 4.

[0089] In a preferred embodiment, the atom between the carbonyl of the first functional group of-C(=O)ORx type and / or-C(=O)-type and the carbonyl of the second functional group of-C(=O)ORx type and / or-C(=O)-type comprises a straight-chain saturated or unsaturated hydrocarbon, which optionally comprises one or more heteroatoms. One or more of the carbon atoms can be substituted, for example, substituted by a functional group selected from the group consisting of, for example, C1-C4 alkyl and an alcohol functional group.

[0090] Preferred linking moieties between the first functional group and the second functional group in a' functional group pair include -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2-N-CH2-, -CH2-N-CH2-CH2-, -CH2-O-CH2-, ... .

[0091] Preferred compounds A contain a' functional groups of the type -C(=O)ORx. Examples of such compounds A include dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.

[0092] Other preferred compounds A containing a' functional groups of the C(=O)ORx type include: monomethyl succinate, monomethyl glutarate, monomethyl adipate, monomethyl pimelate, monomethyl suberate, monomethyl azelaic acid, monomethyl sebacate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl azelaic acid, and dimethyl sebacate.

[0093] Some other examples of compounds A preferably comprising a' functional group of the type -C(=O)ORx include:

[0094]

[0095]

[0096] In other embodiments, at least a portion of the atoms between the carbonyl of the first functional group and the carbonyl of the second functional group in the functional group pair of -C(=O)ORx type is a part of the cyclic structure. The cyclic structure can be substituted by one or more groups, for example, by an alkyl, an alcohol functional group and / or an amine functional group.

[0097] The cyclic structure may include an aromatic or non-aromatic structure. The cyclic structure may include a carbocyclic compound or a heterocyclic compound, such as a cyclic structure containing one or more heteroatoms (such as oxygen or nitrogen). The cyclic structure preferably includes a monocyclic structure.

[0098] Preferred ring structures include 6-membered ring structures, which are aromatic or non-aromatic, substituted or unsubstituted.

[0099] Specific examples include dimethyl phthalate and dimethyl cyclohexane-1,2-dicarboxylate. Other preferred examples are given below:

[0100]

[0101] In case compound A comprises a cyclic carboxylic anhydride, succinic anhydride, glutaric anhydride and adipic anhydride are preferred.

[0102] It is clear that at least one compound A may also contain functional groups other than the a' functional groups of the -C(=O)ORx type and / or -C(=O)- type, for example one or more amine functional groups, one or more alcohol functional groups, one or more thiol functional groups and / or one or more -C(=O)ORy functional groups, where Ry is selected from the group consisting of H and C1-C4 alkyl, preferably methyl or ethyl.

[0103] For the sake of completeness, functional groups of the -C(=O)ORx type and / or -C(=O)- type which do not belong to a functional group pair of the -C(=O)ORx type as described above are not considered as a' functional group but as an additional functional group.

[0104] Compound B

[0105] As described above, at least one compound B has a number of b' of primary amine functional groups. Optionally, at least one compound B further comprises b'' additional functional groups. b' is an integer equal to or greater than 2, such as 2, 3, 4 or 5, and b'' is an integer equal to or greater than 0, such as 0, 1, 2, 3 or 5.

[0106] Each of the b' primary amine functional groups belongs to a functional group pair including a first primary amine functional group and a second primary amine functional group. The number of atoms between the first primary amine functional group and the second primary amine functional group is at least 5. Each of the b' primary amine functional groups is preferably directly attached to a primary carbon atom.

[0107] The atoms between the first primary amine functional group and the second primary amine functional group may include substituted or unsubstituted carbon atoms, or a combination of carbon atoms and one or more heteroatoms (e.g., one or more nitrogen atoms and / or one or more oxygen atoms). Preferably, the atoms between the first primary amine functional group and the second primary amine functional group include at most one heteroatom, such as one oxygen atom or one nitrogen atom.

[0108] For preferred compounds B, the number of atoms between the first primary amine functional group and the second primary amine functional group is at least 6, at least 8, at least 10, at least 12, at least 18, or at least 24.

[0109] Where compound B comprises a cyclic structure and has more than one linker between the first amine functional group and the second amine functional group in the pair of amine functional groups, at least one of these linkers comprises at least 5 atoms, more preferably at least 6, at least 8, at least 10, at least 12, at least 18 or at least 24 atoms, for example at least 5, at least 6, at least 8, at least 10, at least 12, at least 18 or at least 24 carbon atoms.

[0110] Preferably, the shortest linker (i.e., the linker with the fewest number of atoms) among the plurality of linkers between the first amine functional group and the second amine functional group in the amine functional group pair has at least 5 and more preferably at least 6, at least 8, at least 10, at least 12, at least 18 or at least 24 atoms, 2 to 8 atoms, for example at least 5, at least 6, at least 8, at least 10, at least 12, at least 18 or at least 24 carbon atoms.

[0111] In a preferred embodiment, the moiety linking the first primary amine functional group and the second primary amine functional group comprises or consists of a group selected from the group consisting of: C 6-40 Alkyl, C 6-40 Alkenyl, C 6-40 Alkynyl, C 6-24 Aryl, C 6-24 Cycloalkyl, C 6-24 Aryl C 1-40 wherein one or more carbon atoms in the backbone of the alkyl, alkenyl, alkynyl, aryl or cycloalkyl group may be substituted by heteroatoms independently selected from O, S, N and Si; wherein the alkyl, alkenyl, alkynyl, aryl or cycloalkyl group may be unsubstituted or further substituted.

[0112] In a preferred embodiment, at least one compound B comprises an aliphatic amine comprising at least two primary amine functional groups, said primary amine functional groups belonging to a functional group pair comprising a first primary amine functional group and a second primary amine functional group.

[0113] As used herein, fatty amines generally refer to the product of the nitrile process (NitrileProcess) obtained by the polymerization of unsaturated fatty acids. The nitrile process includes the reaction of fatty acids and ammonia to obtain nitrile compounds at high temperatures (> 250°C) in the presence of metal oxide catalysts, and the nitrile compounds produce the required amine monomers after hydrogenation. The fatty amines obtained include a mixture of a cyclic structure and a straight hydrocarbon chain with more than 18 carbon atoms. More preferably, the fatty amines include at least 22 or at least 36 carbon atoms. Preferred examples of fatty amines include amine derivatives of tall oil fatty acids, stearic acid, palm fatty acids, soybean fatty acids, cottonseed fatty acids, oleic fatty acids and linoleic fatty acids.

[0114] The b" additional functional groups include functional groups that are capable of reacting with epoxy functional groups and contain at least one active hydrogen atom.

[0115] Examples of the b″ additional functional group include a primary amine functional group, a secondary amine functional group, an alcohol functional group, a thiol functional group, and a —C(═O)OH functional group.

[0116] For the sake of completeness, primary amine functions which do not belong to an amine functional group pair as defined above are not considered as b' functional groups but as b" further functional groups.

[0117] Examples of suitable compounds B are given in Table 1.

[0118] Table 1

[0119]

[0120] Other suitable compounds B include: 4,7-dioxadecane-1,10-diamine, diethylene glycol bis(3-aminopropyl) ether, Jeffamine D230 and D400, Jeffamine XTJ-504 and XTJ-511, pentaethylenehexamine (PEHA), hexamethylenediamine (HMDA), N-(2-aminoethyl)-1,3-propylenediamine, N,N'-bis(3-aminopropyl)ethylenediamine and 3,9-bis(3-aminopropyl) 2,4,8,10-tetraoxaspiro(5,5)undecane.

[0121] Compound C

[0122] At least one compound C comprises c' epoxy functional groups, wherein c' is an integer equal to or greater than 2. Two c' epoxy functional groups are connected by an epoxy linking moiety. Each of the epoxy linking moieties of compound C can be independently selected. Preferably, the epoxy linking moiety comprises or consists of a group selected from the group consisting of: C 1-40 Alkyl, C 2-40 Alkenyl, C 2-40 Alkynyl, C 5-24 Aryl, C 3-24 Cycloalkyl, C 6-24 Aryl C 1-40 wherein one or more carbon atoms in the skeleton of the alkyl, alkenyl, alkynyl, aryl or cycloalkyl group may be substituted by heteroatoms independently selected from O, S, N and Si; wherein the alkyl, alkenyl, alkynyl, aryl or cycloalkyl group may be unsubstituted or further substituted.

[0123] Examples of suitable compounds of formula (VII) are given in Table 2.

[0124] Table 2

[0125]

[0126]

[0127] Therefore, in a preferred embodiment, the method described herein is provided, wherein at least one compound C is a compound selected from the group consisting of diglycidyl ether, triglycidyl ether, diglycidyl amine, triglycidyl amine, diglycidyl isocyanurate and triglycidyl isocyanurate, more preferably a compound selected from the group consisting of tris(4-hydroxyphenyl)methane triglycidyl ether; trimethylolpropane triglycidyl ether; bisphenol A diglycidyl ether; bisphenol F diglycidyl ether; bisphenol C diglycidyl ether; bisphenol E diglycidyl ether; bisphenol BP diglycidyl ether; bisphenol FC diglycidyl ether; bisphenol Phenol Z diglycidyl ether; 1,6-hexanediol diglycidyl ether; 1,4-butanediol diglycidyl ether; triglycidyl isocyanurate; hydrogenated bisphenol A diglycidyl ether; hydrogenated bisphenol F diglycidyl ether; hydrogenated bisphenol C diglycidyl ether; hydrogenated bisphenol E diglycidyl ether; hydrogenated bisphenol BP diglycidyl ether; hydrogenated bisphenol FC diglycidyl ether; hydrogenated bisphenol Z diglycidyl ether; 1,6-naphthalene diglycidyl ether; neopentyl glycol diglycidyl ether; poly(propylene glycol) diglycidyl ether; 4,4'-methylenebis(N,N-diglycidylaniline); and N,N-diglycidyl-4-glycidyloxyaniline.

[0128] In a specific embodiment of the present invention, at least one compound C is an epoxidized polydiene or a copolymer thereof, an epoxidized vegetable oil or a copolymer thereof, or an epoxidized terpene or a copolymer thereof, preferably an epoxidized cyclic terpene, most preferably an epoxidized cyclic monoterpene. Preferred epoxidized polydienes are epoxidized natural rubber, epoxidized poly(1,4-butadiene) and epoxidized styrene-butadiene rubber. Preferred epoxidized vegetable oils are epoxidized soybean oil, epoxidized castor oil, epoxidized sunflower oil and epoxidized linseed oil. Preferred epoxidized terpenes are epoxidized limonene, epoxidized terpineol, epoxidized humulene, epoxidized myrcene, epoxidized linalool, epoxidized citronellol and epoxidized pinene.

[0129] It is clear that at least one compound C may contain functional groups other than c' epoxy functional groups, for example one or more amine functional groups, one or more alcohol functional groups, one or more thiol functional groups and / or one or more -C(=O)ORx functional groups, where Rx is selected from the group consisting of H and C1-C4 alkyl, preferably methyl or ethyl.

[0130] Compound D

[0131] As mentioned above, at least one compound D has a number d' of further functional groups. d' is an integer equal to or greater than 1, for example 2, 3, 4 or 5.

[0132] The d' additional functional groups include functional groups that are capable of reacting with the epoxy functional group and contain at least one active hydrogen atom.

[0133] Examples of the d′ additional functional groups include a primary amine functional group, a secondary amine functional group, an alcohol functional group, a thiol functional group, and a —C(═O)OH functional group.

[0134] In a preferred embodiment, compound D comprises poly(oxy(methyl-1,2-ethanediyl):

[0135]

[0136] Other examples of compound D include polyethylene glycol (PEG)-based diols and triols, and polypropylene glycol (PPG)-based diols and triols.

[0137] Compound D can be selected to reduce or increase the viscosity and cure rate of the mixture.

[0138] Compound E

[0139] As mentioned above, at least one compound E has a number e' of primary amine functional groups. e' is an integer equal to or greater than 1, such as 2, 3, 4 or 5. Preferably, e' is equal to 1.

[0140] Compound E does not include a functional group pair including a first primary amine functional group and a second primary amine functional group, wherein the number of atoms between the first primary amine functional group and the second primary amine functional group is at least 5.

[0141] Preferred compounds E contain one primary amine function. In case compound E contains more than one primary amine function as e', these primary amine functions may be the same or may be different.

[0142] At least one compound E may also contain additional functional groups (in addition to the e' primary functional groups). The additional functional groups are referred to as e'' additional functional groups. Such e'' additional functional groups include, for example, functional groups that can react with epoxy functional groups and contain at least one active hydrogen atom. Examples of e'' additional functional groups include: secondary amine functional groups, alcohol functional groups, thiol functional groups and -C(=O)OH functional groups.

[0143] Preferred examples of compound E include N-aminoethylpiperazine, N-methyl-1,3-diaminopropane and N-ethyl-N-methylpropane-1,3-diamine.

[0144] In a first preferred method, in step a), a compound A comprising a' functional groups of the -C(=O)ORx type and / or -C(=O)- type is contacted with a compound B comprising b' primary amine functional groups. At the beginning of step a), the combined molar amount of the b' primary amine functional groups is greater than (e.g., substantially greater than) the combined molar amount of a' functional groups of the -C(=O)ORx type and / or -C(=O)- type , so that in step b), b' primary amine functions having active hydrogen atoms are present to react with c' epoxide functions of at least one compound C.

[0145] Such a first preferred method comprises the following steps:

[0146] a) contacting at least one compound A with at least one compound B, thereby obtaining a mixture comprising or consisting of a curing agent,

[0147] wherein the at least one compound A has a' functional groups of the -C(=O)ORx type and / or -C(=O)- type, wherein a' is an integer equal to or greater than 2, and wherein Rx of each functional group is independently selected from the group consisting of H and C1-C4 alkyl, and wherein in the case where compound A has a' functional groups of the -C(=O)- type, compound A is a cyclic carboxylic anhydride,

[0148] wherein each of the a' functional groups of the -C(=O)ORx type and / or -C(=O)- type belongs to a functional group pair comprising a first functional group and a second functional group, wherein the number of atoms between the carbonyl group of the first functional group and the carbonyl group of the second functional group is in the range of 2 to 8, and

[0149] wherein the at least one compound B has b' primary amine functional groups, wherein b' is an integer equal to or greater than 2, wherein each of the b' primary amine functional groups belongs to a functional group pair including a first primary amine functional group and a second primary amine functional group, wherein the number of atoms between the first primary amine functional group and the second primary amine functional group is at least 5, wherein each of the b' primary amine functional groups is directly attached to a primary carbon atom,

[0150] wherein during step a), a dynamic bond is formed by reaction of at least a portion of the a' functional groups of -C(=O)ORx type and / or -C(=O)- type with at least a portion of the b' primary amine functional groups,

[0151] b) contacting said mixture obtained in step a) with at least one compound C, thereby obtaining an epoxy-derived covalent adaptive network,

[0152] wherein the at least one compound C has c' epoxy functional groups, wherein c' is an integer equal to or greater than 2,

[0153] Therein, during step b), permanent bonds are formed by reaction of at least a portion of the at least c′ epoxy functional groups with active hydrogen atoms of functional groups capable of reacting with epoxy functional groups present in the mixture.

[0154] in

[0155] - Greater than ,

[0156] - Ratio is in the range of 0.5 to 1.5, and

[0157] - In x> In the case of is equal to or greater than 0.4, or when x< In the case of Equal to or greater than 0.4,

[0158] in

[0159] n i It is functional Compound A i The number of millimoles (mmol),

[0160] n j It is functional Compound B j The number of millimoles (mmol),

[0161] n k It is functional Compound C i The number of millimoles (mmol),

[0162] x is the total number of active hydrogen atoms of all functional groups capable of reacting with epoxy functional groups present at the beginning of step b). Preferably, x is the total number of active hydrogen atoms of all b' functional groups capable of reacting with epoxy functional groups that have not yet reacted with a' primary amine functional groups and that are present at the beginning of step b).

[0163] In a second preferred process, in step a), a compound A comprising a' functional groups of the -C(=O)ORx type and / or -C(=O)- type is contacted with a compound B comprising b' primary amine functions and b" further functional groups. The b" further functional groups are capable of reacting with epoxy functions and comprise at least one active hydrogen atom. In step b), the active hydrogen atoms of the b' primary amine functions which have not yet reacted with the a' functional groups of the -C(=O)ORx type and / or -C(=O)- type and the active hydrogen atoms of the b" further functional groups react with c' epoxy functions of at least one compound C.

[0164] Such a second preferred method comprises the following steps:

[0165] a) contacting at least one compound A with at least one compound B, thereby obtaining a mixture comprising or consisting of a curing agent,

[0166] wherein the at least one compound A has a' functional groups of -C(=O)ORx type and / or -C(=O)- type, wherein a' is an integer equal to or greater than 2, and wherein Rx of each functional group is independently selected from the group consisting of H and C1-C4 alkyl, and wherein in the case where compound A has a'-C(=O)-type functional groups, compound A is a cyclic carboxylic anhydride,

[0167] wherein each of the a' functional groups of the -C(=O)ORx type and / or -C(=O)- type belongs to a functional group pair comprising a first functional group and a second functional group, wherein the number of atoms between the carbonyl group of the first functional group and the carbonyl group of the second functional group is in the range of 2 to 8, and

[0168] wherein at least one compound B has b' primary amine functional groups and has b'' additional functional groups, wherein b' is an integer equal to or greater than 2 and b'' is an integer equal to or greater than 1, wherein each of the b' primary amine functional groups belongs to a functional group pair including a first primary amine functional group and a second primary amine functional group, wherein the number of atoms between the first primary amine functional group and the second primary amine functional group is at least 5, each of the b' primary amine functional groups is directly attached to a primary carbon atom, wherein the b'' additional functional groups are selected from the group consisting of a primary amine functional group, a secondary amine functional group, an alcohol functional group, a thiol functional group and a -C(=O)OH functional group,

[0169] wherein during step a), a dynamic bond is formed by reaction of at least a portion of the a' functional groups of -C(=O)ORx type and / or -C(=O)- type with at least a portion of the b' primary amine functional groups,

[0170] b) contacting said mixture obtained in step a) with at least one compound C, thereby obtaining an epoxy-derived covalent adaptive network,

[0171] wherein the at least one compound C has c' epoxy functional groups, wherein c' is an integer equal to or greater than 2,

[0172] Therein, during step b), permanent bonds are formed by reaction of at least a portion of the c′ epoxy functional groups with active hydrogen atoms of functional groups capable of reacting with epoxy functional groups present in the mixture.

[0173] in

[0174] - Equal to or greater than ,

[0175] - Ratio is in the range of 0.5 to 1.5, and

[0176] - In x> In the case of is equal to or greater than 0.4, or when x< In the case of Equal to or greater than 0.4,

[0177] in

[0178] n i It is functional Compound A i The number of millimoles (mmol),

[0179] n j It is functional Compound B j The number of millimoles (mmol),

[0180] n k It is functional Compound C i The number of millimoles (mmol),

[0181] x is the total number of active hydrogen atoms of all functional groups present at the beginning of step b) which are capable of reacting with epoxy functional groups. Moreover, x is preferably the total number of active hydrogen atoms of all b' functional groups present at the beginning of step b) which have not reacted with a' functional groups of the -C(=O)ORx type and / or -C(=O)- type and all b"' additional functional groups present at the beginning of step b).

[0182] In a third preferred process, compound A comprising a' functional groups of the -C(=O)ORx type and / or of the -C(=O)- type, compound B comprising b' primary amine functions and optionally b" further functional groups, and compound E comprising e' primary amine functions and optionally e" further functional groups are contacted in step a). The b" further functional groups and / or the e" further functional groups are preferably capable of reacting with epoxy functions and preferably comprise at least one active hydrogen atom.

[0183] Such a third preferred method comprises the following steps:

[0184] a) contacting at least one compound A with at least one compound B and with at least one compound E, thereby obtaining a mixture comprising or consisting of a curing agent,

[0185] wherein the at least one compound A has a' functional groups of the -C(=O)ORx type and / or -C(=O)- type, wherein a' is an integer equal to or greater than 2, and wherein Rx of each functional group is independently selected from the group consisting of H and C1-C4 alkyl, and wherein in the case where compound A has a' functional groups of the -C(=O)- type, compound A is a cyclic carboxylic anhydride,

[0186] wherein each of the a' functional groups of the -C(=O)ORx type and / or -C(=O)- type belongs to a functional group pair comprising a first functional group and a second functional group, wherein the number of atoms between the carbonyl group of the first functional group and the carbonyl group of the second functional group is in the range of 2 to 8, and

[0187] wherein at least one compound B has b' primary amine functional groups and optionally b'' additional functional groups, wherein b' is an integer equal to or greater than 2 and b'' is an integer equal to or greater than 0, wherein each of the b' primary amine functional groups belongs to a functional group pair comprising a first primary amine functional group and a second primary amine functional group, wherein the number of atoms between the first primary amine functional group and the second primary amine functional group is at least 5, and each of the b' primary amine functional groups is directly attached to a primary carbon atom. In the case where at least one compound B comprises b'' additional functional groups, such additional functional groups are preferably selected from the group consisting of a primary amine functional group, a secondary amine functional group, an alcohol functional group, a thiol functional group and a -C(=O)OH functional group,

[0188] wherein at least one compound E has e' primary amine functional groups and optionally comprises e" additional functional groups, wherein e' is an integer equal to or greater than 1 and e" is an integer equal to or greater than 0, and wherein compound E does not comprise a functional group pair comprising a first primary amine functional group and a second primary amine functional group, wherein the number of atoms between the first primary amine functional group and the second primary amine functional group is at least 5,

[0189] wherein, during step a), a dynamic bond is formed by reaction of at least a portion of the a' functional groups of -C(=O)ORx type and / or -C(=O)- type with at least a portion of the b' primary amine functional groups of the at least one compound D, and optionally by reaction of at least a portion of the a' functional groups of -C(=O)ORx type and / or -C(=O)- type with at least a portion of the e' primary amine functional groups of the at least one compound E,

[0190] b) contacting said mixture obtained in step a) with at least one compound C, thereby obtaining an epoxy-derived covalent adaptive network,

[0191] wherein the at least one compound C has c' epoxy functional groups, wherein c' is an integer equal to or greater than 2,

[0192] Therein, during step b), permanent bonds are formed by reaction of at least a portion of the at least c' epoxy functional groups with active hydrogen atoms of functional groups capable of reacting with epoxy functional groups present in the mixture.

[0193] in

[0194] - Equal to or greater than ,

[0195] - Ratio is in the range of 0.5 to 1.5, and

[0196] - In x> In the case of is equal to or greater than 0.4, or when x< In the case of Equal to or greater than 0.4,

[0197] in

[0198] n i It is functional Compound A i The number of millimoles (mmol),

[0199] n j It is functional Compound B j The number of millimoles (mmol),

[0200] n k It is functional Compound C i The number of millimoles (mmol),

[0201] x is the total number of active hydrogen atoms of all functional groups capable of reacting with epoxy functional groups present at the beginning of step b). Preferably, x is the total number of active hydrogen atoms of all b' functional groups present at the beginning of step b) that have not reacted with a' functional group of the -C(=O)ORx type and / or -C(=O)- type, the total number of active hydrogen atoms of all b' additional functional groups present at the beginning of step b), and the total number of active hydrogen atoms of all e' functional groups present at the beginning of step b) that have not reacted with a' functional group of the -C(=O)ORx type and / or -C(=O)- type, and the total number of active hydrogen atoms of all e' additional functional groups present at the beginning of step b).

[0202] In a fourth preferred process, in step a), a compound A comprising a' functional groups of the -C(=O)ORx type and / or of the -C(=O)- type is contacted with a compound B comprising b' primary amine functional groups and optionally b" further functional groups. The b" further functional groups are preferably capable of reacting with epoxy functional groups and preferably comprise at least one active hydrogen atom.

[0203] In step b), at least one compound D is added to the starting mixture. At least one compound D contains d' as one or more additional functional groups. d' additional functional groups can react with epoxy functional groups and contain at least one active hydrogen atom. In step b), the active hydrogen atoms of d' additional functional groups can react with c' epoxy functional groups of at least one compound C. It is clear that the active hydrogen atoms of b' primary amine functional groups that have not yet reacted with a' functional group of -C(=O)ORx type and / or -C(=O)-type and the active hydrogen atoms of b'' additional functional groups can also react with c' epoxy functional groups of at least one compound C.

[0204] Such a fourth preferred method comprises the following steps:

[0205] a) contacting at least one compound A with at least one compound B, thereby obtaining a mixture comprising or consisting of a curing agent,

[0206] wherein the at least one compound A has a' functional groups of -C(=O)ORx type and / or -C(=O)- type, wherein a' is an integer equal to or greater than 2, and wherein Rx of each functional group is independently selected from the group consisting of H and C1-C4 alkyl, and wherein in the case where compound A has a' functional groups of -C(=O)- type, compound A is a cyclic carboxylic anhydride,

[0207] wherein each of the a' functional groups of the -C(=O)ORx type and / or -C(=O)- type belongs to a functional group pair comprising a first functional group and a second functional group, wherein the number of atoms between the carbonyl group of the first functional group and the carbonyl group of the second functional group is in the range of 2 to 8, and

[0208] wherein at least one compound B has b' primary amine functional groups and has b'' additional functional groups, wherein b' is an integer equal to or greater than 2 and b'' is an integer equal to or greater than 0, wherein each of the b' primary amine functional groups belongs to a functional group pair comprising a first primary amine functional group and a second primary amine functional group, wherein the number of atoms between the first primary amine functional group and the second primary amine functional group is at least 5, and each of the b' primary amine functional groups is directly connected to a primary carbon atom. In the case where at least one compound B comprises b'' additional functional groups, such additional functional groups are preferably selected from the group consisting of a primary amine functional group, a secondary amine functional group, an alcohol functional group, a thiol functional group and a -C(=O)OH functional group,

[0209] wherein during step a), a dynamic bond is formed by reaction of at least a portion of the a' functional groups of -C(=O)ORx type and / or -C(=O)- type with at least a portion of the b' primary amine functional groups,

[0210] b) contacting said mixture obtained in step a) further comprising at least one compound D with at least one compound C, thereby obtaining an epoxy-derived covalent adaptive network,

[0211] wherein the at least one compound C has c' epoxy functional groups, wherein c' is an integer equal to or greater than 2,

[0212] wherein the at least one compound D has d' additional functional groups, wherein d' is an integer equal to or greater than 1 and, wherein the d' additional functional groups are selected from the group consisting of: a primary amine functional group, a secondary amine functional group, an alcohol functional group, a thiol functional group and a -C(=O)OH functional group,

[0213] Therein, during step b), permanent bonds are formed by reaction of at least a portion of the at least c' epoxy functional groups with active hydrogen atoms of functional groups capable of reacting with epoxy functional groups present in the mixture.

[0214] in

[0215] - Equal to or greater than ,

[0216] - Ratio is in the range of 0.5 to 1.5, and

[0217] - In x> In the case of is equal to or greater than 0.4, or when x< In the case of Equal to or greater than 0.4,

[0218] in

[0219] n i It is functional Compound A i The number of millimoles (mmol),

[0220] n j It is functional Compound B j The number of millimoles (mmol),

[0221] n k It is functional Compound C i The number of millimoles (mmol),

[0222] x is the total number of active hydrogen atoms of all functional groups capable of reacting with epoxy functional groups present at the beginning of step b). Preferably, x is the total number of active hydrogen atoms of all b' functional groups present at the beginning of step b) that have not reacted with a' functional groups of the -C(=O)ORx type and / or -C(=O)- type, the total number of active hydrogen atoms of all b" additional functional groups present at the beginning of step b), and the total number of active hydrogen atoms of all d' functional groups present at the beginning of step b).

[0223] According to a second aspect of the present invention, a composition comprising an epoxy-based covalent adaptive network is provided, and the composition can be obtained by the above method.

[0224] According to a third aspect of the present invention, there is provided a use of a composition comprising an epoxy-based covalent adaptive network, preferably an epoxy-based covalent adaptive network obtainable by the above method. The composition comprising the epoxy-based covalent adaptive network is used, for example, as an adhesive or a coating.

[0225] In a specific embodiment, the composition comprising the epoxy-based covalent adaptive network is used as a packaging material for electronic components. BRIEF DESCRIPTION OF THE DRAWINGS

[0226] The present invention will be discussed in more detail below with reference to the accompanying drawings, in which:

[0227] - Figure 1 The synthesis strategy of a polyamide resin (Example 1) is shown, which is obtained starting from the methyl ester of a dicarboxylic acid, the trifunctional amine tris(2-aminoethyl)amine (TREN) as a crosslinker and the difunctional Priamine 1074 as a chain extender;

[0228] - Figure 2The synthesis strategy of the composition comprising the epoxy-based covalent adaptive network according to the present invention (Example 2) is shown, which is synthesized starting from the methyl ester of a dicarboxylic acid, the trifunctional amine tris(2-aminoethyl)amine (TREN) and 1,4-butanediol diglycidyl ether;

[0229] - Figure 3 The thermal stability of Example 1 and Example 2 is shown by plotting the isothermal TGA measurements for the composition of Example 1 measured at 200°C over 120 minutes and the isothermal TGA measurements for the composition of Example 2 measured at 200°C and 250°C;

[0230] - Figure 4 The relaxation time as a function of temperature is plotted to show the difference in the dynamic behavior of Example 1 and Example 2;

[0231] - Figure 5 and Figure 6 Depicts the unnormalized stress-relaxation data of Example 1 and Example 2 at different temperatures, respectively;

[0232] - Figure 7 The thermal stability (isothermal TGA) of Examples 007B, 009A and 009B at 200°C for 120 minutes is shown;

[0233] - Figure 8 The thermal stability (isothermal TGA) of Examples 011B, 011C and 018K at 200°C for 120 minutes is shown;

[0234] - Fig. 9 The thermal stability (isothermal TGA) of Examples 012A and 016B at 250°C for 120 minutes is shown;

[0235] - Fig.10 The thermal stability (isothermal TGA) of Examples 024B, 026A, and 026B at 250°C for 120 minutes is shown;

[0236] - Fig.11a , 11b and 11c show the synthesis strategy, stress-relaxation behavior and shear viscosity diagram of Example 007B, respectively;

[0237] - Figures 12 to 22 show the synthesis strategy, stress-relaxation behavior and shear viscosity graphs of Examples 009A, 009B, 011B, 011C, 018K, 012A, 16D, 024B, 026A, 026B and 027B;

[0238] - Fig.23a , 23band 23c show creep data, shear viscosity plot (obtained from stress-relaxation measurements), and zero shear viscosity plot (obtained from creep measurements) for Example 016C, respectively;

[0239] - Fig.24 Frequency sweep data for Example 024B is shown. DETAILED DESCRIPTION

[0240] The present invention will be described with reference to specific embodiments and with reference to certain drawings, but the invention is not limited thereto but only by the claims. The drawings are schematic and non-limiting. For illustrative purposes, the dimensions of some elements in the drawings may be exaggerated and not drawn to scale. The dimensions and relative dimensions do not correspond to actual implementations of the invention.

[0241] When referring to an end-point of a range, the end-point of the range is included.

[0242] When describing the present invention, the terms used are to be interpreted in accordance with the following definitions unless otherwise specified.

[0243] When two or more items are listed, the term 'and / or' means that any one of the listed items may be used alone or any combination of two or more of the listed items may be used.

[0244] Various compositions were synthesized and evaluated using the characterization procedures given below.

[0245] Thermogravimetric analysis (TGA) was performed on a Mettler-Toledo TGA / SDTA 851e instrument. Isothermal TGA measurements were performed at 10 °K.min under nitrogen atmosphere. -1 The heating rate was 200 °C or 250 °C for 120 min.

[0246] The 1 / 700 Mettler Toledo instrument was used under nitrogen atmosphere at 10 K.min -1 The heating rate is 10K.min -1 Differential scanning calorimetry (DSC) was performed at a cooling rate of 1.5 ℃. Several measurement cycles were performed from -50 °C to 150 °C. The glass transition temperature (T g ).

[0247] Attenuated total reflectance Fourier transform infrared (ATR-FTIR) analysis was performed on a Perkin-Elmer Spectrum 1000 FTIR infrared spectrometer equipped with a diamond ATR probe.

[0248] The network is (re)processed using compression molding. The sample is cut or ground into small pieces with a diameter size of about 1 to 2 mm and placed in a steel mold. The mold is transferred to a hot plate press at 200°C or 250°C and pressed at a pressure of 2 to 4 metric tons for 15 to 90 minutes. The sample is taken out after the mold is cooled to ~ 80 to 100°C.

[0249] Stress-relaxation experiments were performed on samples with a diameter of 8 mm and a thickness of 1 mm using an Anton-Paar MCR 302 rheometer with a plate diameter of 8 mm. Stress-relaxation experiments were then performed using a shear strain of 0.5% and a constant force of 1 N. By converting the relaxation modulus ( , in Pa) data are fitted to a single exponential decay (according to formula (1): (1) Single Maxwell, we can get the relaxation time ( , unit is s), and according to formula (2): (2), the relaxation time can be related to the shear viscosity ( , in Pa·s) and shear modulus Related. Initial relaxation modulus ( , in Pa) is obtained from the stress-relaxation data at 1 s. The function of temperature enables the determination of the mobility or dynamic behavior of epoxy-derived covalent adaptive networks. Relative to 1000 / T (K -1 ) function graph, the activation energy ( , unit is kJ·mol -1 ).

[0250] Frequency sweep experiments were performed using an Anton-Paar MCR rheometer with a strain of 0.5% while applying a normal force of 1 N, and the range from 0.01 to 100 rad·s was screened by tracking the evolution of G′ and G″ at a constant temperature. −1 Subsequently, the same process is repeated at different temperatures from high to low.

[0251] Creep experiments were also performed at different temperatures (50 to 120 °C in 10 °C intervals) on an Anton-Paar MCR rheometer using an applied force of 1 N. A shear stress (σ, in Pa) of 2000 Pa was applied for 5000 s, and the shear strain was monitored as a function of time. The creep rate value ( , unit is s -1 ), and the creep rate value is similar to the zero shear viscosity ( , in Pa) according to formula (3): (3) As shown. Monitoring The function of temperature enables the determination of the mobility or dynamic behavior of epoxy-derived covalent adaptive networks. Relative to 1000 / T (K -1 ) function graph, the activation energy ( , unit is kJ·mol -1 ).

[0252] Example

[0253] according to Figure 1 The polyamide resin (Example 1) was synthesized according to the synthetic strategy shown. Figure 2 The synthetic strategy shown was used to synthesize a composition comprising an epoxy-based covalent adaptive network according to the present invention (Example 2). The details of the synthesis of Example 1 and Example 2 are given below.

[0254] Figures 11 to 22 show the synthesis strategy, stress-relaxation behavior and shear viscosity diagram of specific embodiments. In the shear viscosity diagram, Relative to 1000 / T (unit: K -1 ) function graph.

[0255] Example 1

[0256] Dimethyl glutarate (1.83 g, 11.4 mmol, 1 eq.), TREN (0.67 g, 4.57 mmol, 0.4 eq.) and Priamine 1074 (2.5 g, 4.57 mmol, 0.4 eq.) were mixed in a 20 mL polypropylene cup using a DAC 150.1 FVZ high-speed mixer (typical mixing conditions: mixing at 2500 rpm for 2 minutes). The cup was then placed in an oven at 100° C. for 24 hours to induce network formation. Afterwards, the network was further cured at 100° C. under vacuum for 24 hours.

[0257] Example 2

[0258] Dimethyl glutarate (0.79 g, 4.92 mmol, 1 eq) and Priamine 1074 (3.5 g, 6.40 mmol, 1.3 eq) were first mixed in a 20 mL polypropylene cup using a DAC 150.1 FVZ high-speed mixer (typical mixing conditions: mixing at 2500 rpm for 2 minutes). The cup was then placed in an oven at 80 ° C for 24 hours to prepare the dynamic curing agent. Next, 1,4-butanediol diglycidyl ether (0.59 g, 2.95 mmol, 0.6 eq) was added to the mixture, and high-speed mixing was repeated until a uniform viscous liquid was obtained. Afterwards, the network was heated in an oven at 80 ° C for 4 hours to induce curing. Subsequently, the network was cured at 100 ° C under vacuum for 24 hours.

[0259] Previously described in this article Figure 3-6 Selected results of characterization performed on Example 1 (comparative example) and Example 2 (an example according to the invention) are shown. Figure 3 It can be observed that, even at a temperature of 250° C., the weight loss of the composition according to the invention is significantly lower. Figure 4 It is shown that Example 1 has higher thermal stability and higher processing temperature than Example 2. Figure 5 and Figure 6 Shows the relaxation modulus (in Pa) versus relaxation time (unit: s) is a functional relationship.

[0260] Other embodiments

[0261] According to the method of the present invention, a series of compositions comprising epoxy-based covalent adaptive networks according to the present invention were synthesized starting from different combinations of compounds A, B, C and E given in Tables 3, 4, 5 and 6, respectively. The formulations of multiple examples are given in Tables 7, 8 and 9.

[0262] Table 3: Examples of Compound A

[0263]

[0264] Table 4: Examples of Compound B

[0265]

[0266] Table 5: Examples of Compound C

[0267]

[0268] Table 6: Examples of Compound E

[0269]

[0270] Previously described in this article Figure 7-10 The thermal stability is shown based on the composition shown in Table 7. The example containing a portion of fatty amine (Priamine 1074) shows higher thermal stability.

[0271] Figures 11-22 show the synthesis strategy, stress-relaxation behavior and shear viscosity diagrams of specific embodiments. Starting from different combinations of compounds A, B, C and E, the optimal balance between crosslink density and material flow is depicted. The glass transition temperature (T g ). Despite leading to a highly cross-linked network, a sharp viscosity drop (i.e. activation energy values ​​above 200 kJ.mol -1 ). The observed viscosity drop is the result of both reversible chain scission (modulus loss) and exchange of dissociative intermediates (relaxation). As a result, these epoxy-derived covalent adaptive networks show sufficient (re)processability only at higher temperatures.

[0272] The results of creep experiments and corresponding viscosity graphs compared with stress-relaxation data for specific embodiments are shown in Figure 23. Large differences in dynamic behavior are observed between 200°C and 250°C (high activation energy or sharp viscosity drop from high temperature stress-relaxation) and between 60°C and 120°C (low activation energy or low viscosity drop from low temperature creep experiments).

[0273] Fig.24 The results of frequency sweep experiments of specific examples are shown. Long-term heating at higher temperatures does not lead to significant degradation or reduction of material properties, because heating from 250°C to 190°C results in recovery of crosslink density, and heating at 10 6 Up to 10 7 Pa high plateau storage modulus values.

[0274] Table 7

[0275]

[0276] Table 8

[0277]

[0278] Table 9

[0279]

Claims

1. A method for preparing a composition comprising an epoxy-based covalent adaptive network, the method comprising the following steps: a) contacting at least one compound A with at least one compound B, thereby obtaining a mixture comprising a curing agent, wherein the at least one compound A has a' functional groups of the -C(=O)ORx type and / or -C(=O)- type, wherein a' is an integer equal to or greater than 2, and wherein Rx of each functional group is independently selected from the group consisting of H and C1-C4 alkyl, wherein each of the a' functional groups of -C(=O)ORx type and / or -C(=O)- type belongs to a functional group pair including a first functional group and a second functional group, wherein the number of atoms between the carbonyl group of the first functional group and the carbonyl group of the second functional group is in the range of 2 to 8, and wherein in the case where the at least one compound A comprises a functional group having a -(C=O)- type as the first functional group and the second functional group, the at least one compound A comprises a cyclic carboxylic acid anhydride, wherein the first functional group and the second functional group belong to the carboxylic acid functional group of the at least one compound A, and wherein the at least one compound B has b' primary amine functional groups, wherein b' is an integer equal to or greater than 2, wherein each of the b' primary amine functional groups belongs to a functional group pair including a first primary amine functional group and a second primary amine functional group, wherein the number of atoms between the first primary amine functional group and the second primary amine functional group is at least 5, wherein each of the b' primary amine functional groups is directly attached to a primary carbon atom, wherein during step a), a dynamic bond is formed by reaction of at least a portion of the a' functional groups of -C(=O)ORx type and / or -C(=O)- type with at least a portion of the b' primary amine functional groups, b) contacting said mixture obtained in step a) with at least one compound C, thereby obtaining an epoxy-derived covalent adaptive network, wherein the at least one compound C has c' epoxy functional groups, wherein c' is an integer equal to or greater than 2, wherein, during step b), permanent bonds are formed by reaction of at least a portion of the at least c' epoxy functional groups with active hydrogen atoms of functional groups capable of reacting with epoxy functional groups present in the mixture, in - Equal to or greater than , - Ratio is in the range of 0.5 to 1.5, and - In x> In the case of is equal to or greater than 0.4, or when x< In the case of Equal to or greater than 0.4, in n i It is functional Compound A i The number of millimoles, n j It is functional Compound B j The number of millimoles, n k It is functional Compound C i The number of millimoles, x is the total number of active hydrogen atoms of all functional groups present at the beginning of step b) which are capable of reacting with epoxy functional groups.

2. The method according to claim 1, wherein the number of atoms between the carbonyl group of the first functional group and the carbonyl group of the second functional group in the functional group pair of a' functional groups of -C(=O)ORx type and / or -C(=O)- type is 2, 3 or 4.

3. The method according to any one of the preceding claims, wherein at least a portion of the atoms between the carbonyl group of the first functional group and the carbonyl group of the second functional group in the functional group pair of -C(=O)OR type and / or -C(=O)- type is part of a cyclic structure, which is optionally substituted.

4. The method according to any one of the preceding claims, wherein the at least one compound A has a' functional groups of the -C(=O)ORx type, wherein each of the a' functional groups of the -C(=O)ORx type belongs to a functional group pair comprising a first functional group and a second functional group.

5. The method according to any one of the preceding claims, wherein at least a portion of the atoms between the carbonyl group of the first functional group and the carbonyl group of the second functional group in the functional group pair of the -C(=O)ORx type comprises a linear saturated or unsaturated hydrocarbon, and optionally one of the atoms between the carbonyl group of the first functional group and the carbonyl group of the second functional group is substituted.

6. The method according to any one of the preceding claims, wherein the first primary amine functional group and the second primary amine functional group in the functional group pair of b' primary amine functional groups are connected by a linking moiety, the linking moiety comprising or consisting of a group selected from the group consisting of: C 6-40 Alkyl, C 6-24 Alkenyl, C 6-40 Alkynyl, C 6-24 Aryl, C 6-24 Cycloalkyl, C 6-24 Aryl C 1-40 Alkyl; wherein one or more carbon atoms in the backbone of the alkyl, alkenyl, alkynyl, aryl or cycloalkyl group may be substituted by heteroatoms independently selected from O, S, N and Si, and wherein the alkyl, alkenyl, alkynyl, aryl or cycloalkyl group may be unsubstituted or further substituted.

7. The method according to any one of the preceding claims, wherein the functional group comprising at least one active hydrogen atom and capable of reacting with an epoxy functional group is selected from the group consisting of a primary amine functional group, a secondary amine functional group, an alcohol functional group, a thiol functional group and a -C(=O)OH functional group.

8. The process according to any one of the preceding claims, wherein at least one compound E is present in step a), wherein the at least one compound E comprises e' primary amine functional groups and does not comprise a functional group pair of b' primary amine functional groups, wherein e' is an integer equal to or greater than 1, and the at least one compound E is present in an amount of up to 10% by weight of the total amount of the at least one compound B. in, During step a), dynamic bonds are formed by reaction of at least a portion of the a' functional groups of -C(=O)ORx type and / or -C(=O)- type with at least a portion of the b' primary amine functional groups of the at least one compound B, and optionally by reaction of at least a portion of the a' functional groups of -C(=O)ORx type and / or -C(=O)- type with at least a portion of the e' primary amine functional groups of the at least one compound E.

9. The process according to any one of the preceding claims, wherein at least one compound D is present in the mixture of step b), wherein the at least one compound D has d' functional groups containing at least one active hydrogen atom capable of reacting with an epoxy functional group, wherein d' is an integer equal to or greater than 1, and the at least one compound D is present in an amount of up to 10% by weight of the mixture at the beginning of step b).

10. The process according to claim 1 , wherein the functional groups comprising at least one active hydrogen atom and capable of reacting with epoxy functional groups include b′ functional groups of the at least one compound B that have not reacted with one of the a′ functional groups of the at least one compound A, or include b″ additional functional groups of the at least one compound B, or include e′ functional groups of the at least one compound E, or include d′ functional groups of the at least one compound D present in the mixture at the beginning of step b).

11. A composition comprising an epoxy-derivatized covalent adaptive network, said composition being obtainable by the method of any one of claims 1 to 10.

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