Double hardening type vitriol

Abstract

The present invention provides a) at least one R on the phenol ring * The present invention relates to a method for synthesizing ester and acrylate moieties of benzoxazine monomers, comprising the steps of: a) reacting a phenolic hydroxyl group-containing compound with a group with a carboxylic acid compound at a temperature of 25°C to 200°C for 1 to 72 hours in the presence of a Brønsted acid-type catalyst and under an inert atmosphere to obtain a phenol-terminated oligomer or molecule; b) reacting the phenol-terminated oligomer or molecule with a mixture of an aldehyde compound selected from the amino alcohol of formula (V), formaldehyde, and paraformaldehyde, and a primary amine at a temperature of 50°C to 200°C for 1 to 12 hours under an inert atmosphere to produce a compound of formula (VII); and c) reacting the compound obtained in step b) with a compound having an acrylate or methacrylate group.

Description

[Technical Field]

[0001] This invention relates to the field of dual-curable benzoxazine derivative vitrimers, methods for producing the same, and the use of the vitrimers in various applications. [Background technology]

[0002] Vitrimers are polymeric materials that, due to the dynamic properties of their covalent network structure resulting from reversible chemical bonding, allow materials to be repaired, recycled, and reprocessed like thermoplastics. These exchange reactions are triggered by external stimuli, most frequently temperature. The viscosity of vitrimers gradually decreases upon heating, giving the network structure malleability while relieving internal stresses. The integrity of the network structure across the entire range of applications ensures mechanical and solvent resistance.

[0003] Dynamic transesterification reactions have attracted considerable interest over the past decade, following a prototype vitrimer developed by Leibler et al. in 2011 (D. Montarnal, M. Capelot, F. Tournilhac, and L. Leibler, Science, 2011, pp. 334, 965-968). These chemical exchanges, induced between ester bonds and hydroxyl groups at high temperatures, are responsible for topological rearrangement. Transesterification mechanisms have been implemented in crosslinked network structures to design self-healing, recyclable, and reworkable materials with tunable properties.

[0004] Demongeot et al. (A. Demongeot, R. Groote, H. Goossens, T. Hoeks, F. Tournilhac, and L. Leibler, Macromolecules, 2017, 50(16), pp. 6117-6127) adapted the concept of vitrimers to commercially available thermoplastics. Crosslinked polybutylene terephthalate (PBT) vitrimers based on transesterification were successfully prepared by reactive extrusion. In addition to improving the manufacturing techniques and the range of possible network structures, the global environmental protection situation is calling on the scientific community to promote sustainable polymers derived from naturally occurring raw materials. Altuna et al. (FI Altuna, V. Pettarin, and R. Williams, Green Chem., 2013, 15, pp. 3360-3366) attempted to produce a completely bio-based polyester exhibiting properties reminiscent of vitrimers, starting from epoxidized soybean oil and an aqueous citric acid solution. Furthermore, Legrand et al. (A. Legrand and C. Soulie-Ziakovic, Macromolecules, 2016, 49, pp. 5893-5902) have expanded the scalability of the application of vitrimer reticular structures by developing silica-reinforced epoxy vitrimer nanocomposites with enhanced properties.

[0005] Polybenzoxazines are a novel type of thermosetting resin with outstanding mechanical and thermal properties. Like many other thermosetting resins, they cannot be remolded, reprocessed, or recycled. A few examples showing a reasonable level of repairability have been reported (L. Zhang, Z. Zhao, Z. Dai, L. Xu, F. Fu, T. Endo, X. Liu, ACS Macro. Lett. 2019, 8, 5, pp. 506-511 and Arslan M., Kiskan B., Y. Yagci, Sci. Rep. 2017, 7, 5207).

[0006] The applicant has shown that several different chemical structures of polybenzoxazine type vitrimers exhibit, in particular, self-healing, reformability, reworkability, high strength, and low melt viscosity due to the benzoxazine portion of the starting monomer used to produce the corresponding vitrimer by polymerization. WO 2021 / 180562 A1 relates to vitrimers obtained by polymerization of disulfide-containing benzoxazine monomers. WO 2022 / 122735 A1 and WO 2021 / 250024 relate to vitrimers obtained by polymerization of ester-containing benzoxazine monomers.

[0007] The publication "3D printing of dual-cure benzoxazine networks" by Jeremy J. Weigand et al., Polymer 189 (2020) 122193, discloses a benzoxazine monomer suitable for 3D printing, whose structure does not contain an ester moiety or a free aliphatic hydroxyl group for obtaining a vitrimer.

[0008] Vitrimers, particularly those derived from benzoxazine monomers, especially ester-containing benzoxazine monomers, still seem to need to exhibit improved properties for specific applications. In some cases, the monomers exhibit some 3D printing capability, but heating is required after the 3D printing process to obtain the corresponding 3D-molded vitrimer. The main drawback of this heating process is the loss of the 3D-molded structure, i.e., the inability to obtain a polybenzoxazine vitrimer with a 3D-printed structure. Furthermore, there is a need for several vitrimers that exhibit lower viscosity, higher Tg, and better mechanical properties at room temperature compared to those already existing. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] International Publication No. 2021 / 180562

Patent Document 2

Patent Document 3

Non-Patent Document

[0010]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Non-Patent Document 4

Non-Patent Document 5

Non-Patent Document 6

Non-Patent Document 7

Summary of the Invention

[0011] This invention overcomes one of the previous drawbacks and relates to a benzoxazine monomer containing ester and acrylate moieties of formula (I).

[0012] [ka]

[0013] During the ceremony, R1 is

[0014] [ka]

[0015] And, R2 is

[0016] [ka]

[0017] And, R3 is

[0018] [ka]

[0019] And, R a This is selected from the group consisting of linear or branched C1-C6 alkyl or alkoxy groups, linear or branched C2-C6 alkenyl or alkylene oxy groups, substituted or unsubstituted linear or branched C2-C6 alkynyl groups, and -C-linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl groups; R * H, OH and O-linear or branched C1-C6 alkyl groups, linear or branched C1-C 15 Alkyl alkyl group or C2-C 15 Alkenyl group or

[0020] [ka]

[0021] Selected from the group consisting of; R'', R ** R is independently a linear or branched C1-C6 alkyl or alkoxy group; a linear or branched C2-C6 alkenyl or alkylene oxy group; a substituted or unsubstituted linear or branched C2-C6 alkynyl group; at least one linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted o-, m-, p-phenyl group, cyclo(C3-C6 alkyl) group or heterocyclo(C3-C6 alkyl) group (where the heteroatom is selected from N, S, and O); (CH2) n3 -Phenyl group, -(CH2) n1 -O-(CH2) n2 -(CH3) base, (where n1 and n2 are independent integers from 1 to 10),

[0022] [ka]

[0023] and

[0024] [ka]

[0025] Selected from the group consisting of; R''' is Me, H, or CN; n3 is an integer between 1 and 10; however, 1 ≤ n < 50, and x > 0, y > 0, and z ≥ 0, and independently of n, x + y + z = 1; x, y, and z represent the ratio between benzoxazine groups and methacrylate groups when prepared from amino alcohols and other amines.

[0026]

number

[0027] Here,

[0028]

Number

[0029] where n アミノアルコール is the number of amino alcohols, and n アミン represents the number of amines (excluding the number of amino alcohols), and n アクリレート corresponds to the number of acrylate / methacrylate groups, and n 総官能基 is the total number of functional groups in the benzoxazine ring.

[0030] The values of x and z depend on the molar ratio between the number of amines (n アミン ) and the number of amino alcohols (n アルコール ) used to form the benzoxazine ring. The value of y depends on the rate of conversion of the amino alcohol in the acrylate / methacrylate functional group.

[0031] The benzoxazine monomer containing the ester and acrylate moieties of the present invention is advantageously suitable for obtaining a polybenzoxazine vitrimer by a dual curing procedure, i.e., a procedure involving successive curing steps, which is very advantageously a 3D printing procedure, in which case the 3D-formed structure in the polybenzoxazine vitrimer is maintained, contrary to known polybenzoxazine vitrimers. This is explained by the fact that known benzoxazine monomers that give rise to vitrimers exhibit (i) viscosities that are too high for 3D printing, (ii) need to be post-cured after printing, and (iii) are not UV curable.

[0032] The preparation of polybenzoxazine vitrimers derived from benzoxazine monomers containing ester and acrylate moieties according to the present invention comprises a double curing procedure including a first curing step by UV-treated polymerization, which allows for polymerization of the acrylate moiety and fixation of the shape of the resulting structure. Following the first curing step, a second curing step is performed by thermal treatment of the benzoxazine moiety of the benzoxazine monomer containing ester and acrylate moieties, wherein the benzoxazine monomer containing ester and acrylate moieties does not melt during the thermal treatment due to the preceding UV treatment for polymerization of the acrylate moiety.

[0033] In this invention, "polybenzoxazine vitrimer" and "double-cured vitrimer" have the same meaning.

[0034] An advantage is that the preparation of such a double-cured vitrimer can be carried out during the 3D printing procedure, or in some embodiments, after the 3D printing procedure.

[0035] The polybenzoxazine vitrimer is obtained as a result of benzoxazine ring-opening and autopolymerization in the benzoxazine monomer containing the ester and acrylate moieties of the present invention, performed by or during a second curing step under heating. The particular monomer as a starting material can advantageously exhibit a low viscosity at 25°C, typically 50 to 10,000 mPa.s, preferably 100 to 10,000 mPa.s, and more preferably 200 to 3,000 mPa.s. In some further embodiments, the viscosity at 25°C may be 3,000 to 8,000 mPa.s. For the remainder of this document, benzoxazine vitrimer always refers to the polymerized form of an ester-linked benzoxazine monomer.

[0036] The properties of the double-cured vitrimer are closely related to the properties of the ester-containing benzoxazine monomer.

[0037] As can be seen from formula (I), the monomer includes a benzoxazine ring moiety that enables crosslinking of the monomer upon heating and facilitates the reprocessing of the resulting benzoxazine vitrimer thanks to the interchangeable ester bonds formed upon crosslinking. The benzoxazine produces thermosetting properties, such as high temperature and flammability, high strength, thermal stability, low water absorption, chemical resistance, low melt viscosity, and near-zero shrinkage.

[0038] The presence of moieties at the ester bond, free aliphatic hydroxyl groups, and acrylate moieties is essential for forming the dynamic network structure of the benzoxazine vitrimer, which allows the material to be recycled, reshaped, and reprocessed. The amines at the hydroxyl group termini allow the oxazine ring to close, enabling transesterification reactions. Therefore, the essential features of the monomer of the present invention rely on the benzoxazine-containing moiety, ester bond, free aliphatic hydroxyl groups, and acrylate moieties. Various groups in R1 and R2 (R * Since R'' and R''' are used as supports for the OH group, ester, and acrylate moieties, their inclusion, even if required, does not impair the effects of the present invention. The Tg of such polybenzoxazine vitrimers can range from -50°C to 250°C, and the elastic modulus is in the range of 0.1 to 4 GPa, which is measured by classical thermomechanical analysis.

[0039] Preferentially, Ra can be selected from the group consisting of linear or branched C1-C4 alkyl or alkoxy groups, linear or branched C2-C4 alkenyl or alkyleneoxy groups, substituted or unsubstituted linear or branched C2-C4 alkynyl groups, and linear or branched C1-C4 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl groups; independently, R * H, OH and O-linear or branched C1-C4 alkyl groups, linear or branched C1-C 10 Alkyl alkyl group or C2-C 10 Alkenyl groups, more preferably linear or branched C1-C6 alkyl groups, C2-C6 alkenyl groups, or C2-C6 alkynyl groups

[0040] [ka]

[0041] A selection can be made from the group consisting of the following:

[0042] Preferably, in the definition of R'', each C atom of the phenyl group, cyclo(C3-C6 alkyl) group, or heterocyclo(C3-C6 alkyl) group may independently have the substituents defined above.

[0043] Furthermore, the benzoxazine monomers containing the ester and acrylate moieties of the present invention may be used in combination with or mixed with other benzoxazine monomers selected from the group consisting of, for example, monofunctional amines crosslinked with diphenol compounds, monophenol compounds crosslinked with diamines, and diamines crosslinked with diphenol compounds, or mixtures thereof, in order to improve the processability of the benzoxazine monomers containing the ester and acrylate moieties during polymerization to obtain their vitrimers (improvement of the viscosity of the resulting mixture: monomer 1 of the present invention and the other monomer (monomer 2)). The properties of the polybenzoxazine derivative vitrimers are closely linked to the properties of the benzoxazine monomers containing the ester and acrylate moieties. The mixture of both monomers 1 and 2 may have a monomer 1:monomer 2 ratio of 1% to 90% by weight.

[0044] Preferably, 1 ≤ n < 40, 1 ≤ n < 30, 1 ≤ n < 20, 1 ≤ n < or 1 ≤ n < 5.

[0045] The present invention also relates to a method for synthesizing a benzoxazine monomer containing the ester and acrylate moieties of formula (I), the method being: a) At least one R on the phenol ring * Phenolic hydroxyl group-containing compounds of formula (II) that include the group: (PhOH)w-Ral-OH (II) (In the formula, Ral has the definition of Ra, and w = 1, 2, or 3) The carboxylic acid compound of formula (III) R-(COOH)n (III) (In the formula, R has the definition of R'', and n has the same definition as above.) Then, the reaction is carried out at a temperature of 25°C to 200°C for 1 to 72 hours in the presence of a Brønsted acid-type catalyst and under an inert atmosphere to obtain a phenol-terminated oligomer or molecule (compound (IV)).

[0046] b) Compound (IV), - Amino alcohol of formula (V):

[0047] [ka]

[0048] - Aldehyde compounds selected from formaldehyde and paraformaldehyde of the following formula,

[0049] [ka]

[0050] (In the formula, m is an integer between 8 and 100) - Primary amine of formula (VI) R ** -NH2(VI) The process involves reacting a mixture of the following at a temperature of 50°C to 200°C for 1 to 12 hours under an inert atmosphere to produce a compound of formula (VII), and

[0051] c) A step of reacting compound (VII) with a compound having an acrylate or methacrylate group, wherein the compound is at least one defined by the following compounds (VIII) to (XII): (i) (meth)acrylate chloride of formula (VIII) in a polar solvent at a temperature of -5°C to 25°C

[0052] [ka]

[0053] ; or (ii) Methyl (meth)acrylate of formula (IX) in the presence of a catalyst and polymerization inhibitor

[0054] [ka]

[0055] ; or (iii) (meth)acrylic acid of formula (X) in a solvent at temperatures from -10°C to reflux in the presence of a catalyst and azodicarboxylate.

[0056] [ka]

[0057] ; or (iv) Excess (meth)acrylic acid of formula (X) in the presence of a catalyst; or (v) (meth)acrylic anhydride of formula (XI) or asymmetric anhydride of formula (XII) in the presence of a catalyst

[0058] [ka]

[0059] (In the formula, - R'''' is H or CH3, - R''"' is either CH3 or C2H5) A step to obtain a benzoxazine monomer containing the ester and acrylate moiety of formula (I) by reacting at a temperature of -10°C to 50°C for 12 to 48 hours. The process includes the following steps: However, at least one R of the phenolic acid derivative * When R is in the ortho position relative to the -OH group, * H is H.

[0060] In this method, R, Ra, R * , R ** And R'' has a definition for equation (I).

[0061] According to this method, the "z" value can be 0 independently of the "x" value (z=0), which means that in some embodiments, the primary amine may be excluded. Compounds of formula (V), amino alcohols, are used in both cases.

[0062] The applicant has shown that a specific starting reactant yields a benzoxazine monomer containing an ester and an acrylate moiety, which then polymerizes to produce a polybenzoxazine derivative vitrimer containing benzoxazine.

[0063] Neither reactive diluents nor solvents are required in steps a) and b). Other advantages of the resulting monomer are as described above, particularly its low viscosity at 25°C, typically 1000-10000 mPa.s, and more preferably 200-3000 mPa.s, and high Tg value.

[0064] Step a) can be advantageously carried out at a temperature range of 80°C to 170°C, most preferably 100°C to 140°C for the best synthesis yield higher than 95%, and the selected temperature depends on the properties of the reactants, i.e., the melting temperature of the reactant medium.

[0065] Advantageously, step a) is carried out for 12 to 48 hours, or more favorably, 12 to 36 hours for a maximum yield of at least 95%, with the duration based on the reaction kinetics.

[0066] Brønsted acid catalysts are commonly used in Fischer esterification and include p-toluenesulfonic acid (p-TSA), hydrochloric anhydride (HCl), phosphoric acid (H3PO4), methaneic acid (CH3-CO2H), sulfuric acid, tosylic acid, and Lewis acids, such as scandium(III) triflate. The catalyst content is typically 0.5% to 2% by weight.

[0067] In step a), the stoichiometric ratio of the starting reactants, the phenolic hydroxyl group-containing compound:carboxylic acid compound, is preferably n equivalents:1.0 equivalent, and a 1.0 equivalent oligomer or molecule of the phenol terminus (compound (IV)) is produced.

[0068] Step a) can be carried out under inert atmosphere conditions, for example, by using Ar or N gas.

[0069] The second step of the method, step b), corresponds to an optional Mannich condensation reaction in the presence of a catalyst between the phenol-terminated oligomer or molecule ((IV)) of step a) and an aldehyde compound selected from amino alcohols (formula (V)), formaldehyde, and paraformaldehyde, as well as a primary amine of formula (VI). Thus, since step b) does not require the use of an external catalyst, step b) can be carried out in a simpler manner. Step b) enables the formation of R1 and R3.

[0070] Step b) can be carried out under inert atmosphere conditions, for example, by using Ar or N gas.

[0071] Advantageously, the amino alcohol in formula (V) is R * It is a linear amino alcohol containing a group and having a primary amine moiety and an aliphatic hydroxyl moiety for obtaining an oxazine ring in the highest yield and under the best reaction conditions.

[0072] The amino alcohol of formula (V) may more preferably be selected from the group consisting of 2-aminoethanol, 2-amino-2-methylpropanol, 5-aminopentan-1-ol, heptaminol, 2-(2-aminoethoxy)ethanol, and diglycolamine, or mixtures thereof.

[0073] Primary amines are R as defined above ** Includes the base.

[0074] The primary amine may be further selected from the group consisting of allylamine, methylamine, ethylamine, propylamine, butylamine, isopropylamine, hexylamine, cyclohexylamine, stearylamine, 2-aminofluorene, aminophenylacetylene, propargyl etheraniline, 4-aminobenzonitrile, furfurylamine, and aniline, or mixtures thereof.

[0075] In step b), the stoichiometric ratios of the starting reactants, phenol-terminated oligomers or molecules (IV):amino alcohol (V):primary amine (VI):paraformaldehyde, are preferably 1.0 equivalent:n(x+y):nz:2.0n(x+y+z), which yields 1.0 equivalent of compound (VII). In some further examples, the stoichiometric ratios may be 1.0 equivalent:2.0 equivalent:0.0 equivalent:4.0 equivalent, which yields 1.0 equivalent of compound (VII).

[0076] The specific range of stoichiometric ratios depends on the equivalent proportions of the amino alcohol and primary amine. It should be noted that there is a minimum amount required for the reaction to occur. For example, the relative molar percentages of the amino alcohol to the relative molar percentages of the primary amine derivative are 10 mol% to 90 mol%, respectively. This also means that the primary amine may be omitted (0 mol%), and instead, only the amino alcohol may be used (100 mol%). Furthermore, the selected range of stoichiometric ratios for both the amino alcohol / amine and paraformaldehyde is preferable to avoid the formation of linear and / or aliphatic byproducts of the reaction, such as oxazolidines, triaza derivatives, or condensed derivatives.

[0077] The temperature range for step b) is preferably 70°C to 150°C, more preferably 70°C to 120°C, which enables obtaining a maximum conversion yield of at least 75%.

[0078] Advantageously, step b) is carried out for 1 to 8 hours, preferably 1 to 5 hours, for a maximum yield of at least 75%.

[0079] The third step of the method, step c), is the reaction of compound (VII) of step b) with a compound having an acrylate and / or methacrylate group, the latter of which is at least one of compounds (VIII) to (XII), or a mixture thereof.

[0080] In one embodiment, step c) may be carried out by a classical acylation reaction with compound (VIII)-(meth)acrylate chloride-, typically with compound (VII) from step b), in the absence of a suitable catalyst, or preferably in the presence of a catalyst / hydrogen absorber selected from triethylamine (TEA), pyridine, N,N-diisopropylethylamine (DIPEA), and NN-dimethylaniline, in a polar solvent selected from acetonitrile, chloroform, dichloromethane, and N,N-dimethylformamide (DMF), preferably at a temperature of -5 to 15°C for 12 to 48 hours.

[0081] According to another embodiment, step c) may be carried out for 12 to 48 hours by a typically classical re-esterification reaction using compound (IX)-methyl (meth)acrylate- in the presence of a catalyst such as sodium or magnesium alcoholate and a polymerization inhibitor such as p-oxydiphenylamine, with preferred simultaneous distillation of the resulting azeotropic mixture consisting of methanol and methyl ether.

[0082] Step c) may be carried out using compound (X)-(meth)acrylic acid- by ​​a classical Mitsunobu reaction, which typically involves the presence of a catalyst such as triphenylphosphine and an azodicarboxylate such as diethyl azodicarboxylate (DEAD) or diisopropyl azodicarboxylate (DIAD), in a solvent such as tetrahydrofuran (THF) or toluene, at a temperature from -10°C to reflux for 12 to 48 hours.

[0083] According to an alternative embodiment using compound (X)-(meth)acrylic acid, step c) may be carried out by a classical esterification reaction using an excess of the (meth)acrylic acid for 12 to 48 hours, preferably in the presence of an acidic catalyst selected from p-toluenesulfonic acid (p-TCA), sulfuric acid (H2SO4), and methanesulfonic acid (CF3SO3H), accompanied by simultaneous distillation of the resulting azeotropic mixture, for example, toluene or cyclohexane and water.

[0084] In another embodiment, step c) may be carried out by a classical acylation reaction using compound (XI)-(meth)acrylic anhydride- or compound (XII)-(meth)acrylic asymmetric anhydride-, preferably in the presence of a catalyst selected from p-toluenesulfonic acid (p-TCA), sulfuric acid (H2SO4), and anhydride ZnCl2, at a temperature range of -5°C to 15°C.

[0085] Step c) enables the formation of R2.

[0086] Advantageously, the total synthesis may generally not require further monomer purification for the present invention to be carried out. However, if necessary, monomer purification may be carried out by some known technique (vacuum, distillation, resolubilization, extraction with water, a base such as NaOH, or brine, etc.) for example during and / or thereafter. The solvent used may also be removed, if necessary, by classical practices such as the use of low-pressure removal equipment.

[0087] The reaction mixtures in both steps a) and b) are stirred using a classical mechanical stirrer or any non-limiting means.

[0088] The method can be carried out on a laboratory or industrial scale using a suitable container and by any known means familiar to those skilled in the art.

[0089] In step c), the stoichiometric ratio of the starting reactant compound VII: compounds having an acrylate or methacrylate group (VIII-XII) is preferably 1.0 equivalent:3.0ny equivalent, producing a benzoxazine monomer containing 1.0 equivalent of the ester and acrylate moiety. In some embodiments, the "ny" value may be 0.1-10, more preferably 0.5-2.

[0090] The present invention also relates to a method for preparing a polybenzoxazine derivative vitrimer, comprising a first curing step of UV-treated polymerization of a benzoxazine monomer (formula (I)) containing an ester and acrylate moiety, which can be obtained by the present invention or the method described above, and a second curing step of heat treatment following polymerization of the benzoxazine moiety of the benzoxazine monomer containing an ester and acrylate moiety.

[0091] In the present invention, "derivative" means that the resulting vitrimer is obtained by polymerization of the benzoxazine monomer of the present invention and is derived therefrom. Therefore, "polybenzoxazine derivative vitrimer" and "polybenzoxazine vitrimer" have the same meaning.

[0092] The preparation of the polybenzoxazine vitrimer derived from a benzoxazine monomer containing an ester and acrylate moiety according to the present invention comprises a double curing procedure including a first curing step by UV-treated polymerization, which allows for the polymerization of the acrylate moiety of the compound of formula (I) and the fixation of the shape of the resulting structure. Following the first curing step, a second curing step is performed by heat treatment, which involves polymerization of the benzoxazine moiety of the benzoxazine monomer containing the ester and acrylate moiety. This monomer does not melt during the heat treatment thanks to the prior UV treatment for polymerization of the acrylate moiety.

[0093] In this invention, "polybenzoxazine vitrimer" and "double-cured vitrimer" have the same meaning.

[0094] An advantage is that the preparation of such a double-cured vitrimer can be carried out during the 3D printing procedure or, in some embodiments, after the 3D printing procedure.

[0095] Ring-opening and self-polymerization of benzoxazine in the benzoxazine monomer containing the ester and acrylate portions of the present invention, performed by a second curing step or under heating during that step, yields the polybenzoxazine vitrimer.

[0096] The first curing step is carried out using a classical apparatus for performing the first step (UV curing) at typical wavelengths of 30 nm to 500 nm, preferably 280 to 450 nm, in the presence of a classical radical initiator in a percentage by weight (%) which may be 1% to 5% by weight.

[0097] The second curing step is carried out by thermally induced ring-opening polymerization of benzoxazine at a temperature range of 100°C to 250°C, preferably 120°C to 200°C, for 1 to 10 hours.

[0098] The polymerization duration depends on the curing temperature (second curing step) and / or the properties of the benzoxazine monomer containing a single ester. The polymerization temperature is selected to be higher than the temperature required to synthesize a given monomer. Generally, the higher the polymerization temperature, the shorter the curing duration. For example, at a polymerization temperature of 250°C, the curing duration may be at least 1 hour, while at a polymerization temperature of 100°C, the curing duration may be 10 hours or less. Preferably, the curing temperature may be 140°C to 200°C, more preferably 120°C to 180°C, with the latter range resulting in a curing duration of 1.5 to 3 hours, preferably 1.5 to 2.5 hours. Polymerization can be carried out by any known heating means, such as forced or natural convection, conduction, laser beams and infrared beams.

[0099] The method may also include a post-polymerization step, which may preferably be a heating step carried out at a higher temperature than the polymerization heating step.

[0100] The present invention also relates to polybenzoxazine derivative vitrimers that can be obtained by the above method and which may exhibit at least one of the following characteristics: (i) 100°C to 250°C; preferably 130°C to 220°C, more preferably 130°C to 190°C v (Topology (topoly) freezing temperature) value, and (ii) Relaxation temperature value ≥ T, which is 100°C to 300°C, preferably 130°C to 200°C, and more preferably 130°C to 180°C. v value.

[0101] Vitrimmer T v The value generally depends on the properties and content of the catalyst in step b), if present.

[0102] The relaxation temperature typically corresponds to the relaxation temperature of the vitrimer after applying physical deformation such as strain, e.g., torsion, and without any signs of vitrimer degradation.

[0103] To the advantage, Vitrimer also, A relaxation time of -0.5 seconds to 2 hours, preferably 1 second to 1 hour, more preferably 5 seconds to 50 minutes. Conventionally, the relaxation time is defined as the time it takes for a sample to relax to a value corresponding to 1 / e(0.37) of its original modulus of elasticity. Generally, the higher the temperature, the shorter the relaxation time. For example, the relaxation time is about 150 minutes to 200 seconds at temperatures of 120°C to 170°C, and ≤200, preferably 100 seconds to 20 seconds, in the temperature range of 150°C to 200°C.

[0104] In some embodiments, the vitrimer can be deformed by 0.1% to 100% of its initial size;

[0105] - The activation energy related to the relaxation time may be 50 kJ / mol to 200 kJ / mol, preferably 70 kJ / mol to 170 kJ / mol, more preferably 100 kJ / mol to 160 kJ / mol; and

[0106] - The processing temperature may be 100°C to 250°C, preferably 130°C to 250°C, more preferably 150°C to 200°C, and most preferably 150°C to 170°C. It may also show at least one feature selected from the group consisting of the following.

[0107] The vitrimer according to the present invention, obtained through the monomer of the present invention, subsequently exhibits relaxation time and temperature, which are several functional properties that characterize its characteristics.

[0108] The vitrimer according to the present invention may also, very preferably, behave as a thermosetting resin and / or exhibit insolubility in many solvents such as water, CHCl3, CH2Cl2, DMF, THF, toluene and / or xylene, ketones, alcohols or carboxylic acids, without being limited. Swelling properties are observed to the extent of 0-500% of its initial weight. Swelling experiments may be performed in various solvents, such as acetone, chloroform and water, to evaluate the formation of a crosslinked reticular structure. Among these, chloroform is the solvent in which the vitrimer exhibits a maximum swelling ratio of about 100%. In acetone and water, the vitrimer swells by 40-50% and 20-30%, respectively.

[0109] The vitrimer of the present invention exhibits self-healing, reshaping, reworkable, recyclable, and reversible adhesive properties.

[0110] The vitrimer can constitute an intermediate layer between at least two substrates, such as metals, polymers, glass, and ceramic materials. The resulting composite material can be prepared by setting a benzoxazine monomer containing at least one ester between two considered substrates and then curing it at a temperature that produces a vitrimer without altering the integrity of the substrates. Each substrate may be different from the others.

[0111] The metal substrate is not limited and may be aluminum, iron, steel, etc.

[0112] The polymer substrate may be polycarbonate, acrylic, polyamide, polyethylene, or terephthalate.

[0113] Benzoxazine vitrimers can then be advantageously used in a wide range of fields of science and technology, such as electronics, aerospace, defense, and automotive.

[0114] The present invention also, a) Benzoxazine monomers containing the ester and acrylate moiety of formula (I), and b) Additional compounds of at least one organic molecular type, with or without a benzoxazine moiety. This also relates to composition A, which contains [the specified element].

[0115] Preferably, the organic molecular type may be a polymer containing or not containing a benzoxazine moiety.

[0116] Additional compounds may be used to enhance the properties of the monomer, vitrimer, or both (i.e., viscosity, mechanical, and thermal properties).

[0117] The polymer may be an epoxy resin, bismaleimide resin, phenolic resin or benzoxazine resin, polyurethane, polyamide, polyolefin, polyester, or rubber. Benzoxazine derivatives containing the ester of formula I may be used in a weight ratio of 0.1 to 80% of the final composition.

[0118] The compound of formula (I) can be used to impart vitrimer properties (self-healing, reworkability, etc.) to the polymers described above.

[0119] The present invention also, a) Benzoxazine monomers containing the ester and acrylate moiety of formula (I), and b) Materials selected from the group consisting of fillers, fibers, pigments, dyes, and plasticizers The same applies to composition B, which contains [the specified substance].

[0120] Additional compounds may be used to enhance the properties of monomers, vitrimers, or both (i.e., viscosity, mechanical, and thermal properties).

[0121] The additional compounds could be carbon fibers, glass fibers, clay, carbon black, silica, carbon nanotubes, graphene, or any means known for thermal or mechanical reinforcement of composites.

[0122] The present invention also relates to the use of the vitrimer according to the present invention as a reversible adhesive, sealant, coating, or encapsulation system for substrates selected from the group consisting of metals, polymers, glass, and ceramic materials. Preferably, the metals and polymers are as defined above.

[0123] The present invention is described in more detail in the following embodiments with reference to the attached drawings. [Brief explanation of the drawing]

[0124] [Figure 1] Figure 1 shows an example of the synthesis of a compound of formula (I) with z=0, x=0.35, and y=0.65, i.e., an AZA-TYR-mea / methbenzoxazine monomer containing a free aliphatic hydroxyl group and a methacrylate group. [Figure 2] Figure 2 shows the 1H NMR spectrum of the benzoxazine monomer containing the AZA-TYR-mea0.35 / meth0.65 ester from Example 1. [Figure 3] Figure 3 shows the rheological measurement of UV curing of a benzoxazine monomer containing the AZA-TYR-mea0.35 / meth0.65 ester from Example 1. [Figure 4] Figure 4 shows the curing of the UV-printed vitrimer (a) from Example 1, which yields the materials listed in (b). [Figure 5] Figure 5 shows an example of the synthesis of an AZA-TYR-mea / methbenzoxazine monomer containing free aliphatic hydroxyl groups and methacrylate groups with z=0, x=0.7, and y=0.3 (Example 3). [Figure 6] Figure 6 shows the 1H NMR spectrum of the benzoxazine monomer containing the AZA-TYR-mea0.7 / meth0.3 ester from Example 3. [Figure 7] Figure 7 shows the rheological measurement of UV curing of a benzoxazine monomer containing the AZA-TYR-mea0.7 / meth0.3 ester from Example 3. [Figure 8] Figure 8 shows the curing of UV-printed vitrimer (a) from Example 3. [Figure 9] Figure 9 shows the evolution of the relaxation modulus of the double-cured vitrimer from Example 3. [Figure 10] Figure 10 shows an example of the synthesis of the AZA-TYR-mea / fa / methbenzoxazine monomer with z=0.5, x=0.25, and y=0.25 (Example 5). [Figure 11] Figure 11 shows the 1H NMR spectrum of the benzoxazine monomer containing the AZA-TYR-mea0.25 / fa0.5 / meth0.25 ester from Example 5, with z=0.25, x=0.25, and y=0.5. [Figure 12] Figure 12 shows an example of the synthesis of AZA-TYR-meth benzoxazine monomer containing free aliphatic hydroxyl groups and methacrylate groups in Comparative Example 6. [Figure 13] Figure 13 shows the 1H NMR spectrum of the benzoxazine monomer containing the AZA-TYR-meth ester from Example 6. [Figure 14] Figure 14 shows the UV curing of AZA-TYR-meth in Example 6. [Examples]

[0125] [Example 1]: Synthesis of benzoxazine containing free aliphatic groups, ester groups, and methacrylate groups from 1,9-nonanedioc acid (AZA) 2-(4-hydroxyphenyl)ethanol (TYR) as a phenolic acid derivative, monoethanolamine (MEA) as a primary amine having an aliphatic OH group, and methacryloyl chloride (MCl) as a methacrylate.

[0126] The AZA-TYR-mea / methbenzoxazine monomer containing free aliphatic hydroxyl and methacrylate groups was synthesized in three steps (Figure 1). The first step, step a), corresponds to the Fischer esterification of 1,9-nonanediic acid (azelaic acid, AZA) (1 equivalent) and 2-(4-hydroxyphenyl)ethanol (tyrosol, TYR) (2 equivalents) in the presence of p-toluenesulfonic acid introduced in a catalytic amount (0.5 wt.%). The reactants were melted together at 130°C and stirred mechanically for 24 hours to obtain (AZA-TYR) (1 equivalent).

[0127] The second step, step b), corresponds to the Mannich condensation of AZA-TYR (1 equivalent) with monoethanolamine (mea) (2 equivalents) and paraformaldehyde (PFA) (4 equivalents). All of these reactants were stirred together by mechanical stirring and reacted in the molten state at 70°C for 8 hours (and at 85°C for 2 hours) to obtain AZA-TYR-mea benzoxazine containing free aliphatic hydroxyl groups.

[0128] In the above embodiment, the primary amine is removed, and monoethanolamine (MEA) is used to produce both parts (primary amine and amino alcohol).

[0129] The third step, step c), corresponds to the methacrylate of AZA-TYR-mea with methacryloyl chloride (6 equivalents). AZA-TYR-mea was dried under reduced pressure overnight to remove trace amounts of water. In this way, AZA-TYR-mea was solubilized in dry CH2Cl2. Triethylamine (TEA, 6 equivalents) was added to the solution as a catalyst, and the mixture was poured into an ice bath. Then, methacryloyl chloride was added as droplets, the solution was allowed to return to room temperature, and stirred overnight to obtain AZA-TYR-mea / meth with z=0, x=0.35, and y=0.65.

[0130] Figure 2 shows the benzoxazine monomer containing AZA-TYR-mea / meth ester. 1 The 1H NMR spectrum (AVANCE III HD Bruker spectrometer) is shown. Here, z=0, x=0.35, and y=0.65.

[0131] [Example 2] Two-step vitrimer synthesis from AZA-TYR-mea / meth (z=0, x=0.35, y=0.65)

[0132] The UV curing of AZA-TYR-mea / meth in Example 1 was monitored by rheological measurements in Figure 3. The rheogram was performed under the following conditions: 10 Hz, constant amplitude of 0.1%; 25 mm plate. The test was performed by exposing the material to UV light using an Omnicure device (output, wavelength), and gelation was achieved after 14 seconds.

[0133] AZA-TYR-mea / meth was also 3D printed using a Hyrel System 30 M printer equipped with an extrusion vessel printhead combined with a 356 nm UV lamp. A 20 gauge needle nozzle was used to deposit a 0.45 mm thick layer. Extrusion occurred at room temperature on a print platform at an extrusion rate of 1350 pulses / μm, with the UV lamp operating continuously to produce the honeycomb structure shown in Figure 4(a). A curing process at 170°C for 1 hour was performed to solidify the UV-cured structure and produce the material shown in Figure 4(b).

[0134] [Example 3]: Synthesis of benzoxazines containing free aliphatic groups, ester groups, and methacrylate groups from 1,9-nonanodioic acid (AZA), 2-(4-hydroxyphenyl)ethanol (TYR) as a phenolic acid derivative, monoethanolamine (mea) as a primary amine having an aliphatic OH group, and methacryloyl chloride (MCL) as a methacrylate.

[0135] AZA-TYR-mea / methbenzoxazine monomers containing free aliphatic hydroxyl and methacrylate groups were synthesized in three steps (Figure 5). The first step, step a), corresponds to the Fischer esterification of 1,9-nonanediol (cyclohexanediol, AZA) (2 equivalents) and 2-(4-hydroxyphenyl)ethanol (tyrosol, TYR) (1 equivalent) in the presence of p-toluenesulfonic acid introduced in a catalytic amount (0.5 wt.%). The reactants were melted together at 130°C and stirred mechanically for 24 hours to obtain (AZA-TYR) (1 equivalent).

[0136] The second step, step b), corresponds to the Mannich condensation of AZA-TYR (1 equivalent) with monoethanolamine (mea) (2 equivalents) and paraformaldehyde (PFA) (4 equivalents). All of these reactants were stirred together by mechanical stirring and reacted in the molten state at 70°C for 8 hours (85°C for 2 hours) to obtain AZA-TYR-mea benzoxazine containing free aliphatic hydroxyl groups.

[0137] In the above embodiment, the primary amine is removed, and monoethanolamine (MEA) is used to produce both parts (primary amine and amino alcohol).

[0138] The third step, step c), corresponds to the methacrylate of AZA-TYR-mea with methacryloyl chloride (0.65 equivalents). AZA-TYR-mea was dried under reduced pressure overnight to remove trace amounts of water. In this way, AZA-TYR-mea was solubilized in dry CH2Cl2. Triethylamine (TEA, 0.65 equivalents) was added to the solution as a catalyst, and the mixture was poured into an ice bath. Then, methacryloyl chloride was added as droplets, the solution was allowed to return to room temperature, and stirred overnight to obtain AZA-TYR-mea / meth with z=0, x=0.7, and y=0.3.

[0139] Figure 6 shows the benzoxazine monomer containing AZA-TYR-mea / meth ester. 1 The 1H NMR spectrum (AVANCE III HD Bruker spectrometer) is shown, where z=0.25, x=0.25, y=0.5, and the benzoxazine monomer containing the AZA-TYR-mea0.25 / fa0.5 / meth0.25 ester is shown. 1 The 1H NMR spectrum is shown.

[0140] The UV curing of AZA-TYR-mea / meth in Example 3 was monitored by rheological measurements in Figure 7. The rheogram was performed under the following conditions: 10 Hz, constant amplitude of 0.1%; on a 25 mm plate. The test was performed by exposing the material to UV light using an Omnicure device (output, wavelength), and gelation was achieved after 24 seconds.

[0141] AZA-TYR-mea / meth was also 3D printed using a Hyrel System 30 M printer equipped with an extrusion vessel printhead combined with a 356 nm UV lamp. A 20 gauge needle nozzle was used to deposit a 0.45 mm thick layer. Extrusion occurred at room temperature on a print platform at an extrusion rate of 1350 pulses / μm, with the UV lamp operating continuously to produce the honeycomb structure shown in Figure 8a. A curing process at 170°C for 1 hour was performed to solidify the UV-cured structure and produce the material shown in Figure 8b.

[0142] [Example 4]: Two-step vitrimer synthesis from AZA-TYR-mea / meth at z=0, x=0.7, y=0.3

[0143] The UV curing of AZA-TYR-mea / meth in Example 3 was monitored by rheological measurements in Figure 7. The rheogram was performed under the following conditions: 10 Hz, constant amplitude of 0.1%; on a 25 mm plate. The test was performed by exposing the material to UV light using an Omnicure device (output, wavelength), and gelation was achieved after 34 seconds.

[0144] AZA-TYR-mea / meth was also 3D printed using a Hyrel System 30 M printer equipped with an extrusion vessel printhead combined with a 356 nm UV lamp. A 20 gauge needle nozzle was used to deposit a 0.45 mm thick layer. Extrusion occurred at room temperature on a print platform at an extrusion rate of 1350 pulses / μm, with the UV lamp operating continuously to produce the honeycomb structure shown in Figure 8. A curing process at 170°C for 1 hour was performed to solidify the UV-cured structure and produce the material shown in Figure 8b.

[0145] The viscoelastic properties of the AZA-TYR-mea / meth bicured vitrimer were measured by stress relaxation experiments recorded at 1% shear strain on an Anton Paar Physica MCR 302 rheometer in torsional mode (Figure 4). The relaxation times of the polymer were clearly significant and were recorded at 150°C, 160°C, and 170°C (Figure 9).

[0146] [Example 5]: Synthesis of benzoxazines containing free aliphatic groups, ester groups, and methacrylate groups from 1,9-nonanodioic acid (AZA) and 2-(4-hydroxyphenyl)ethanol (TYR) as a phenolic acid derivative, furfurylamine (fa) as a primary amine and monoethanolamine (mea) as a primary amine having an aliphatic OH group, and methacryloyl chloride (MCL) as a methacrylate.

[0147] The AZA-TYR-mea / fa / methbenzoxazine monomer containing free aliphatic hydroxyl and methacrylate groups was synthesized in three steps (Figure 10). The first step, step a), corresponds to the Fischer esterification of 1,9-nonanediic acid (azelaic acid, AZA) (1 equivalent) and 2-(4-hydroxyphenyl)ethanol (floretic acid, TYR) (2 equivalents) in the presence of p-toluenesulfonic acid introduced in a catalytic amount (0.5 wt.%). The reactants were melted together at 130°C and stirred by mechanical stirring for 24 hours to obtain (AZA-TYR) (1 equivalent).

[0148] The second step, step b), corresponds to the Mannich condensation of AZA-TYR (1 equivalent) with furfurylamine (fa) (0.5 equivalents), monoethanolamine (mea) (1.5 equivalents), and paraformaldehyde (PFA) (4 equivalents). All of these reactants were stirred together by mechanical stirring and reacted in the molten state at 70°C for 8 hours to obtain AZA-TYR-mea / fa benzoxazine containing free aliphatic hydroxyl groups.

[0149] The third step, step c), corresponds to the methacrylate of AZA-TYR-mea / fa with methacryloyl chloride (6 equivalents). AZA-TYR-mea / fa was dried overnight under reduced pressure to remove trace amounts of water. In this way, AZA-TYR-mea / fa was solubilized in dry CH2Cl2. Triethylamine (TEA, 6 equivalents) was added to the solution as a catalyst, and the mixture was poured into an ice bath. Then, methacryloyl chloride was added as droplets, the solution was allowed to return to room temperature, and stirred overnight to obtain AZA-TYR-mea / fa / meth with z=0.25, x=0.25, and y=0.5.

[0150] Figure 11 shows the benzoxazine monomer containing AZA-TYR-mea / fa / meth ester. 1 The 1H NMR spectrum (AVANCE III HD Bruker spectrometer) is shown. Here, z=0.25, x=0.25, and y=0.5.

[0151] [Example 6 (Comparative Example, Not the Present Invention)]: Synthesis of benzoxazines containing ester and methacrylate groups but free aliphatic groups, from 1,9-nonanediic acid (AZA), 2-(4-hydroxyphenyl)ethanol (TYR) as a phenolic acid derivative, monoethanolamine (mea) as a primary amine having an aliphatic OH group, and methacryloyl chloride (MCL) as a methacrylate.

[0152] AZA-TYR-methbenzoxazine monomers containing free aliphatic hydroxyl and methacrylate groups were synthesized in three steps (Figure 12). The first step, step a), corresponds to the Fischer esterification of 1,9-nonanediic acid (azelaic acid, AZA) (1 equivalent) and 2-(4-hydroxyphenyl)ethanol (tyrosol, TYR) (2 equivalents) in the presence of p-toluenesulfonic acid introduced in a catalytic amount (0.5 wt.%). The reactants were melted together at 130°C and stirred by mechanical stirring for 24 hours to obtain (AZA-TYR) (1 equivalent).

[0153] The second step, step b), corresponds to the Mannich condensation of AZA-TYR (1 equivalent) with monoethanolamine (mea) (2 equivalents) and paraformaldehyde (PFA) (4 equivalents). All of these reactants were stirred together by mechanical stirring and reacted in the molten state at 70°C for 8 hours to obtain AZA-TYR-mea benzoxazine containing free aliphatic hydroxyl groups.

[0154] In the above example, the primary amine is removed, and monoethanolamine (MEA) is used to produce both parts (primary amine and amino alcohol).

[0155] The third step, step c), corresponds to the methacrylate of AZA-TYR-mea with methacryloyl chloride (6 equivalents). AZA-TYR-mea was dried overnight under reduced pressure to remove trace amounts of water. In this way, AZA-TYR-mea was solubilized in dry CH2Cl2. Triethylamine (TEA, 6 equivalents) was added to the solution as a catalyst, and the mixture was poured into an ice bath. Then, methacryloyl chloride was added as droplets, the solution was allowed to return to room temperature, and stirred overnight to obtain AZA-TYR-mea / meth with x=z=0, y=1.

[0156] Figure 13 shows the benzoxazine monomer containing AZA-TYR-meth ester. 1 The 1H NMR spectrum (AVANCE III HD Bruker spectrometer) is shown.

[0157] [Example 7 (Comparative Example, Not the Present Invention)] Two-step vitrimer synthesis from AZA-TYR-mea / meth (x=z=0, y=1).

[0158] The UV curing of AZA-TYR-meth in Example 6 was monitored by rheological measurements in Figure 14. The rheogram was performed under the following conditions: 10 Hz, constant amplitude of 0.1%; on a 25 mm plate. The test was performed by exposing the sample to UV light using an Omnicure device (power output, wavelength), and gelation was achieved after 4 seconds.

[0159] A rectangular bar measuring 10mm x 5mm x 1mm was prepared by exposing the resin to UV curing for 5 minutes, and then heat-cured at 170°C for 1 hour.

[0160] The viscoelastic properties of the AZA-TYR-meth double-cured vitrimer were measured by stress relaxation experiments recorded on an Anton Paar Physica MCR 302 rheometer in torsional mode under 1% shear strain. The polymer could not relax at any temperature because it contained no aliphatic -OH groups that could dynamically exchange with ester bonds.

[0161] conclusion The presence of moieties in the ester bonds, free aliphatic hydroxyl groups, and acrylate moieties in the monomers of the present invention is essential for forming a dynamic network structure of benzoxazine vitrimers that allows the material to be recycled, reshaped, and reprocessed. The resulting vitrimers exhibit, in particular, relaxation times and temperatures that consequently distinguish them from vitrimers known in the art.

Claims

1. A benzoxazine monomer containing the ester and acrylate moieties of formula (I). 【number】 [In the formula, R １ teeth, 【number】 And, R ２ teeth, 【number】 And, R ３ teeth, 【number】 And, R ａ is selected from the group consisting of a linear or branched C １ -C ６ alkyl or alkoxy group, a linear or branched C ２ -C ６ alkenyl or alkyleneoxy group, a substituted or unsubstituted linear or branched C ２ -C ６ alkynyl group, and -C-linear or branched C １ -C ６ alkyl or C ２ -C ６ alkenyl-substituted or unsubstituted phenyl group; R ＊ These are H, OH and O-linear or branched C １ ~C ６ Alkyl, linear, or branched C １ ~C １５ Alkyl alkyl group or C ２ ~C １５ Alkenyl group or 【number】 Selected from the group consisting of; R'', R ＊＊ And R can independently be linear or branched C １ ~C ６ Alkyl or alkoxy group; linear or branched C ２ ~C ６ Alkenyl or alkylene oxy group; substituted or unsubstituted linear or branched carbon atoms. ２ ~C ６ Alkynyl group; at least one linear or branched carbon chain １ ~C ６ Alkyl or C ２ ~C ６ Alkenyl-substituted or unsubstituted o-, m-, p-phenyl groups, cyclo(C) ３ ~C ６ Alkyl group or heterocyclo(C) ３ ~C ６ (alkyl) group (where the heteroatom is selected from N, S, and O); (CH ２ ) ｎ３ - Phenyl group, - (CH ２ ) ｎ１ -O-(CH ２ ) ｎ２ - (CH ３ ) base (where n1 and n2 are independent integers from 1 to 10), 【number】 and 【number】 Selected from the group consisting of; R''' is Me, H, or CN; n3 is an integer between 1 and 10; however, 1 ≤ n < 50, and x > 0, y > 0, and z ≥ 0, and independently of n, x + y + z = 1; x, y, and z represent the ratio between benzoxazine groups and methacrylate groups when prepared from amino alcohols and other amines. [Math 1] Here, [Math 2] n アミノアルコール n is the number of amino alcohols, アミン n represents the number of amines (excluding the number of amino alcohols), アクリレート n corresponds to the number of acrylate / methacrylate groups, 総官能基 [This is the total number of functional groups present in the benzoxazine ring.]

2. Ra is linear or branched C １ ~C ４ Alkyl or alkoxy group, linear or branched C ２ ~C ４ Alkenyl or alkylene oxy group, substituted or unsubstituted linear or branched carbon. ２ ~C ４ Alkynyl group, and linear or branched carbon １ ~C ４ Alkyl or C ２ ~C ６ Selected from the group consisting of alkenyl-substituted or unsubstituted phenyl groups; independently, R ＊ However, H, OH and O-linear or branched C １ ~C ４ Alkyl, linear, or branched C １ ~C １０ Alkyl alkyl group or C ２ ~C １０ Alkenyl groups, more preferably linear or branched carbon atoms. １ ~C ６ Alkyl alkyl group, C ２ ~C ６ Alkenyl group or C ２ ~C ６ Alkynyl group or 【Transformation 8】 A monomer selected from the group consisting of the following, according to claim 1.

3. In the definition of R'', a phenyl group, a cyclo(C) ３ ~C ６ Alkyl group or heterocyclo(C) ３ ~C ６ The monomer according to claim 1 or 2, wherein each C atom of the alkyl group independently has a substituent as defined in claim 1 or 2.

4. A method for synthesizing a benzoxazine monomer containing the ester and acrylate moiety of formula (I), At least one R on the phenol ring ＊ Phenolic hydroxyl group-containing compounds of formula (II) that include the group: (PhOH)w-Ral-OH (II) (In the formula, Ral has the definition of Ra, and w = 1, 2, or 3) The carboxylic acid compound of formula (III) R-(COOH)n (III) (In the formula, R has the definition of R'' as shown in any of claims 1 to 3, and n has the same definition as described in claim 1.) The process involves reacting the phenol-terminated oligomer or molecule (compound (IV)) at a temperature of 25°C to 200°C for 1 to 72 hours in the presence of a Brønsted acid-type catalyst and under an inert atmosphere. a) Compound (IV), - Amino alcohol of formula (V): 【Chemistry 9】 - Aldehyde compounds selected from formaldehyde and paraformaldehyde of the following formula, 【Chemistry 10】 (In the formula, m is an integer between 8 and 100.) - Primary amine of formula (VI) R ＊＊ -NH ２ (VI) A step of reacting a mixture of with at a temperature of 50°C to 200°C for 1 to 12 hours under an inert atmosphere to produce a compound of formula (VII), and b) A step of reacting compound (VII) with a compound having an acrylate or methacrylate group, wherein the compound is at least one defined by the following compounds (VIII) to (XII): (i) (meth)acrylate chloride of formula (VIII) in a polar solvent at a temperature of -5 to 25°C 【Chemistry 11】 ; or (ii) Methyl (meth)acrylate of formula (IX) in the presence of a catalyst and polymerization inhibitor 【Chemistry 12】 ; or (iii) (meth)acrylic acid of formula (X) in a solvent at temperatures from -10°C to reflux in the presence of a catalyst and azodicarboxylate. 【Chemistry 13】 ; or (iv) Excess (meth)acrylic acid of formula (X) in the presence of a catalyst; or (v) (meth)acrylic anhydride of formula (XI) or asymmetric anhydride of formula (XII) in the presence of a catalyst 【Chemistry 14】 (In the formula, - R'''' is H or CH ３ And, - R''"' is CH ３ or C ２ H ５ (is) A step to obtain a benzoxazine monomer containing the ester and acrylate moiety of formula (I) by reacting at a temperature of -10°C to 50°C for 12 to 48 hours. The process includes the following steps: However, at least one R of the phenolic acid derivative ＊ When R is in the ortho position relative to the -OH group, ＊ The method is H.

5. The method according to claim 4, wherein the stoichiometric ratio of the starting reactants in step a) is n equivalents:1.0 equivalents of the phenolic hydroxyl group-containing compound:carboxylic acid compound, and a phenol-terminated oligomer or molecule (compound (IV)) of 1.0 equivalent is produced.

6. The amino alcohol in formula (V) is R ＊ The method according to claim 4 or 5, wherein the linear amino alcohol contains a group and has a primary amine moiety and an aliphatic hydroxyl moiety.

7. The method according to any one of claims 4 to 6, wherein the primary amine is selected from the group consisting of allylamine, methylamine, ethylamine, propylamine, butylamine, isopropylamine, hexylamine, cyclohexylamine, stearylamine, 2-aminofluorene, aminophenylacetylene, propargyl etheraniline, 4-aminobenzonitrile, furfurylamine, and aniline, or a mixture thereof.

8. The method according to any one of claims 4 to 7, wherein the stoichiometric ratio of each of the starting reactants in step b) the phenol-terminated oligomer or molecule (IV):amino alcohol (V):primary amine (VI):paraformaldehyde is 1.0 equivalent:n(x+y):nz:2.0n(x+y+z), and 1.0 equivalent of compound (VII) is produced.

9. The method according to any one of claims 4 to 8, wherein the temperature range of step b) is 70°C to 150°C, more preferably 70°C to 120°C, and step b) is carried out for 1 hour to 8 hours, preferably 1 hour to 5 hours, for a maximum yield of at least 75%.

10. The method according to any one of claims 4 to 9, wherein step c) is carried out by an acylation reaction with compound (VII)-(meth)acrylate chloride- in a polar solvent selected from acetonitrile, chloroform, dichloromethane and N,N-dimethylaniline, at a temperature of -5 to 15°C, in the absence of any suitable catalyst, or preferably in the presence of a catalyst / hydrogen absorber selected from triethylamine (TEA), pyridine, N,N-diisopropylethylamine (DIPEA) and N-N-dimethylaniline.

11. The method according to any one of claims 4 to 9, wherein step c) is carried out by a re-esterification reaction using compound (IX)-methyl (meth)acrylate- in the presence of a catalyst such as sodium or magnesium alkoxide and a polymerization inhibitor such as p-oxydiphenylamine, accompanied by simultaneous distillation of the resulting azeotropic mixture.

12. The method according to any one of claims 4 to 9, wherein step c) is carried out by a Mitsunobu reaction using compound (X)-(meth)acrylic acid- in a solvent such as tetrahydrofuran (THF) or toluene at a temperature from -10°C to reflux, in the presence of a catalyst such as triphenylphosphine and an azodicarboxylate such as diethyl azodicarboxylate (DEAD) or diisopropyl azodicarboxylate (DIAD).

13. Step c) uses an excess of (meth)acrylic acid-compound (X), preferably p-toluenesulfonic acid (p-TCA), sulfuric acid (H ２ SO ４ ) and methanesulfonic acid (CF ３ SO ３ The method according to any one of claims 4 to 9, wherein the esterification reaction is carried out by simultaneous distillation of the resulting azeotropic mixture in the presence of an acidic catalyst selected from H).

14. Step c) is carried out by an acylation reaction in the temperature range of -5 °C to 15 °C, preferably using compound (XI)-(meth)acrylic anhydride- or compound (XII)-(meth)acrylic asymmetric anhydride- and in the presence of a catalyst selected from p-toluenesulfonic acid (p-TCA), sulfuric acid (H ２ SO ４ ), and anhydrous ZnCl ２ ), according to any one of claims 4 to 9.

15. The method according to any one of claims 4 to 14, wherein the stoichiometric ratio of the starting reactants in step c) is 1.0 equivalent:3.0 ny equivalents of compound VII:compounds having an acrylate or methacrylate group (VIII to XII), and the method produces a benzoxazine monomer containing 1.0 equivalent of an ester and an acrylate moiety.

16. A method for preparing a polybenzoxazine derivative vitrimer, comprising: a first curing step of UV-treated polymerization of a benzoxazine monomer containing an ester and acrylate moiety of formula (I) that can be obtained by any one of claims 1 to 3 or by the method described in any one of claims 4 to 15; and a second curing step of heat treatment following the polymerization of the benzoxazine moiety of the benzoxazine monomer containing the ester and acrylate moiety.

17. The method according to claim 16, wherein the first curing step is carried out in the presence of a radical initiator in a percentage by weight (% wt) of 1% to 5% by weight.

18. The method according to claim 16 or 17, wherein the second curing step is carried out at a temperature range of 100°C to 250°C, preferably 120°C to 200°C, for 1 to 10 hours.

19. It can be obtained by the method described in any of claims 16 to 18, and has the following characteristics: (i) T 100°C to 250°C; preferably 130°C to 220°C, more preferably 130°C to 190°C ｖ Value, and (ii) Relaxation temperature value ≥ T, which is 100°C to 300°C, preferably 130°C to 200°C, and more preferably 130°C to 180°C. ｖ value A polybenzoxazine derivative vitrimer exhibiting at least one of the following.

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