Dual curable glass-like polymer

Abstract

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

Description

[0001] The present invention relates to the field of dually curable benzobisindol derivative vitrimers and their manufacturing process as well as the use of said vitrimers in various applications. TECHNICAL FIELD

[0002] Vitrimers are polymeric materials as their dynamic nature of the covalent network resulting from reversible chemical bonds allows the material to heal, recycle and reprocess like thermoplastic materials. These exchange reactions are triggered by external stimuli, most commonly temperature. The viscosity of vitrimers gradually decreases upon heating, giving malleability to the network while allowing internal stress relaxation. Network integrity throughout the range of applications ensures mechanical and solvent resistance.

[0003] Following the prototypical vitrimers developed by Leibler et al. in 2011 (D. Montarnal, M. Capelot, F. Tournilhac and L. Leibler, Science, 2011, 334, 965-968), dynamic ester transesterification reactions have triggered a broad interest in the past decade. These chemical exchanges induced between ester bonds and hydroxyl groups at elevated temperatures are responsible for topological rearrangements. The transesterification mechanism is implemented in crosslinked networks to design self-healing, recyclable and reprocessable 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), 6117-6127) adapted the glassy polymer concept to commercially available thermoplastics. By reactive extrusion, cross-linked polybutylene terephthalate (PBT) glassy polymers based on ester transesterification exchange were successfully prepared. In addition to improving the potential scope and manufacturing techniques of these networks, the global environmental context has motivated the scientific community to promote sustainability polymers derived from naturally occurring feedstocks. Altuna et al. (F. I. Altuna, V. Pettarin, and R. Williams, Green Chem., 2013, 15, 3360-3366) endeavored to produce a fully bio-based polyester (showing properties reminiscent of glassy polymers) starting from epoxidized soybean oil and aqueous citric acid solution. Furthermore, Legrand et al. (A. Legrand and C. Soulie-Ziakovic, Macromolecules, 2016, 49, 5893-5902) were able to extend the scalability of the application of glassy polymer networks by developing silica-reinforced epoxy-type glassy polymer nanocomposites with enhanced properties.

[0005] Polybenzoxazines are a new class of thermoset materials with outstanding mechanical and thermal properties. Like many other thermosets, they cannot be reshaped, reprocessed, or recycled. Some examples have been reported showing reasonable levels of healability (L. Zhang, Z. Zhao, Z. Dai, L. Xu, F. Fu, T. Endo, X. Liu, ACS Macro. Lett. 2019, 8, 5, 506-511, and Arslan M., Kiskan B., Yagci, Sci. Rep. 2017, 7, 5207).

[0006] The applicant has shown that some different chemical structures of polybenzoxazine type vitrimer exhibit in particular self-healing, reshaping, reworkability, high strength, and low melt viscosity properties due to the benzoxazine moiety of the starting monomer used for the production of the corresponding vitrimer by its polymerization. WO 2021 / 180562 A1 relates to vitrimers obtained by polymerization of a disulfide containing benzoxazine monomer. WO 2022 / 122735 A1 and WO 2021 / 250024 relate to vitrimers obtained by polymerization of an ester containing benzoxazine monomer.

[0007] The publication “3D printing of dual-cure benzoxazine networks” by Jeremy J. Weigand et al., Polymer 189 (2020) 122193 discloses benzoxazine monomers suitable for 3D printing, the structure of which neither comprises an ester moiety nor a free aliphatic hydroxyl group for obtaining a vitrimer.

[0008] It appears that vitrimers, in particular those derived from benzoxazine monomers, in particular ester containing benzoxazine monomers, still need to provide improved properties for specific uses. In some cases, the monomers exhibit some 3D printing capabilities, but after the 3D printing step, they need to be heated to obtain the corresponding 3D shaped vitrimer. The main drawback of this heating step is the loss of the 3D shaped structure, i.e. the polybenzoxazine vitrimer of the 3D printed structure cannot be obtained. Moreover, some vitrimers exhibiting lower viscosity at room temperature, higher Tg, higher mechanical properties compared to those already existing are needed.

[0009] The present invention eliminates one of the aforementioned drawbacks and relates to an ester and acrylate moiety containing benzoxazine monomer of formula (I),

[0010] (I)

[0011] wherein

[0012] R1is ,

[0013] R2is , and

[0014] R3is ,

[0015] wherein

[0016] R aselected from the group consisting of linear or branched C1-C6alkyl or alkoxy, linear or branched C2-C6alkenyl or alkyleneoxy, substituted or unsubstituted linear or branched C2-C6alkynyl, and -C-linear or branched C1-C6alkyl or C2-C6alkenyl substituted or unsubstituted phenyl;

[0017] R selected from the group consisting of H, OH and O-linear or branched C1-C6alkyl, linear or branched C1-C 15 alkyl or C2-C 15 alkenyl or

[0018] , , or ;

[0019] R'', R and R are independently selected from the group consisting of linear or branched C1-C6alkyl or alkoxy; linear or branched C2-C6alkenyl or alkyleneoxy; substituted or unsubstituted linear or branched C2-C6alkynyl; at least one linear or branched C1-C6alkyl or C2-C6alkenyl substituted or unsubstituted ortho-, meta-, para-phenyl, cyclo(C3-C6alkyl), or heterocyclic(C3-C6alkyl), wherein the heteroatoms are selected from N, S and O; (CH2) n3 -phenyl, -(CH2) n1 -O-(CH2) n2 -(CH3) group, wherein n1 and n2 are independently an integer from 1 to 10; ; and ;

[0020] R''' is Me, H or CN;

[0021] n3 is an integer from 1 to 10;

[0022] with the proviso that

[0023] 1 < n < 50 and x > 0, y > 0 and z ≥ 0, and, independently of n, x + y + z = 1 ;

[0024] x, y, z represent the ratio between the benzodiazepine group and the methacrylate group at the time of preparation from the aminoalcohol and the other amine,

[0025]

[0026]

[0027]

[0028] wherein ,and It is the amount of amino alcohols. This indicates the amount of amines (excluding the amount of amino alcohols). Corresponding to the number of acrylate / methacrylate groups, and It is the total number of functional groups attached to the benzo[a]azine ring.

[0029] The values ​​of x and z depend on the amine (n) used to prepare the benzo[a]azine ring. 胺 ) and amino alcohols (n 醇 The molar ratio between the number of acrylates and methacrylates. The value of y depends on the conversion rate of the amino alcohol in the acrylate / methacrylate functional groups.

[0030] The benzo[a]azine monomers of the present invention, containing ester and acrylate moieties, are advantageously suited for obtaining polybenzo[a]azine-based glass polymers via a dual curing process (i.e., involving consecutive curing steps), which is particularly advantageously a 3D printing process, wherein the 3D-formed structure is maintained in the polybenzo[a]azine-based glass polymers compared to known polybenzo[a]azine-based glass polymers. This is explained by the fact that known benzo[a]azine monomers that produce glass-like polymers (i) exhibit too high a viscosity for 3D printing, (ii) require post-printing curing, and (iii) are not UV-curable.

[0031] The preparation of polybenzoxazine glass polymers derived from the present invention, comprising ester and acrylate moieties of benzoxazine monomers, involves a dual curing process, including a first curing step via UV treatment polymerization, which undergoes polymerization of the acrylate moieties, allowing the shape of the resulting structure to be fixed. The first curing step is followed by a second curing step via heat treatment, which undergoes polymerization of the benzoxazine moieties of the benzoxazine monomers comprising ester and acrylate moieties, during which the benzoxazine monomers do not melt due to the prior UV treatment used for the polymerization of the acrylate moieties.

[0032] In the context of this invention, "polybenzo[a]azine-based glass polymer" and "double-cured glass-like polymer" have the same meaning.

[0033] The advantage is that the preparation of such double-cured glass-like polymers can be carried out during the 3D printing process, or even after the 3D printing process in some embodiments.

[0034] The polybenzoxazine glass polymers of the present invention are produced by ring-opening and self-polymerization of benzoxazine in a benzoxazine monomer containing ester and acrylate moieties, carried out during or at a second curing step under heat. As a starting product, the particular monomers can advantageously exhibit low viscosity at 25°C, typically 50-10000 mPa·s, preferably 100-10000 mPa·s, and more preferably 200-3000 mPa·s. In some other embodiments, the viscosity at 25°C can be 3000 to 8000 mPa·s. For the remainder of this document, benzoxazine glass polymers will always refer to the polymerized form of the ester-bonded benzoxazine monomer.

[0035] The glass-like polymer properties obtained through double curing are closely related to the properties of the ester-containing benzo[a]azine monomer.

[0036] As can be seen from formula (I), the monomer includes a benzo[a]azine ring moiety, which allows the monomer to crosslink upon heating, and the exchangeable ester bonds formed during crosslinking promote the reprocessing of the resulting benzo[a]azine glass polymer. Benzo[a]azine imparts thermosetting properties (e.g., high-temperature and flammability), high strength, thermal stability, low water absorption, chemical resistance, low melt viscosity, and near-zero shrinkage.

[0037] The presence of the ester bond, free aliphatic hydroxyl group, and acrylate moiety is essential for the formation of a dynamic network of benzo[a]azine glass polymers, allowing the material to be recycled, reshaped, and reprocessed. The hydroxyl-terminated amine allows for the closure of the azine ring and permits ester transfer reactions. Therefore, the essential characteristics of the monomers of this invention depend on the benzo[a]azine moiety, the ester bond, the free aliphatic hydroxyl group, and the acrylate moiety. The various groups in R1 and R2 (R...) Even if necessary, R'' and R''' will not sufficiently impair the effects of the invention, as they serve as supports for the OH groups, esters, and acrylate moieties. Such polybenzoxazine glass polymers can have a Tg ranging from -50°C to 250°C, and an elastic modulus in the range of 0.1-4 GPa, which is measured by classical thermomechanical analysis.

[0038] Preferably, Ra can be selected from: straight-chain or branched C1-C4 alkyl or alkoxy, straight-chain or branched C2-C4 alkenyl or alkeneoxy, substituted or unsubstituted straight-chain or branched C2-C4 alkynyl, and straight-chain or branched C1-C4 alkyl or C2-C6 alkenyl-substituted or unsubstituted phenyl groups; and independently,

[0039] R Selectable from H, OH, and O-straight-chain or branched C1-C4 alkyl groups, straight-chain or branched C1-C groups 10 Alkyl or C2-C 10 Alkenyl, more preferably straight-chain or branched C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl or

[0040] , , or .

[0041] Preferably, in the definition of R'', each C atom of the phenyl, cyclic (C3-C6 alkyl), or heterocyclic (C3-C6 alkyl) group may independently carry a substituent as defined above.

[0042] Furthermore, the benzo[a]azine monomer containing ester and acrylate moieties of the present invention can be used in combination or mixture with another benzo[a]azine monomer, such as a monofunctional amine bridged with a bisphenol compound, a monophenolic compound bridged with a diamine, and a diamine bridged by a bisphenol compound, or a mixture thereof, to improve the processability of the benzo[a]azine monomer containing ester and acrylate moieties during polymerization to obtain its glass-like polymer (improving the viscosity of the resulting mixture (the monomer of the present invention, monomer 1, and the other monomer (monomer 2))). The glass-like polymer properties of polybenzo[a]azine derivatives are closely related to the properties of the benzo[a]azine monomer containing ester and acrylate moieties. The monomer 1:monomer 2 ratio in the mixture of monomers 1 and 2 can be 1% to 90% by weight.

[0043] Preferably, 1≤n<40, 1≤n<30, 1≤n<20, 1≤n< or 1≤n<5.

[0044] The present invention also relates to a process for synthesizing a benzo[a]azine monomer of formula (I) containing an ester and an acrylate moiety, comprising the following steps:

[0045] a) In the presence of a Brønsted acid catalyst and under an inert atmosphere, at a temperature of 25°C to 200°C, a phenolic ring containing at least one R A compound containing a phenolic hydroxyl group of formula (II) reacts with a carboxylic acid compound of formula (III) for 1 hour to 72 hours to obtain a phenol-terminated oligomer or molecule (compound (IV)):

[0046] (II)

[0047] in

[0048] Ral has R a The definition is given, and w = 1, 2, or 3;

[0049] (III),

[0050] Where R has the definition of R'', and n has the same definition as above.

[0051] b) Under an inert atmosphere, react compound (IV) with a mixture of the following substances at a temperature of 50°C to 200°C for 1 hour to 12 hours to provide compound (VII):

[0052] - Amino alcohols of formula (V):

[0053] (V)

[0054] - Aldehyde compounds, selected from formaldehyde and formula Paraformaldehyde, where m is an integer from 8 to 100.

[0055] - Primary amines of formula (VI)

[0056] (VI),

[0057] and

[0058] c) Reacting compound (VII) with a compound having an acrylate or methacrylate group at a temperature of -10°C to 50°C for 12 to 48 hours to obtain a benzo[a]azine monomer of formula (I) containing an ester and an acrylate moiety, said compound being at least one of compounds (VIII)-(XII).

[0059] (i) (meth)acryloyl chloride of formula (VIII)

[0060] (VIII)

[0061] In polar solvents, at temperatures ranging from -5°C to 25°C; or

[0062] (ii) Methyl methacrylate of formula (IX)

[0063] (IX)

[0064] In the presence of catalysts and polymerization inhibitors; or

[0065] (iii) (Meth)acrylic acid of formula (X)

[0066] (X)

[0067] In the presence of a catalyst and azodicarboxylic acid ester, in a solvent, at a temperature from -10°C to reflux; or

[0068] (iv) Excess (meth)acrylic acid of formula (X), in the presence of a catalyst; or

[0069] (v) (meth)acrylic anhydride of formula (XI) or asymmetric acid anhydride of formula (XII)

[0070] (XI) (XII)

[0071] In the presence of a catalyst;

[0072] in

[0073] - R'''' is H or CH3;

[0074] - R''''' is CH3 or C2H5;

[0075] The condition is that at least one R of the phenolic acid derivative When the -OH group is in the ortho position, then R For H.

[0076] In this process, R, R a R R R'' has the definition given in equation (I).

[0077] According to this process, the value of "z" can be 0 (z=0), which is independent of the value of "x", meaning that the primary amine can be omitted in some embodiments. The compound (amino alcohol) of formula (V) is used for both.

[0078] The applicant has demonstrated that specific starting reactants provide benzo[a]azine monomers containing ester and acrylate moieties, which, upon polymerization, yield polybenzo[a]azine derivative glass polymers containing polymerized benzo[a]azine.

[0079] Steps a) and b) do not require reactive diluents and solvents. Other advantages of the obtained monomers are those mentioned above, especially exhibiting low viscosity at 25°C, typically 1000-10000 mPa·s, better 200-3000 mPa·s, and high Tg values.

[0080] Step a) can be advantageously carried out at a temperature in the range of 80°C to 170°C, most preferably 100°C to 140°C, to obtain an optimal synthesis yield of over 95%, the selected temperature depending on the properties of the reactants, i.e., the melting temperature of the reactant medium.

[0081] Advantageously, step a) is carried out for 12 to 48 hours, more preferably 12 to 36 hours, to obtain at least 95% of the highest yield, and the duration is based on reaction kinetics.

[0082] Brønsted acid-type catalysts are those commonly used in Fischer esterification, including p-toluenesulfonic acid (p-TSA), anhydrous hydrochloric acid (HCl), phosphoric acid (H3PO4), formic acid (CH3-CO2H), sulfuric acid, tosylic acid, and Lewis acids such as scandium(III) trifluoromethanesulfonate. The catalyst content is typically from 0.5% to 2% by weight.

[0083] The starting reactant in step a) is a compound containing phenolic hydroxyl groups. The corresponding stoichiometry of the carboxylic acid compound can preferably be n equivalents: 1.0 equivalents, to obtain 1.0 equivalents of phenol-terminated oligomers or molecules (compound (IV)).

[0084] Step a) can be carried out under an inert atmosphere, for example by using Ar or N gas.

[0085] The second step of the process, step b), involves a Mannich condensation reaction, corresponding to the phenol-terminated oligomer or molecule ((IV)) of step a), with an amino alcohol (formula (V)), an aldehyde compound selected from formaldehyde and paraformaldehyde, and a primary amine of formula (VI), optionally in the presence of a catalyst. Therefore, step b) is carried out in a more convenient manner since no external catalyst is required. Step b) allows the formation of R1 and R3.

[0086] Step b) can be carried out under an inert atmosphere, for example by using Ar or N gas.

[0087] Advantageously, the amino alcohols of formula (V) include R A group consisting of a primary amine moiety and an aliphatic hydroxyl moiety, a straight-chain amino alcohol, is used to obtain the α-azine ring in the highest yield and under optimal reaction conditions.

[0088] The amino alcohol of formula (V) may more preferably be selected from 2-aminoethanol, 2-amino-2-methylpropanol, 5-aminopent-1-ol, heptaminol, 2-(2-aminoethoxy)ethanol, and diethylene glycolamine, or mixtures thereof.

[0089] Primary amines include R as defined above. Group.

[0090] The primary amine may be further selected from allylamine, methylamine, ethylamine, propylamine, butylamine, isopropylamine, hexylamine, cyclohexylamine, stearylamine, 2-aminofluorene, aminophenylacetylene, propyne ether aniline, 4-aminobenzyl nitrile, furfurylamine and aniline, or mixtures thereof.

[0091] In step b), the stoichiometry of the starting reactants—phenol-terminated oligomers or molecules (IV): amino alcohol (V): primary amine (VI): paraformaldehyde—is preferably 1.0 equivalent: n(x+y): nz: 2.0n(x+y+z) to obtain 1.0 equivalent of compound (VII). In some other embodiments, the stoichiometry may be 1.0 equivalent: 2.0 equivalent: 0.0 equivalent: 4.0 equivalent to obtain 1.0 equivalent of compound (VII).

[0092] The specific stoichiometric range depends on the respective equivalence ratio of the amino alcohol and the primary amine. It should be noted that there exists a minimum amount required for the reaction to occur. For example, the relative molar percentage of the amino alcohol relative to the relative molar percentage of the primary amine derivative is 10 mol% relative to 90 mol%. This also means that the primary amine (0 mol%) can be omitted, and only the amino alcohol (100 mol%) can be used. Furthermore, the selected stoichiometric range of both the amino alcohol / amine and paraformaldehyde preferably avoids the formation of linear and / or aliphatic byproducts, such as sulfadiazine, triaza derivatives, or condensation derivatives.

[0093] The temperature range of step b) is preferably 70°C to 150°C, more preferably 70°C to 120°C, allowing a maximum conversion yield of at least 75%.

[0094] Advantageously, step b) is carried out for 1 to 8 hours, preferably 1 to 5 hours, with a maximum yield of at least 75%.

[0095] The third step of the process, step c), is the reaction of compound (VII) of step b) with a compound having acrylate and / or methacrylate groups, the latter being at least one of compounds (VIII)-(XII) or a mixture thereof.

[0096] In an embodiment, step c) can be carried out typically with compound (VIII) ((meth)acryloyl chloride) via a classical acylation reaction with compound (VII) of step b), in the absence of any suitable catalyst or in the presence of a catalyst / hydrogen absorber, in a polar solvent, preferably at a temperature of -5 to 15°C, for 12 to 48 hours, wherein the catalyst / hydrogen absorber is preferably selected from, but not limited to, triethylamine (TEA), pyridine, N,N-diisopropylethylamine (DIPEA), and N,N-dimethylaniline, and the polar solvent is selected from, but not limited to, acetonitrile, chloroform, dichloromethane, and N,N-dimethylformamide (DMF).

[0097] According to another embodiment, step c) can be carried out typically by compound (IX) (methyl methacrylate) via a classical re-esterification reaction in the presence of a catalyst (such as sodium alkoxide or magnesium alkoxide) and a polymerization inhibitor (such as p-oxydiphenylamine), wherein preferably the azeotropic mixture obtained by simultaneous distillation is sustained for 12-48 hours, the azeotropic mixture being, for example, composed of methanol and dimethyl ether.

[0098] Step c) can be carried out typically by the classical Mitsunobu reaction with compound (X) ((meth)acrylic acid), which involves a reaction in the presence of a catalyst such as triphenylphosphine and an azodicarboxylic acid ester 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.

[0099] According to an alternative embodiment using compound (X) ((meth)acrylic acid), step c) can be carried out by an excess of the (meth)acrylic acid via a classical esterification reaction in the presence of an acidic catalyst, preferably selected from p-toluenesulfonic acid (p-TCA), sulfuric acid (H2SO4), and methanesulfonic acid (CF3SO3H), wherein the resulting azeotropic mixture (e.g., composed of toluene or cyclohexane and water) is simultaneously distilled, for a duration of 12-48 hours.

[0100] According to another embodiment, step c) can be carried out by compound (XI) ((meth)acrylic anhydride) or compound (XII) ((meth)acrylic acid asymmetric anhydride) via a classical acylation reaction in the presence of a catalyst in a temperature range of -5°C to 15°C, preferably selected from p-toluenesulfonic acid (p-TCA), sulfuric acid (H2SO4) and anhydrous ZnCl2.

[0101] Step c) allows the formation of R2.

[0102] Advantageously, for the implementation of this invention, the entire synthesis can generally be carried out without any further monomer purification. However, if necessary, for example during and / or after step c), monomer purification can be performed by any known technique (vacuum, distillation, redissolution, extraction with water, alkalis such as NaOH, or brine, etc.). When used, the solvent can also be removed as needed by classical methods, for example using a low-pressure removal device.

[0103] Use a classic mechanical stirrer or any non-restrictive means to stir the reaction mixture of steps a) and b).

[0104] This process can be implemented on a laboratory or industrial scale using any known means known to those skilled in the art, using appropriate containers.

[0105] In step c), the stoichiometry of the starting reactant compound VII (compounds with acrylate or methacrylate groups, VIII-XII) is preferably 1.0 equivalent: 3.0 ny equivalent, yielding 1.0 equivalent of a benzo[a]azine monomer containing both ester and acrylate moieties. In some embodiments, the value of "ny" can be from 0.1 to 10, more preferably from 0.5 to 2.

[0106] The present invention also relates to a process for preparing polybenzoxazine derivative glass polymers, comprising a first curing step of UV treatment polymerization of a benzoxazine monomer (formula (I)) containing ester and acrylate moieties obtained by the present invention or by the above process, followed by a second curing step performed by heat treatment of the polymerization of the benzoxazine moieties of the benzoxazine monomer containing ester and acrylate moieties.

[0107] In the context of this invention, "derivative" refers to the glass-like polymer obtained and derived through the polymerization of the benzo[a]azine monomer of this invention. Therefore, "polybenzo[a]azine derivative glass-like polymer" or "polybenzo[a]azine glass-like polymer" has the same meaning.

[0108] The preparation of polybenzoxazine glass polymers derived from the present invention, comprising ester and acrylate moieties of benzoxazine monomers, involves a dual curing process, including a first curing step via UV treatment polymerization, which undergoes polymerization of the acrylate moieties of the compound of formula (I), allowing the shape of the resulting structure to be fixed. The first curing step is followed by a second curing step via heat treatment, which undergoes polymerization of the benzoxazine moieties of the benzoxazine monomers comprising ester and acrylate moieties, during which the benzoxazine monomers do not melt due to the prior UV treatment used for the polymerization of the acrylate moieties.

[0109] In the context of this invention, "polybenzo[a]azine-based glass polymer" and "double-cured glass-like polymer" have the same meaning.

[0110] The advantage is that the preparation of such double-cured glass-like polymers can be carried out during the 3D printing process, or even after the 3D printing process in some embodiments.

[0111] The polybenzoxazine-based glass polymer is produced by ring-opening and self-polymerization of benzoxazine in the ester and acrylate moieties of the present invention during a second curing step under heat or during such step.

[0112] The first curing step is carried out in the classical presence of a free radical initiator, which may be 1% to 5% by weight, using a classical apparatus for carrying out the first step (UV curing) at typical wavelengths of 30 nm to 500 nm, preferably 280 and (to) 450 nm.

[0113] The second curing step is carried out by thermally triggered ring-opening polymerization of benzo[a]azine at a temperature range of 100°C to 250°C, preferably 120°C to 200°C, for 1 hour to 10 hours.

[0114] The polymerization duration depends on the curing temperature (second curing step) and / or the properties of the benzo[a]azine monomer containing the monoester. For a given monomer, the polymerization temperature is chosen to be higher than the temperature required for monomer synthesis. Generally, the higher the polymerization temperature, the shorter the curing duration. For example, when the polymerization temperature is 250°C, the curing duration can be at least 1 hour, and for a polymerization temperature of 100°C, the curing duration can be no more than 10 hours. Preferably, the curing temperature can be from 140°C to 200°C, more preferably from 120°C to 180°C, the latter range providing a curing duration of 1.5 hours to 3 hours, preferably 1.5 hours to 2.5 hours. Polymerization can be carried out by any known heating means (e.g., forced or natural convection, conduction, laser beams, and infrared beams).

[0115] The process may also include a post-polymerization step consisting of a heating step, which may preferably be carried out at a higher temperature than the polymerization heating step.

[0116] This invention also relates to polybenzoxazine derivative glass polymers, which can be obtained by the above process and exhibit at least one of the following characteristics:

[0117] (i) T 100°C to 250°C, preferably 130°C to 220°C, more preferably 130°C to 190°C v (Topological freezing temperature) value, and

[0118] (ii) A relaxation temperature value of 100°C to 300°C, preferably 130°C to 200°C, more preferably 130°C to 180°C, wherein ≥ T v value.

[0119] Glass-like polymer T v The value typically depends on the nature and amount of the catalyst (if present) in step b).

[0120] Relaxation temperature typically corresponds to the relaxation temperature of a glass-like polymer after applying strain (e.g., physical deformation such as torsion) without observing degradation of the glass-like polymer.

[0121] Advantageously, glass-like polymers can also exhibit at least one of the following characteristics:

[0122] - Relaxation time of 0.5 seconds to 2 hours, preferably 1 second to 1 hour, and more preferably 5 seconds to 50 minutes. Relaxation time is conventionally defined as the time it takes for a sample to relax to a value corresponding to 1 / e(0.37) of its original modulus. Generally, the higher the temperature, the shorter the relaxation time. For example, at temperatures between 120°C and 170°C, the relaxation time is about 150 minutes to 200 seconds, and within the temperature range of 150°C to 200°C, the relaxation time is ≤200 minutes, preferably 100 seconds to 20 seconds.

[0123] In some embodiments, the glass-like polymer can be deformed between 0.1% and 100% of its initial size;

[0124] - The activation energy related to the relaxation time can be from 50 kJ / mol to 200 kJ / mol, preferably from 70 kJ / mol to 170 kJ / mol, more preferably from 100 kJ / mol to 160 kJ / mol; and

[0125] - The processing temperature can be from 100°C to 250°C, preferably from 130°C to 250°C, more preferably from 150°C to 200°C, and most preferably from 150°C to 170°C.

[0126] The glass-like polymers obtained from the monomers of this invention exhibit relaxation times and temperatures, which are characteristics of their properties.

[0127] The glass-like polymer according to the invention also preferably exhibits thermosetting and / or insoluble properties in a variety of solvents, without limitation, such solvents as water, CHCl3, CH2Cl2, DMF, THF, aromatic solvents (e.g., toluene and / or xylene), ketones, alcohols, or carboxylic acids. Swelling properties are observed to be from 0% to 500% of their initial weight. Swelling experiments can be performed in various solvents, such as acetone, chloroform, and water, to evaluate the formation of cross-linked networks. Chloroform is the solvent in which the glass-like polymer exhibits the highest swelling ratio of approximately 100%. In acetone and water, the glass-like polymer swells by 40%-50% and 20%-30%, respectively.

[0128] The glass-like polymer of the present invention exhibits self-healing, reshaping, reprocessable, recyclable, and reversible adhesive properties.

[0129] Glass-like polymers can form an intermediate layer between at least two substrates (e.g., metals, polymers, glass, and ceramic materials). The resulting composite material can be prepared by placing at least one ester-containing benzo[a]azine monomer between two considered substrates, followed by curing at a temperature at which the glass-like polymer is provided, without altering the integrity of the substrates. Each substrate can be different from the others.

[0130] The metallic substrate is unrestricted and can be aluminum, iron, steel, etc.

[0131] The polymer substrate can be polycarbonate, acrylic, polyamide, polyethylene or terephthalate.

[0132] Then, benzo[a]azine glass polymers can be advantageously used in a variety of non-limiting technical fields, such as electronics, aerospace, defense and automotive.

[0133] The present invention also relates to composition A, which comprises:

[0134] a) A benzoxazine monomer of formula (I) containing ester and acrylate moieties, and

[0135] b) At least one or more other compounds of the organic molecular type, with or without the benzo[a]azine moiety.

[0136] Preferably, the organic molecular type can be a polymer with or without a benzo[a]azine moiety.

[0137] Other compounds can be used to enhance the properties (i.e., viscosity, mechanical and thermal properties) of monomers or glass-like polymers or both.

[0138] The polymer can be epoxy resin, bismaleimide resin, phenolic resin, benzo[a]azine resin, polyurethane, polyamide, polyolefin, polyester, or rubber. Ester-containing benzo[a]azine derivatives of Formula I can be used at a weight ratio of 0.1 to 80% of the final composition.

[0139] The compounds of formula (I) can be used to provide the above polymers with glass-like polymer properties (self-healing, reprocessing, etc.).

[0140] The present invention also relates to composition B, which comprises:

[0141] a) A benzoxazine monomer of formula (I) containing ester and acrylate moieties, and

[0142] b) Materials selected from fillers, fibers, pigments, dyes and plasticizers.

[0143] Other compounds can be used to enhance the properties (i.e., viscosity, mechanical and thermal properties) of monomers or glass-like polymers or both.

[0144] Other compounds can be carbon fibers, glass fibers, clay, carbon black, silica, carbon nanotubes, graphene, or any known means of thermal or mechanical reinforcement of the composite.

[0145] The present invention also relates to the use of the glass-like polymer according to the invention as a reversible adhesive, sealant, coating, or encapsulation system for a substrate selected from metals, polymers, glass, and ceramic materials. Preferably, the metals and polymers are as defined above.

[0146] The present invention will be described in more detail in the following embodiments with reference to the accompanying drawings.

[0147] Figure 1 It is an example of a synthetic compound of formula (I) (an AZA-TYR-mea / meth benzoxazine monomer containing free aliphatic hydroxyl groups and methacrylate groups, wherein z=0, x=0.35 and y=0.65).

[0148] Figure 2 The benzo[a]azine monomer containing AZA-TYR-mea0.35 / meth0.65 ester shown in Example 1 is an example of this. 1 H NMR spectrum.

[0149] Figure 3 Rheological measurements of UV-cured benzo[a]azine monomer containing AZA-TYR-mea0.35 / meth0.65 esters of Example 1 are shown.

[0150] Figure 4 The curing of UV-printed glass-like polymer (a) from Example 1 is shown, resulting in the material given in (b).

[0151] Figure 5 This is an example of synthesizing an AZA-TYR-mea / meth benzo[a]azine monomer containing free aliphatic hydroxyl groups and methacrylate groups (where z=0, x=0.7 and y=0.3 (Example 3)).

[0152] Figure 6 The benzo[a]azine monomer containing AZA-TYR-mea0.7 / meth0.3 ester shown in Example 3 is an example of this. 1 H NMR spectrum.

[0153] Figure 7 Rheological measurements of UV-cured benzo[a]azine monomer containing AZA-TYR-mea0.7 / meth0.3 esters are shown in Example 3.

[0154] Figure 8 The curing of UV-printed glass-like polymer (a) from Example 3 is shown.

[0155] Figure 9 The evolution of the relaxation modulus of the double-cured glass-like polymer from Example 3 is shown.

[0156] Figure 10 This is an example of synthesizing AZA-TYR-mea / fa / meth benzoxazine monomer (where z=0.5, x=0.25 and y=0.25 (Example 5)).

[0157] Figure 11 The example shown is a benzo[a]azine monomer containing AZA-TYR-mea0.25 / fa0.5 / meth0.25 esters (where z=0.25, x=0.25 and y=0.5). 1 H NMR spectrum.

[0158] Figure 12 This is an example of the synthesis of the AZA-TYR-meth benzoxazine monomer containing free aliphatic hydroxyl groups and methacrylate groups, as described in Comparative Example 6.

[0159] Figure 13 The benzo[a]azine monomer containing AZA-TYR-meth ester shown in Example 6 is an example of this. 1 H NMR spectrum.

[0160] Figure 14 The UV curing of AZA-TYR-meth in Example 6 is shown.

[0161] Example 1 Benzocyanine is synthesized from 1,9-azeliaic acid (AZA) 2-(4-hydroxyphenyl)ethanol (TYR) as a phenolic acid derivative, monoethanolamine (mea) as a primary amine with aliphatic OH groups, and methacryloyl chloride (MCl) as a methacrylate ester, containing free aliphatic groups, ester groups, and methacrylate groups.

[0162] The AZA-TYR-mea / meth benzoxazine monomer containing free aliphatic hydroxyl groups and methacrylate groups was synthesized in three stages. Figure 1 The first step, step a), corresponds to the Fischer esterification between 1,9-nonanedioc 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 are placed together in molten form at 130 °C and stirred mechanically for 24 hours to provide (AZA-TYR) (1 equivalent).

[0163] 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 these reactants were stirred together by mechanical stirring and reacted in a molten form at 70°C for 8 hours (2 hours at 85°C) to obtain AZA-TYR-mea benzo[a]azine containing free aliphatic hydroxyl groups.

[0164] In the described embodiment, the primary amine is omitted, and monoethanolamine (mea) is used to provide both components (primary amine and amino alcohol).

[0165] Step 3, step c), corresponds to the methacrylation of AZA-TYR-mea using methacryloyl chloride (6 equivalents). AZA-TYR-mea is dried overnight under reduced pressure to remove trace amounts of water. It is then dissolved in dry CH2Cl2. Triethylamine (TEA, 6 equivalents) is added to the solution as a catalyst, and the mixture is poured into an ice bath. Then, methacryloyl chloride is added dropwise, and the solution is restored to room temperature and stirred overnight to obtain AZA-TYR-mea / meth, where z=0, x=0.35, and y=0.65.

[0166] Figure 2 The benzo[a]azine monomer containing AZA-TYR-mea / meth ester is shown. 1 1H NMR spectrum (AVANCE III HDBruker spectrometer), where z=0, x=0.35 and y=0.65.

[0167] Example 2. Two-step glassy polymer synthesis from AZA-TYR-mea / meth (z = 0, x = 0.35 and y = 0.65)

[0168] pass Figure 3 Rheological measurements were performed to monitor the UV curing of AZA-TYR-mea / meth in Example 1. The rheological diagram was obtained under the following conditions: 10 Hz with a constant amplitude of 0.1%; 25 mm plate. Testing was conducted using an Omnicure device (power, wavelength) exposed to UV light, achieving gelation after 14 seconds.

[0169] AZA-TYR-mea / meth was also 3D printed using a Hyrel System 30 M printer, which features an extrusion-type memory printhead combined with a 356nm UV lamp. A 20-gauge needle nozzle was used to deposit a layer with a thickness of 0.45mm. Extrusion was performed at room temperature on a printing platform at an extrusion rate of 1350 pulses / μm, with the UV lamp continuously on, providing... Figure 4The honeycomb structure in (a) was subjected to a curing step at 170°C for 1 hour to consolidate the UV-cured structure, resulting in... Figure 4 The material is given in (b).

[0170] Example 3 Benzocyanine is synthesized from 1,9-azeliaic acid (AZA) and 2-(4-hydroxyphenyl)ethanol (TYR) as phenolic acid derivatives, monoethanolamine (mea) as a primary amine with aliphatic OH groups, and methacryloyl chloride (MCl) as a methacrylate ester, containing free aliphatic groups, ester groups, and methacrylate groups.

[0171] The AZA-TYR-mea / meth benzoxazine monomer containing free aliphatic hydroxyl groups and methacrylate groups was synthesized in three stages. Figure 5 The first step, step a), corresponds to the Fischer esterification between 1,9-azelaic acid (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 are placed together in molten form at 130 °C and stirred mechanically for 24 hours to provide (AZA-TYR) (1 equivalent).

[0172] 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 these reactants were stirred together by mechanical stirring and reacted in a molten form at 70°C for 8 hours (2 hours at 85°C) to obtain AZA-TYR-mea benzo[a]azine containing free aliphatic hydroxyl groups.

[0173] In the described embodiment, the primary amine is omitted, and monoethanolamine (mea) is used to provide both components (primary amine and amino alcohol).

[0174] Step 3, step c), corresponds to the methacrylation of AZA-TYR-mea using methacryloyl chloride (0.65 equivalents). AZA-TYR-mea is dried overnight under reduced pressure to remove trace amounts of water. It is then dissolved in dry CH2Cl2. Triethylamine (TEA, 0.65 equivalents) is added to the solution as a catalyst, and the mixture is poured into an ice bath. Then, methacryloyl chloride is added dropwise, and the solution is restored to room temperature and stirred overnight to provide AZA-TYR-mea / meth where z=0, x=0.7, and y=0.3.

[0175] Figure 6 The benzo[a]azine monomer containing AZA-TYR-mea / meth ester is shown.1 1H NMR spectrum (AVANCE III HDBruker spectrometer), showing the benzo[a]azine monomer (z=0.25, x=0.25 and y=0.5) containing AZA-TYR-mea0.25 / fa0.5 / meth0.25 ester. 1 H NMR spectrum.

[0176] pass Figure 7 Rheological measurements were performed to monitor the UV curing of AZA-TYR-mea / meth in Example 3. The rheological diagram was obtained under the following conditions: 10 Hz with a constant amplitude of 0.1%; 25 mm plate. Testing was conducted using an Omnicure device (power, wavelength) exposed to UV light, achieving gelation after 24 seconds.

[0177] AZA-TYR-mea / meth was also 3D printed using a Hyrel System 30 M printer, which features an extrusion-type memory printhead combined with a 356nm UV lamp. A 20-gauge needle nozzle was used to deposit a layer with a thickness of 0.45mm. Extrusion occurred at room temperature on a printing platform at an extrusion rate of 1350 pulses / μm, with the UV lamp continuously on, providing... Figure 8 The honeycomb structure in a was subjected to a curing step at 170°C for 1 hour to solidify the UV-cured structure, resulting in... Figure 8 The materials are given in b.

[0178] Example 4: Two-step glassy polymer synthesis from AZA-TYR-mea / meth (z = 0, x = 0.7 and y = 0.3) Figure 7

[0179] pass Figure 8 Rheological measurements were performed to monitor the UV curing of AZA-TYR-mea / meth in Example 3. The rheological diagram was obtained under the following conditions: 10 Hz with a constant amplitude of 0.1%; 25 mm plate. Testing was conducted using an Omnicure device (power, wavelength) exposed to UV light, achieving gelation after 34 seconds.

[0180] AZA-TYR-mea / meth was also 3D printed using a Hyrel System 30 M printer, which features an extrusion-type memory printhead combined with a 356nm UV lamp. A 20-gauge needle nozzle was used to deposit a layer with a thickness of 0.45mm. Extrusion was performed at room temperature on a printing platform at an extrusion rate of 1350 pulses / μm, with the UV lamp continuously on, providing... Figure 8 The honeycomb structure in the image was then subjected to a curing step at 170°C for 1 hour to solidify the UV-cured structure, resulting in... Figure 4 The materials are given in b.

[0181] The viscoelastic properties of the double-cured glass-like polymer AZA-TYR-mea / meth were measured by stress relaxation experiments recorded in torsional mode at 1% shear strain on an Anton Paar Physica MCR 302 rheometer. Figure 9 The relaxation time of the polymer was clearly visible and recorded at 150℃, 160℃, and 170℃. Example 5 ).

[0182] Figure 10 Benzocyanine containing free aliphatic groups, ester groups, and methacrylate groups is synthesized from 1,9-azelic acid (AZA) and 2-(4-hydroxyphenyl)ethanol (TYR) as phenolic acid derivatives, furfurylamine (fa) as a primary amine, monoethanolamine (mea) as a primary amine with aliphatic OH groups, and methacryloyl chloride (MCl) as a methacrylate.

[0183] The AZA-TYR-mea / fa / meth benzoxazine monomer containing free aliphatic hydroxyl groups and methacrylate groups was synthesized in three stages. Figure 11 The first step, step a), corresponds to the Fischer esterification between 1,9-nonanedioc acid (azelaic acid, AZA) (1 equivalent) and 2-(4-hydroxyphenyl)ethanol (phloroglucinol, TYR) (2 equivalents) in the presence of p-toluenesulfonic acid introduced in a catalytic amount (0.5 wt%). The reactants are placed together in molten form at 130 °C and stirred mechanically for 24 hours to provide (AZA-TYR) (1 equivalent).

[0184] The second step, step b), corresponds to the Mannich condensation of AZA-TYR (1 equivalent) with furfurylamine (fa) (0.5 equivalent), monoethanolamine (mea) (1.5 equivalent), and paraformaldehyde (PFA) (4 equivalent). All these reactants were stirred together by mechanical stirring and reacted in a molten form at 70°C for 8 hours to obtain AZA-TYR-mea / fa benzo[a]azine containing free aliphatic hydroxyl groups.

[0185] Step 3, step c), corresponds to the methacrylation of AZA-TYR-mea / fa using methacryloyl chloride (6 equivalents). AZA-TYR-mea / fa is dried overnight under reduced pressure to remove trace amounts of water. It is then dissolved in dry CH2Cl2. Triethylamine (TEA, 6 equivalents) is added to the solution as a catalyst, and the mixture is poured into an ice bath. Then, methacryloyl chloride is added dropwise, and the solution is restored to room temperature and stirred overnight to provide AZA-TYR-mea / fa / meth where z = 0.25, x = 0.25, and y = 0.5.

[0186] Example 6 (comparative, not according to the invention): The diagram shows a benzo[a]azine monomer containing AZA-TYR-mea / fa / meth ester (where z = 0.25, x = 0.25, and y = 0.5). 1 H NMR spectroscopy (AVANCE III HD Bruker spectrometer).

[0187] Figure 12 Benzocyanine (BCC) containing ester and methacrylate groups but lacking free aliphatic groups was synthesized from 1,9-azelic acid (AZA) and 2-(4-hydroxyphenyl)ethanol (TYR) as phenolic acid derivatives, monoethanolamine (mea) as a primary amine with aliphatic OH groups, and methacryloyl chloride (MCl) as a methacrylate ester.

[0188] The AZA-TYR-meth benzoxazine monomer containing free aliphatic hydroxyl groups and methacrylate groups was synthesized in three stages. Figure 13 The first step, step a), corresponds to the Fischer esterification between 1,9-nonanedioc 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 are placed together in molten form at 130 °C and stirred mechanically for 24 hours to provide (AZA-TYR) (1 equivalent).

[0189] 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 these reactants are stirred together by mechanical stirring and reacted in molten form at 70°C for 8 hours to provide AZA-TYR-mea benzo[a]azine containing free aliphatic hydroxyl groups.

[0190] In the described embodiment, the primary amine is omitted, and monoethanolamine (mea) is used to provide both components (primary amine and amino alcohol).

[0191] Step 3, step c), corresponds to the methacrylation of AZA-TYR-mea using methacryloyl chloride (6 equivalents). AZA-TYR-mea is dried overnight under reduced pressure to remove trace amounts of water. It is then dissolved in dry CH2Cl2. Triethylamine (TEA, 6 equivalents) is added to the solution as a catalyst, and the mixture is poured into an ice bath. Then, methacryloyl chloride is added dropwise, and the solution is restored to room temperature and stirred overnight to obtain AZA-TYR-mea / meth (where x=z=0 and y=1).

[0192] Example 7 (comparative, not according to the invention). Two-step glassy polymer synthesis from AZA-TYR-mea / meth (x = z = 0 and y = 1) The benzo[a]azine monomer containing AZA-TYR-meth ester is shown. 1 H NMR spectroscopy (AVANCE III HDBruker spectrometer).

[0193] Figure 14 Conclusion

[0194] pass ​ Rheological measurements were performed to monitor the UV curing of AZA-TYR-meth in Example 6. The rheological diagram was obtained under the following conditions: 10 Hz with a constant amplitude of 0.1%; 25 mm plate. Testing was conducted using an Omnicure device (power, wavelength) exposed to UV light, achieving gelation after 4 seconds.

[0195] A 10mm diameter was prepared by exposing the resin to UV curing for 5 minutes. 5mm Cut 1mm rectangular strips and then heat-cur them at 170°C for 1 hour.

[0196] The viscoelastic properties of the double-cured glass-like polymer AZA-TYR-meth were measured by stress relaxation experiments recorded in torsional mode at 1% shear strain on an Anton Paar Physica MCR 302 rheometer. The polymer could not relax regardless of temperature because it contained no aliphatic OH groups capable of dynamically exchanging with ester bonds.

[0197] ​

[0198] The presence of ester bonds, free aliphatic hydroxyl groups, and acrylate moieties in the monomers of this invention is essential for the formation of a dynamic network of benzo[a]azine-based glass polymers, thereby allowing the material to be recycled, reshaped, and reprocessed. The resulting glass polymers exhibit particularly good relaxation times and temperatures, which distinguishes them from glass polymers known in the art.

Claims

1. A benzoxazine monomer of formula (I) containing ester and acrylate moieties, (I) in R1 is , R2 is ,and R3 is , in R a Selected from straight-chain or branched C1-C6 alkyl or alkoxy, straight-chain or branched C2-C6 alkenyl or alkeneoxy, substituted or unsubstituted straight-chain or branched C2-C6 alkynyl, and -C-straight-chain or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl. R Selected from H, OH, and O-straight-chain or branched C1-C6 alkyl groups, straight-chain or branched C1-C 15 Alkyl or C2-C 15 alkenyl or , , ,or ; R''、R R is independently selected from: straight-chain or branched C1-C6 alkyl or alkoxy; straight-chain or branched C2-C6 alkenyl or alkeneoxy; substituted or unsubstituted straight-chain or branched C2-C6 alkynyl; at least one straight-chain or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted ortho-, meta-, para-phenyl, cyclo(C3-C6 alkyl), or heterocyclic (C3-C6 alkyl) wherein the heteroatom is selected from N, S, and O; (CH2) n3 -Phenyl; -(CH2) n1 -O-(CH2) n2 -(CH3) group, wherein n1 and n2 are independently integers from 1 to 10; ;and ; R''' is Me, H, or CN; n3 is an integer from 1 to 10; The condition is 1≤n<50 and x>0, y>0 and z≥0, and, independent of n, x+y+z=1; x, y, and z represent the ratio between benzo[a]azine groups and methacrylate groups when prepared from amino alcohols and other amines. in ,as well as, It is the amount of amino alcohols. This indicates the amount of amines (excluding the amount of amino alcohols). Corresponding to the number of acrylate / methacrylate groups, and It is the total number of functional groups attached to the benzo[a]azine ring.

2. The monomer according to claim 1, wherein R a Selected from straight-chain or branched C1-C4 alkyl or alkoxy, straight-chain or branched C2-C4 alkenyl or alkeneoxy, substituted or unsubstituted straight-chain or branched C2-C4 alkynyl, and straight-chain or branched C1-C4 alkyl or C2-C6 alkenyl-substituted or unsubstituted phenyl groups; and independently, R Selected from H, OH, and O-straight-chain or branched C1-C4 alkyl groups, straight-chain or branched C1-C4 alkyl groups. 10 Alkyl or C2-C 10 Alkenyl, more preferably straight-chain or branched C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl or , , ,or .

3. The monomer according to claim 1 or 2, wherein, In the definition of R'', each C atom of the phenyl, cyclic (C3-C6 alkyl), or heterocyclic (C3-C6 alkyl) group independently carries a substituent as defined in claim 1 or 2.

4. A process for synthesizing benzo[a]azine monomers of formula (I) containing ester and acrylate moieties, comprising the following steps: In the presence of a Brønsted acid catalyst and under an inert atmosphere, at a temperature of 25°C to 200°C, a phenol ring containing at least one R is formed. A compound containing a phenolic hydroxyl group of formula (II) reacts with a carboxylic acid compound of formula (III) for 1 hour to 72 hours to obtain a phenol-terminated oligomer or molecule (compound (IV)): (II) in Ral has the definition of Ra and w = 1, 2 or 3; (III), Wherein R has the definition of R'' given in any one of claims 1-3, and n has the same definition as in claim 1. a) Under an inert atmosphere, react compound (IV) with a mixture of the following substances at a temperature of 50°C to 200°C for 1 hour to 12 hours to provide a compound of formula (VII): - Amino alcohols of formula (V): (V) - Aldehyde compounds, selected from formaldehyde and formula Paraformaldehyde, where m is an integer from 8 to 100. - Primary amines of formula (VI) (WE), and b) Reacting compound (VII) with a compound having an acrylate or methacrylate group at a temperature of -10°C to 50°C for 12 to 48 hours to obtain a benzo[a]azine monomer of formula (I) containing an ester and an acrylate moiety, said compound being at least one of compounds (VIII)-(XII). (i) (meth)acryloyl chloride of formula (VIII) (VIII) In polar solvents, at temperatures ranging from -5 to 25°C; or (ii) Methyl methacrylate of formula (IX) (IX) In the presence of catalysts and polymerization inhibitors; or (iii) (Meth)acrylic acid of formula (X) (X) In the presence of a catalyst and azodicarboxylic acid ester, in a solvent, at a temperature from -10°C to reflux; 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 acid anhydride of formula (XII) (XI) (XII) In the presence of a catalyst; in - R'''' is H or CH3; - R''''' is CH3 or C2H5; The condition is that at least one R of the phenolic acid derivative When the -OH group is in the ortho position, then R For H.

5. The process according to claim 4, wherein the stoichiometry of the starting reactant in step a) is n equivalents: 1.0 equivalents, to obtain 1.0 equivalents of phenol-terminated oligomers or molecules (compound (IV)).

6. The process according to claim 4 or 5, wherein the amino alcohol of formula (V) comprises R A group consisting of a primary amine moiety and an aliphatic hydroxyl moiety of a straight-chain amino alcohol.

7. The process according to any one of claims 4-6, wherein the primary amine is selected from allylamine, methylamine, ethylamine, propylamine, butylamine, isopropylamine, hexylamine, cyclohexylamine, stearylamine, 2-aminofluorene, aminophenylacetylene, propyne ether aniline, 4-aminobenzyl nitrile, furfurylamine and aniline, or mixtures thereof.

8. The process according to any one of claims 4-7, wherein the stoichiometry of the starting reactants phenol-terminated oligomers or molecules (IV): amino alcohol (V): primary amine (VI): paraformaldehyde in step b) is 1.0 equivalent: n(x+y): nz: 2.0n(x+y+z), yielding 1.0 equivalent of compound (VII).

9. The process according to any one of claims 4-8, 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, with a maximum yield of at least 75%.

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

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

12. The process according to any one of claims 4-9, wherein step c) is carried out with compound (X)-(meth)acrylic acid via a Mitsunobu reaction, the Mitsunobu reaction involving a catalyst such as triphenylphosphine and an azodicarboxylic acid ester 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.

13. The process according to any one of claims 4-9, wherein step c) is carried out by esterification of an excess of (meth)acrylic acid compound (X) in the presence of an acidic catalyst, while distilling the resulting azeotropic mixture, wherein the acidic catalyst is preferably selected from p-toluenesulfonic acid (p-TCA), sulfuric acid (H2SO4), and methanesulfonic acid (CF3SO3H).

14. The process according to any one of claims 4-9, wherein step c) is carried out by acylation of compound (XI)-(meth)acrylic anhydride or compound (XII)-(meth)acrylic acid asymmetric anhydride in the presence of a catalyst in a temperature range of -5°C to 15°C, wherein the catalyst is preferably selected from p-toluenesulfonic acid (p-TCA), sulfuric acid (H2SO4) and anhydrous ZnCl2.

15. The process according to any one of claims 4-14, wherein the corresponding stoichiometry of the starting reactant compound VII in step c): the compound (VIII-XII) having an acrylate or methacrylate group is 1.0 equivalent: 3.0 ny equivalent, to obtain 1.0 equivalent of a benzo[a]azine monomer containing the ester and acrylate moieties.

16. A process for preparing polybenzoxazine derivative glass polymers, comprising a first curing step by UV treatment polymerization of a benzoxazine monomer of formula (I) containing ester and acrylate moieties as defined in any one of claims 1-3 or obtainable by the process according to any one of claims 4-15, followed by a second curing step implemented by heat treatment of polymerization of the benzoxazine moieties of the said benzoxazine monomer containing ester and acrylate moieties.

17. The process of claim 16, wherein the first curing step is carried out in the presence of a free radical initiator, wherein the free radical initiator is 1 wt% to 5 wt% by weight.

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

19. A polybenzoxazine derivative glass polymer, which can be obtained by the process described in any one of claims 16-18, and exhibits at least one of 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) A relaxation temperature value of 100°C to 300°C, preferably 130°C to 200°C, more preferably 130°C to 180°C, wherein ≥ T v value.

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