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WO2024028605A1 - Ortho-substituted difunctional bio-benzoxazine compounds, preparation methods and uses thereof - Google Patents

Ortho-substituted difunctional bio-benzoxazine compounds, preparation methods and uses thereof Download PDF

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WO2024028605A1
WO2024028605A1 PCT/GB2023/052051 GB2023052051W WO2024028605A1 WO 2024028605 A1 WO2024028605 A1 WO 2024028605A1 GB 2023052051 W GB2023052051 W GB 2023052051W WO 2024028605 A1 WO2024028605 A1 WO 2024028605A1
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heterocycloalkyl
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Paul Jones
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the invention relates to a class of ortho-substituted benzoxazine compounds useful as a curative and having a high degree of biological based carbon content.
  • the invention is directed to a class of ortho-substituted difunctional benzoxazine compounds comprising two benzoxazine rings, each di-substituted with furfuryl groups, a resin curative composition comprising the benzoxazine compound, processes for preparing the benzoxazines and uses thereof.
  • a benzoxazine is chemical compound comprising a bicyclic ring system containing an oxygen atom and a nitrogen atom within a heterocyclic oxazine ring that is directly fused to a benzene ring.
  • benzoxazines There are several isomers of benzoxazine with the nitrogen and oxygen at differing positions that may be generically referred to as “benzoxazines”, in addition to compounds having differing levels of saturation in the oxazine ring that may also go by the name “benzoxazine”.
  • benzoxazine refers to 3,4-dihydro-2/-/-1 ,3-benzoxazine, which is the benzoxazine monomer most useful in the production of benzoxazine based polymers, the structure of which is shown below.
  • ortho-substituted or any variation thereof, in the context of an ortho-substituted benzoxazine refers to the position adjacent to the carbon atom bonded to the benzoxazine oxygen, the structure of which is shown below with the ortho-substituent denoted as R 4 .
  • Benzoxazines are capable of undergoing ring opening on heating without the need of catalysts and without emitting volatiles, leading to self-polymerisation, which is useful for both providing thermosets and also in curing to reinforce other materials.
  • the benzoxazine polymers formed therefrom are the products of interest for providing suitable molecular weight structures that confer desirable protective properties once fully cured.
  • benzoxazine dates back over 60 years although the low molecular weight species at that time could not offer the performance characteristics now attributed to, and associated with, the polymeric benzoxazines that form the basis of the coating and matrix systems employed today.
  • Commercially available benzoxazines are generally provided by reaction of i) a phenolic compound, which may be phenol, bisphenol, or a substituted derivative thereof, ii) formaldehyde which comes in different concentrations as an aqueous solution of the gas or in polymerized form as paraformaldehyde, and iii) a primary amine which contains one or multiple primary amine groups, but may contain additional secondary or tertiary amine groups and/or other functional groups.
  • the process to synthesise the benzoxazine structure is a Mannich reaction between the primary amine and the aldehyde liberating water to form an iminium ion, followed by cyclisation with the phenolic compound and a second equivalent of aldehyde to form the oxazine ring.
  • the Mannich reaction to form a benzoxazine ring, followed by selfpolymerisation, is shown in Scheme 1 below.
  • benzoxazine polymers for coating and matrix applications are derived from difunctional benzoxazines.
  • the resultant products have repeating units of a higher molecular weight and form polymers with a higher degree of cross-linkage.
  • a difunctional benzoxazine may also comprise only one benzene ring that is fused to two separate oxazine rings, providing two benzoxazine moieties on a shared benzene ring.
  • bisphenol A is a well-known choice of phenolic compound for this purpose as it comprises two phenol groups capable of transformation into benzoxazines.
  • Cardarez R111 (RTM) depicted below, is a known bisphenol A based benzoxazine useful for providing polymers with a high glass transition temperature (Tg), low water absorption, excellent physical electrical performance, along with excellent fire resistance properties.
  • Tg glass transition temperature
  • ETM flame resistance properties
  • Cardarez R111 (RTM) forms a solid resin when prepared.
  • the present invention is based on the surprising discovery of a new class of orthosubstituted difunctional benzoxazine compounds that are liquids under standard conditions (e.g. at 25 °C and 100 KPa), but provide thermosets with comparable properties, such as viscosity and Tg, whilst also providing greatly increased bio-carbon content and obviating the need for synthesis from formaldehyde.
  • Resin compositions formed from the new class of ortho-substituted difunctional benzoxazine compounds of the present invention also present superior gel times, converting to a solid material more rapidly than conventional benzoxazine resins.
  • the bio-carbon content of the benzoxazines of the present invention is greatly increased by replacing the formaldehyde precursor with furfuraldehyde, also known as furfural.
  • Furfural is an inexpensive, renewable and naturally occurring feedstock derived from the dehydration of sugars, and occurs in a variety of agricultural by-products, including corncobs, oats, wheat bran, and sawdust.
  • Furfural has been used in the synthesis of aryloxazines in the pharmaceutical industry, in particular, napthoxazines have been investigated for potential medicinal properties. See M. S. Al Ajely and A M Noori, Synthesis of New Oxazin Compounds Derived from Furfural. Chalcons and Schiff base, LOJ pharmacol., 2019, 1(3), 66-71. and S. A. Ozturkcan and T Zuhal, Synthesis and Characterizations of New 1,3-Oxazine Derivatives, J. Chem. Soc. Pak., 2011 , 33(6), 939-944.
  • the ortho-substituted difunctional benzoxazine of the present invention is useful in forming a polymer comprising repeating units formed from an ortho-substituted difunctional benzoxazine to provide a high degree of cross-linkage and a high biocarbon based content.
  • the new class of furfural derived ortho-substituted difunctional benzoxazines of the present invention have also been found to typically be in liquid form at standard conditions (e.g. 25 °C and 100 kPa), which provides numerous advantages in handling, application and use in resin compositions over conventional solid benzoxazine resins.
  • liquid benzoxazines may be combined with a curing catalyst at low temperature (below which reaction of the benzoxazine can be expected) without the risk of unwanted or premature self-polymerisation.
  • a solid benzoxazine compound such as Cardarez R111 (RTM) must be melted before mixing with a catalyst is possible, thus risking undesired self-polymerisation due to the high temperature required for melting.
  • the present invention provides a compound of formula (I): wherein each R group is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- C3 to C20 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , -C(O)OH, -C(O)OR 1 , -C(O)NH 2 , - C(O)NHR 1 , -
  • the present invention provides a compound of formula (II): (H) wherein each R group is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- C3 to C20 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , -C(O)OH, -C(O)OR 1 , -C(O)NH 2 , - C(O)NHR 1
  • the present invention provides a compound of formula (III): wherein R is selected from: Ci to C 2 o alkyl, Ci to C 2 o haloalkyl, C 3 to C 20 cycloalkyl, C 3 to C 2 o heterocycloalkyl, C 2 to C 2 o alkenyl, C 2 to C 2 o alkynyl, Ci to C 2 o alkyl- Ce to Cu aryl, Ci to C 2 o alkyl-C 2 to C9 heteroaryl, Ci to C 2 o alkyl-C 3 to C 2 o cycloalkyl, Ci to C 20 alkyl-C 3 to C heterocycloalkyl, Ci to C 20 alkyloxy, Ci to C 20 alkylamino, -OH, - OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , -C(O)OH, -C(O)OR 1 , -C(O)NH 2 ,
  • the present invention comprises a resin composition comprising a benzoxazine compound of formula (I), (II) or (III), as described herein.
  • the present invention provides the use of a benzoxazine compound of formula (I), (II) or (III), or a resin composition thereof, as described herein, to reinforce a material.
  • the present invention provides a method for preparing a reinforced material, said method comprising: a) contacting a material to be reinforced with a compound of formula (I), (II) or (III), or a resin composition thereof; and b) allowing said compound to self-polymerise to form a reinforced material.
  • the present invention provides a reinforced material prepared, or preparable, by the methods described herein.
  • Figure 1 demonstrates the viscosity vs temperature of the comparative Cardarez R111 (RTM) benzoxazine
  • Figure 2 demonstrates the viscosity development over time of comparative Cardarez R111 (RTM) benzoxazine at 100 °C, 120 °C and 140 °C;
  • Figure 3 demonstrates the gel-time reactivity vs temperature of comparative Cardarez R111 (RTM);
  • Figure 4 demonstrates the gel-time reactivity vs temperature of Compound A
  • Figure 5 demonstrates the Tg development of thermosets cured at 180 °C vs time for a compound A thermoset and a comparative Cardarez R111 (RTM) thermoset;
  • Figure 6 demonstrates the Tg development of Compound A during curing at 140 °C over 1 hour with 3%, 4% or 5% of a ferric chloride catalyst
  • Figure 7 demonstrates the Compound A viscosity build vs time at 60 °C and 100 °C, with 5% ferric chloride catalyst
  • Figure 8 demonstrates the gel times of Compound A in combination with concentrations of 1 , 1.5 and 2 PHR of BCh octyl dimethylamine complex at 160 °C.
  • hydrocarbyl refers to a monovalent or divalent group, comprising hydrogen and carbon atoms, such as a major proportion (i.e., more than 50 %) of hydrogen and carbon atoms, preferably consisting exclusively of hydrogen and carbon atoms.
  • the hydrocarbyl group may be aromatic, saturated aliphatic or unsaturated aliphatic.
  • the hydrocarbyl group may be entirely aliphatic or a combination of aliphatic and aromatic portions.
  • the hydrocarbyl group includes a branched aliphatic chain which is substituted by one or more aromatic groups.
  • hydrocarbyl groups therefore include acyclic groups, as well as groups that combine one or more acyclic portions and one or more cyclic portions, which may be selected from carbocyclic, aryl and heterocyclyl groups.
  • the hydrocarbyl group includes monovalent groups and polyvalent groups as specified and may, for example, include one or more groups selected from alkyl, alkenyl, alkynyl, carbocyclyl (e.g. cycloalkyl or cycloalkenyl), aryl and heterocyclyl.
  • the hydrocarbyl group may contain one or more heteroatoms, such as oxygen, nitrogen, sulphur, silicon or halogen which may be part of a functional group such as an alcohol, ether, carbonyl, ester, carboxylic acid, carbonate, amide, amine, carbamate, urea, thiol, thioether, thioester, thioacid, thioamide, silane organic halide or heterocycle, the hydrocarbyl linker may contain any combination of the above insofar as it is chemically stable.
  • halogens may entirely replace the hydrogen component of the hydrocarbyl group (i.e. the carbon- bonded hydrogens) to give the corresponding halo-substituted analogue.
  • alkyl refers to a monovalent straight- or branched-chain alkyl moiety. Unless specifically indicated otherwise, the term “alkyl” does not include optional substituents.
  • haloalkyl refers to an alkyl group substituted with one or more halogen atoms.
  • halogen refers to any of fluorine, chlorine, bromine, or iodine.
  • alkyloxy refers to an alkyl group substituted with one or more hydroxy groups.
  • alkylamino refers to an alkyl group substituted with one or more primary, secondary, or tertiary amine groups.
  • cycloalkyl refers to a monovalent saturated aliphatic hydrocarbyl moiety containing at least one ring, wherein said ring has at least 3 ring carbon atoms.
  • the cycloalkyl groups mentioned herein may optionally have alkyl groups attached thereto.
  • Examples of cycloalkyl groups include groups that are monocyclic, polycyclic (e.g., bicyclic) or bridged ring system.
  • Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
  • heterocycloalkyl refers to a cycloalkyl group wherein the ring contains at least one heteroatom selected from oxygen, nitrogen, and sulphur.
  • heterocycloalkyl groups include morpholine, piperidine, piperazine and the like.
  • alkenyl refers to a monovalent straight- or branched-chain alkyl group containing at least one carbon-carbon double bond, of either E or Z configuration unless specified.
  • alkynyl refers to a monovalent straight- or branched-chain alkyl group containing at least one carbon-carbon triple bond. Examples of alkenyl groups include ethenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3- butenyl, 1 -pentenyl, 2-pentenyl, 3-pentenyl, 1 -hexenyl, 2-hexenyl, 3-hexenyl and the like.
  • aryl refers to an aromatic carbocyclic ring system.
  • An example of an aryl group includes a group that is a monocyclic aromatic ring system or a polycyclic ring system containing two or more rings, at least one of which is aromatic.
  • Examples of aryl groups include aryl groups that comprise from 1 to 6 exocyclic carbon atoms in addition to ring carbon atoms.
  • Examples of aryl groups include aryl groups that are monovalent or polyvalent as appropriate. Examples of monovalent aryl groups include phenyl, benzyl, naphthyl, fluorenyl, azulenyl, indenyl, anthryl and the like.
  • An example of a divalent aryl group is 1 ,4-phenylene.
  • heteroaryl refers to an aromatic heterocyclic ring system wherein said ring atoms include at least one ring carbon atom and at least one ring heteroatom selected from nitrogen, oxygen and sulphur.
  • heteroaryl groups include heteroaryl groups that are a monocyclic ring system or a polycyclic (e.g. bicyclic) ring system, containing two or more rings, at least one of which is aromatic.
  • heteroaryl groups include those that, in addition to ring carbon atoms, comprise from 1 to 6 exocyclic carbon atoms.
  • heteroaryl groups include those that are monovalent or polyvalent as appropriate.
  • heteroaryl groups include pyridyl, pyrimidyl, thiopheneyl, isoxazolyl and benzo[b]furanyl groups.
  • furfural is the aldehyde used in the Mannich reaction to form the benzoxazine rings.
  • the resulting benzoxazine rings are substituted with furan at the 2- and 4-positions of the oxazine ring.
  • a substituted furfural may be used instead of, or in combination with, unsubstituted furfural.
  • formulae (I), (II) and (III) the optional furfural substituents are defined by R 3 .
  • phenolic compound refers to phenol, optionally substituted with one or more R groups, wherein the R groups are as defined herein.
  • bisphenol compound refers to an organic compound comprising phenol moieties conjoined by a linker attached at any one of the 3-, 4-, or 5- positions, independently, relative to the phenol oxygen, wherein the linker is L 2 as defined herein.
  • the phenol moieties are optionally substituted with one or more R groups at one or more of the 3-, 4-, and/or 5- positions relative to the phenol oxygen that are not occupied by L 2 , wherein the R groups are as defined herein.
  • the present invention relates to a hitherto unknown class of ortho-substituted difunctional benzoxazine compounds comprising two benzoxazine rings di-substituted with furfuryl groups.
  • Two benzoxazine groups may be conjoined by a linker attached to the oxazine nitrogen atoms, or attached to the benzoxazine benzene rings, or the two benzoxazine groups may share a single benzene ring.
  • benzoxazine compounds of the present invention comprise at least one unsubstituted position on the benzene ring to allow for self-polymerisation of the orthosubstituted difunctional benzoxazine compound.
  • unsubstituted herein refers to substitution by a hydrogen atom.
  • the self-polymerisation takes place by thermal ring-opening polymerisation with or without catalyst or co-reactant.
  • Lewis acid catalysts for example, including titanium isopropoxide, aluminium trichloride, Dichloro(methyl)aluminium, aluminium tribromide, iron tribromide, titanium tetrachloride, tin tetrachloride, yttrium trichloride, boron trifluoride (optionally in the form of boron trifluoride complexes, such as BF 3 etherate, BF 3 THF complex, or BF 3 amine complexes such as BF 3 methyl ethyl amine, BF 3 ethyl amine, BF 3 triethyl amine, or BF 3 dimethyl octyl amine, preferably BF 3 methyl ethyl amine), boron trichloride (optionally in the form of boron trichloride (optionally in
  • the result of the selfpolymerisation is a high molecular weight thermoset polymer matrix with a high degree of cross-linkage.
  • Resins comprising the ortho-substituted difunctional benzoxazine compounds of the present invention are therefore useful precursors to poly-benzoxazine polymers.
  • the ortho-substituted difunctional benzoxazine compounds of the present invention are liquids at standard conditions, it may not be necessary to include a solvent or diluent in such a resin. Nevertheless, solvents or diluents may be used to adjust the properties of the resin as is required.
  • the class of benzoxazines of the present invention may be synthesised by a Mannich reaction between an ortho-substituted phenolic compound, a primary amine, and furfural. As would be appreciated, two equivalents of furfural are required for every one equivalent of ortho-substituted phenolic compound and primary amine. As the present class of benzoxazines are difunctional, two equivalents of ortho-substituted phenolic compound and two equivalents of primary amine must be reacted with four equivalents of furfural to provide one equivalent of difunctional benzoxazine. However, two equivalents of the ortho-substituted phenolic compound or two equivalents of the primary amine may be comprised within a single difunctional molecule.
  • one equivalent of an ortho-substituted difunctional phenolic compound or of a difunctional primary amine may be reacted with two equivalents of a primary amine or ortho-substituted phenolic compound, respectively, as well as four equivalents of furfural.
  • the resulting benzoxazine will be difunctional as two benzoxazine rings are formed within the same single molecule. Therefore, the class of ortho-substituted difunctional benzoxazine compounds of the present invention all share the feature of two benzoxazine rings, each substituted with two furan groups and at least one benzoxazine ortho-substituent.
  • the benzoxazine compounds of the present invention have the general formula (I), shown below. wherein each R group is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- C3 to C20 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C 2 o alkylamino, -OH, -OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , -C(O)OH, -C(O)OR 1 , -C(O)NH 2 , -
  • both R 4 groups are other than hydrogen, i.e. both R 4 groups are independently selected from: Ci to C 20 alkyl, Ci to C 20 haloalkyl, C 3 to C 20 cycloalkyl, C 3 to C 2 o heterocycloalkyl, C 2 to C 2 o alkenyl, C 2 to C 2 o alkynyl, Ci to C 2 o alkyl-Ce to C14 aryl, Ci to C 2 o alkyl-C 2 to C9 heteroaryl, Ci to C 2 o alkyl-C 3 to C 2 o cycloalkyl, Ci to C 2 o alkyl-Cs to C heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR 1 , - NH 2 , -NHR 1 , -N 1 2, -C(O)OH, -C(O)OR 1 , -C(O)NH 2
  • R 4 group(s) is/are activating groups.
  • R 4 group(s) is/are -OMe.
  • a compound according to formula (I), wherein one or both R 4 groups are -OMe may be prepared from guaiacol, also known as 2-Methoxy phenol.
  • Guaiacol is a naturally occurring organic compound biosynthesized by a variety of organisms, such as guaiacum or wood creosote. It is also found in essential oils from celery seeds, tobacco leaves, orange leaves, and lemon peels. Guaiacol is also an innocuous compound often used as an expectorant, antiseptic, and local anaesthetic.
  • one or both benzene rings of the benzoxazines are substituted with R groups at the 3-position and/or the 5-position, relative to the oxygen of the benzoxazine ring.
  • Formula (I) comprises two benzoxazine moieties attached at the benzoxazine nitrogen atoms though a divalent hydrocarbyl linker group L 1 .
  • the ortho-substituted difunctional benzoxazine may be derived from a difunctional primary amine, comprising the linker group L 1 , wherein the difunctional primary amine undergoes a Mannich reaction with four equivalents of the furfural and two equivalents of a phenolic compound to form the compound of formula (I).
  • L 1 comprises 2 to 50 carbon atoms, 3 to 50 carbon atoms, 5 to 50 carbon atoms, 2 to 40 carbon atoms, 3 to 40 carbon atoms, 5 to 40 carbon atoms, 2 to 30 carbon atoms, 3 to 30 carbon atoms, 5 to 30 carbon atoms, 2 to 20 carbon atoms, 3 to 20 carbon atoms, or 5 to 20 carbon atoms.
  • L 1 comprises at least one of: i) a heteroatom selected from nitrogen, oxygen, sulphur and silicon; ii) a double or triple carbon-carbon bond; or iii) an aromatic ring, heteroaromatic ring, and/or non-aromatic ring.
  • Table 1 Exemplary list diamines useful in the present invention and their corresponding L 1 linkers.
  • L 1 is a divalent hydrocarbyl linker comprising two rings conjoined by a divalent Ci to Cw alkyl group.
  • the two rings may independently be carbocycles or heterocycles, but are both preferably carbocycles.
  • the two rings may independently be 3- to 14-membered, but are preferably both 6-membered.
  • the two rings may independently be aromatic, saturated or partially saturated, but are preferably saturated. Therefore, the two rings are most preferably cyclohexane.
  • the compound of formula (I) has the general formula (la), shown below.
  • ring A and ring B are independently either aromatic or saturated 6 membered carbon rings, preferably wherein rings A and B are both saturated rings (e.g. both a cyclohexane group);
  • one or two ortho-substituted phenols are used to provide the corresponding ortho-substituted benzoxazine, or phenols bearing further optional substitution may be used to provide corresponding further optional substitution in the resulting benzoxazine.
  • the optional benzoxazine substituents are defined by group R.
  • one position ortho to the phenolic -OH group i.e. either the 2-position or 6- position, must be unsubstituted (i.e. substituted by hydrogen), as well as at least one other position.
  • an unsubstituted ortho position is required for the Mannich reaction to take place to form the benzoxazine ring, and the second unsubstituted position is required for the benzoxazine self-polymerisation to take place.
  • the phenolic precursor must be 2- or 6-unsubsituted in relation to the phenolic oxygen, and must also be unsubstituted at at least one other position, in order to provide a benzoxazine with at least one unsubstituted position for polymerisation.
  • the ortho-position is defined by R 4 , wherein at least one R 4 group, preferably both R 4 groups, is/are an ortho-substituent independently selected from: Ci to C 2 o alkyl, Ci to C20 haloalkyl, C 3 to C20 cycloalkyl, C 3 to C20 heterocycloalkyl, C 2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-C 3 to C20 cycloalkyl, Ci to C20 alkyl-C 3 to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , -C(O)OH, - C(O)OR 1 ,
  • Two identical ortho-substituted phenolic compounds may be used to form a symmetrical ortho-substituted difunctional benzoxazine, or two different phenolic compounds may be used to form an asymmetrical difunctional benzoxazine, where one or both phenol compounds are ortho-substituted as long as both phenolic compounds are unsubstituted at one of the 2- or 6- positions, and at least one other position, in relation to the phenolic oxygen.
  • naturally derived phenolic compounds may be used in order to further increase the content of bio-carbon in the resulting benzoxazine.
  • bio derivable phenolic compound is guaiacol.
  • guaiacol is used as one of the phenolic compounds, more preferably both of the phenolic compounds, giving a compound of formula (I) wherein one, preferably both, R 4 group(s) is/are methoxy.
  • the benzoxazine compounds of the present invention have the general formula (II), shown below. wherein each R group is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-C 6 to C14 aryl, Ci to C20 alkyl-C 2 to C 9 heteroaryl, Ci to C20 alkyl- C3 to C20 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , -C(O)OH, -C(O)OR 1 , -C(O)NH 2 , - C
  • both R 4 groups are other than hydrogen or a direct bond to L 2 , i.e. both R 4 groups are independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- C 3 to C20 cycloalkyl, Ci to C20 alkyl-C 3 to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , -C(O)OH, -C(O)OR 1 , -C(O)NH 2 , -
  • R 4 group(s) is/are activating groups.
  • R 4 group(s) is/are -OMe.
  • a compound according to formula (I), wherein both R 4 groups are -OMe may be prepared from bisguiacol F.
  • Bisguiacol F is a bisphenol compound substituted with a methoxy group at the ortho position of both benzene rings, i.e. two guaiacol groups connected at their 4-positions by a methylene bridge.
  • Bisguiacol F has reduced endocrine disrupting activity compared to bisphenol A and other bisphenol compounds.
  • Bisguiacol F may also be easily prepared from naturally derived guaiacol and vanillyl alcohol, which is derivable from vanilla extract.
  • bisguiacol F thus allows for the replacement of toxic, endocrine disrupting, and hydrocarbon derived chemicals, such as bisphenol A, with innocuous bio-based alternatives.
  • bio-based feedstocks such as bisguaiacol F also significantly increases the percentage of bio-based carbon in the resulting benzoxazine.
  • Formula (II) comprises two benzoxazine moieties linked by a linker L 2 attached to the benzene ring of each benzoxazine.
  • this ortho-substituted difunctional benzoxazine may be derived from an ortho-substituted bisphenol compound.
  • the linker L 2 may be independently attached to each benzene ring at any of the 2-, 3-, 4-, 5- or 6-positions relative to the phenolic oxygen.
  • One of the two ortho i.e. 2- and 6-positions
  • L 2 is a direct bond, or a divalent group selected from C(O), O, S, S(O), S(O) 2 or a hydrocarbyl linker comprising 1 to 50 carbon atoms.
  • L 2 is attached at the 4-position, relative to the benzoxazine oxygen.
  • L 2 is selected from S(O) 2 , CH 2 , C(CH 3 ) 2 , or a divalent benzene ring.
  • L 2 comprises 2 to 50 carbon atoms, 3 to 50 carbon atoms, 5 to 50 carbon atoms, 2 to 40 carbon atoms, 3 to 40 carbon atoms, 5 to 40 carbon atoms, 2 to 30 carbon atoms, 3 to 30 carbon atoms, 5 to 30 carbon atoms, 2 to 20 carbon atoms, 3 to 20 carbon atoms, or 5 to 20 carbon atoms.
  • the linker L 2 may be attached to the resulting benzoxazine benzene ring at any available position, including via R 4 when R 4 is a direct bond. As will be appreciated, where R 4 and L 2 are both direct bonds, then this is equivalent to a single direct bond between the benzoxazine benzene rings. It is preferred that L 2 is attached at the -3, -4, or 5-position, more preferably the 4-position, relative to the benzoxazine oxygen. Many widely commercially available bisphenol compounds comprise linkers L 2 attached at both of the 4-positions relative to the phenolic oxygens, these are generally known as 4,4- bisphenols.
  • Table 2 Exemplary list of ortho-substituted bisphenols useful in the present invention and their corresponding L 2 linkers.
  • the L 2 groups would be conserved during a Mannich reaction and would thus be present in the compound of formula (II) when derived from the corresponding bisphenol compound precursor.
  • the bisphenol compounds listed in Table 2 are all 4,4-bisphenols, the scope of the invention also includes any isomers of these bisphenol compounds wherein the L 2 linker is attached at any combination of the 2-, 3-, 4-, 5- and -6 positions, so long as at least one ortho position, i.e. either the 2- or 6-position remains unsubstituted.
  • At least one unsubstituted position must remain on the resulting benzoxazine for polymerisation to take place.
  • both R 4 groups are other than hydrogen or a direct bond to L 2 and 0 or 1 R groups are present on the benzoxazine ring.
  • the number of possible R groups on each benzoxazine ring is shown in formula (II) as y.
  • a symmetrical bisphenol compound, with the same on each phenol group may be used to form a symmetrical ortho-substituted difunctional benzoxazine, or an asymmetrical bisphenol compound, with differing substituents on each phenol group may be used may be used to form an asymmetrical difunctional benzoxazine, as long as both phenol groups are unsubstituted at one of the 2-or 6-position and at least one other position, in relation to the phenolic oxygen, in both cases the total number of R groups is y + y.
  • the benzoxazine compounds of the present invention have the general formula (III), shown below. wherein R is selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C 3 to C20 heterocycloalkyl, C 2 to C20 alkenyl, C 2 to C20 alkynyl, Ci to C20 alkyl- Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-Cs to C20 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, - OR 1 , -NH 2 , -NHR 1 , -NR 1 2, -C(O)OH, -C(O)OR 1 , -C(O)NH 2 , -C(O)NHR 1
  • the ortho-substituted difunctional benzoxazine may be derived from a 2- subsitututed 1 ,3-benzene-diol. Two oxazine rings are formed on the shared benzene ring, giving an ortho-substituted difunctional benzoxazine with a shared benzene ring and a shared ortho-substituent.
  • the compound of formula (III) may not be substituted at the 5-position of the benzene ring relative to the benzoxazine oxygens which are considered to occupy the 1 - and 3-positions, so that self-polymerisation of the resulting benzoxazine may take place at this position.
  • the corresponding 4- and 6-positions of the benzene ring are occupied carbon atoms that form part of the benzoxazine ring.
  • the compound of formula (III) is substituted at the 2-position, relative to the benzoxazine oxygens which are considered to occupy the 1 - and 3-positions.
  • R is selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-C 6 to C14 aryl, Ci to C20 alkyl-C 2 to C 9 heteroaryl, Ci to C20 alkyl- C3 to C20 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , -C(O)OH, -C(O)OR 1 , -C(O)NH 2 , - C(O)NHR 1 , -C(O)NR 1 2,
  • the 1 ,3-benzene-diol precursor must be unsubstituted at the 4- and 6-positions in order to allow the oxazine rings to be formed at these positions, and the 5-position must be unsubstituted to allow for self-polymerisation of the resulting benzoxazine compound.
  • pyrogallol The corresponding precursor with hydroxy substitution at the 2-position, i.e. 1 ,2,3- benzene-triol, is known as pyrogallol. Pyrogallol is derivable by de-carboxylation of gallic acid, which is found in gallnuts, sumac, witch hazel, tea leaves, oak bark, and other plants.
  • the compounds of any one of Formulae (I), (II) and (III) are selected from those wherein R is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl- C 6 to C14 aryl, Ci to C 29 alkyl-C 2 to C 9 heteroaryl, Ci to C20 alkyl-C 3 to C10 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, - OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , -O(CO)H, -O(CO)R 1 , -NH(CO)H, -NH(CO)R 1 , -NR 1 (CO)
  • the compounds of any one of Formulae (I), (II) and (III) are selected from those wherein R is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , Ce to C14 aryl optionally substituted with one or more R 2 group, or C2 to C9 heteroaryl optionally substituted with one or more R 2 group; preferably -OH; wherein R 1 is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl or C2 to C20 alkenyl; wherein R 2 is independently selected from: Ci to C20 alkyl, -OH, -NH 2 , -OC1 to
  • the compounds of any one of Formulae (I), (II) and (III) are selected from those wherein R is independently selected from: Ci to C10 alkyl, Ci to C10 haloalkyl, C3 to Cw cycloalkyl, C3 to C10 heterocycloalkyl, C2 to Cw alkenyl, C2 to C10 alkynyl, Ci to C alkyl-C 6 to C14 aryl, Ci to C alkyl-C 2 to C 9 heteroaryl, Ci to C alkyl- C3 to C10 cycloalkyl, Ci to C10 alkyl-Cs to Cw heterocycloalkyl, Ci to Cw alkyloxy, Ci to Cw alkylamino, -OH, -OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , -C(O)OH, -C(O)OR 1 , -C(O)NH 2 , - C(O)N
  • the compounds of any one of Formulae (I), (II) and (III) are selected from those wherein R is independently selected from: Ci to Cw alkyl, C 3 to Cw cycloalkyl, C3 to Cw heterocycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, Ci to Cw alkyl- Ce to C14 aryl, Ci to Cw alkyl-C2 to C 9 heteroaryl, Ci to Cw alkyl-Cs to Cw cycloalkyl, Ci to Cw alkyl-C 3 to Cw heterocycloalkyl, Ci to Cw alkyloxy, Ci to Cw alkylamino, -OH, - OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , -O(CO)H, -O(CO)R 1 , -NH(CO)H, -NH(CO)R 1 , -NR 1 (CO)H
  • the compounds of any one of Formulae (I), (II) and (III) are selected from those wherein R is independently selected from: Ci to C alkyl, C 3 to C cycloalkyl, C 3 to Cw heterocycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, Ci to Cw alkyloxy, Ci to Cw alkylamino, -OH, -OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , Ce to C14 aryl optionally substituted with one or more R 2 group, or C 2 to C 9 heteroaryl optionally substituted with one or more R 2 group; preferably -OH; wherein R 1 is independently selected from: Ci to Cw alkyl, C 3 to Cw cycloalkyl or C 2 to Cw alkenyl; wherein R 2 is independently selected from: Ci to Cw alkyl, -OH, -NH 2 , -OC1 to Cw
  • the compounds of any one of Formulae (I) and (II) are selected from those wherein R 4 is independently either hydrogen or selected from: Ci to C20 alkyl, C 3 to C20 cycloalkyl, C 3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C 9 heteroaryl, Ci to C20 alkyl-C 3 to Cw cycloalkyl, Ci to C20 alkyl-C 3 to Cw heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , -O(CO)H, -O(CO)R 1 , -NH(CO)H, - NH(CO)R 1 , -NR 1 (
  • the compounds of any one of Formulae (I) and (II) are selected from those wherein R 4 is independently either hydrogen or selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , C 6 to C14 aryl optionally substituted with one or more R 2 group, or C2 to C9 heteroaryl optionally substituted with one or more R 2 group; preferably -OH; wherein R 1 is independently selected from: Ci to C20 alkyl, C 3 to C20 cycloalkyl or C2 to C20 alkenyl; wherein R 2 is independently selected from: Ci to C20 alkyl, -OH, -NH 2 , -OC
  • the compounds of any one of Formulae (I) and (II) are selected from those wherein R 4 is independently either hydrogen or selected from: Ci to C alkyl, Ci to C10 haloalkyl, C3 to C10 cycloalkyl, C3 to Cw heterocycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, Ci to Cw alkyl-Ce to C14 aryl, Ci to Cw alkyl-C2 to C9 heteroaryl, Ci to Cw alkyl-Cs to Cw cycloalkyl, Ci to Cw alkyl-Cs to Cw heterocycloalkyl, Ci to Cw alkyloxy, Ci to Cw alkylamino, -OH, -OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , -C(O)OH, -C(O)OR 1 , -C(O)NH 2 , - C(OR 1 ,
  • the compounds of any one of Formulae (I) and (II) are selected from those wherein R 4 is independently either hydrogen or selected from: Ci to Cw alkyl, C3 to Cw cycloalkyl, C3 to Cw heterocycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, Ci to Cw alkyl-Ce to C14 aryl, Ci to Cw alkyl-C2 to C9 heteroaryl, Ci to Cw alkyl-Cs to Cw cycloalkyl, Ci to Cw alkyl-Cs to Cw heterocycloalkyl, Ci to Cw alkyloxy, Ci to Cw alkylamino, -OH, -OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , -O(CO)H, -O(CO)R 1 , -NH(CO)H, - NH(CO)R 1 , -NR 1 (
  • the compounds of any one of Formulae (I) and (II) are selected from those wherein R 4 is independently either hydrogen or selected from: Ci to C alkyl, C3 to C10 cycloalkyl, C3 to C10 heterocycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, Ci to Cw alkyloxy, Ci to Cw alkylamino, -OH, -OR 1 , -NH 2 , -NHR 1 , -NR 1 2 , Ce to C14 aryl optionally substituted with one or more R 2 group, or C2 to C9 heteroaryl optionally substituted with one or more R 2 group; preferably -OH; wherein R 1 is independently selected from: Ci to Cw alkyl, C3 to Cw cycloalkyl or C 2 to Cw alkenyl; wherein R 2 is independently selected from: Ci to Cw alkyl, -OH, -NH 2 , -OC1 to
  • the compounds of any one of Formulae (I) and (II) are selected from those wherein R 4 is independently either hydrogen or -OMe. It is preferred that the R group(s) and/or the R 4 groups(s) where they are other than hydrogen present on the benzoxazine ring(s) of compounds of any of Formulae (I), (II) and/or (III) are activating groups.
  • the activating properties of an activating group derive from their ability to donate electrons into an aromatic system, thus enhancing its affinity towards electrophiles, i.e. activating groups are electron donating groups.
  • the degree of electron donation of an electron donating group is proportional to its strength as an activating group.
  • K is the ionisation constant for benzoic acid in water at 25 °C and K x is the ionisation constant in water at 25 °C for a benzoic acid substituted with the electron donating group in question
  • o is the Hammett substituent constant, the more negative the Hammett substituent constant is, the more electron donating the substituent is, and therefore the stronger an activating group the substituent is.
  • the Hammett substituent constant can thus be used to measure the strength of an activating group.
  • the Hammett substituent constant of a substituent will differ depending on its position on the benzoic acid (e.g. -para, -meta or -ortho), the -para, -meta and -ortho Hammett substituent constants thus represent the activating effect the substituent has on the position -para, -meta or -ortho to the substituent, respectively.
  • Hammett substituent constants for substituents at the -ortho position cannot be accurately experimentally calculated due to the interference of steric effects.
  • -ortho Hammett substituent constants can be estimated using density functional theory and are found to closely correspond to the -para Hammett substituent constants.
  • Hammett substituent constants of an electron donating group at the -meta position tend to be significantly smaller than those at the -para and -ortho positions, which gives rise to the preferentially -ortho and - para regioselective directing effects of activating groups.
  • -Meta Hammett substituent constants are thus of little relevance to electrophilic aromatic substitution.
  • the Hammett substituent constant (a) herein refers to the Hammett substituent constant of the substituent in question at the -para position, which is approximately equivalent to the Hammett substituent constant at the -ortho position and corresponds to the increase in reactivity of the aromatic ring with regard to electrophilic aromatic substitution at both the -para and -ortho positions. As would be appreciated, a more negative Hammett substituent constant corresponds to an increase in reactivity.
  • Table 3 provides examples of Hammett substituent constants, as reported by Hammett. P, The Effect of Structure upon the Reactions of Organic Compounds. Benzene Derivatives, J. Am. Chem. Soc., 1937, 59, 1, 96-103 and Hansch. C et al A Survey of Hammett Substituent Constants and Resonance and Field Parameters, Chem. Rev., 1991 , 91, 165-195, as well as Hansch. C, Leo. A, Substituent constants for correlation analysis in chemistry and biology, New York NY: Wiley, 1979. As described hereinabove, Hammett Substituent constants reported in Table 3 are the para Hammett Substituent Constants.
  • the compounds of any one of Formulae (I), (II) and (III) are selected from those wherein R is selected from a substituent having a Hammett substituent constant (a) of less than zero, more preferably less than -0.050, even more preferably less than -0.100, most preferably less than -0.200.
  • R is selected from a substituent having a Hammett substituent constant (a) of less than zero, more preferably less than -0.050, even more preferably less than -0.100, most preferably less than -0.200.
  • the compounds of any one of Formulae (I) and (II) are selected from those wherein one, and preferably both, R 4 group(s) is/are selected from a substituent having a Hammett substituent constant (a) of less than zero, more preferably less than -0.050, even more preferably less than -0.100, most preferably less than - 0.200.
  • R 4 group(s) is/are selected from a substituent having a Hammett substituent constant (a) of less than zero, more preferably less than -0.050, even more preferably less than -0.100, most preferably less than - 0.200.
  • Unsubstituted furfural is a particularly desirable feedstock due to its low toxicity and abundant availability from natural sources.
  • Related furan 2-carbaldehydes are also derivable from natural sources and thus also desirable chemical feedstocks, in particular 5-(Hydroxymethyl)-2-furaldehyde, 5-(methoxymethyl)-2-furaldehyde, and 5-methy-2- furfuraldehyde are preferred furfuraldehydes useful in the present invention.
  • Unsubstituted furfural is the most preferred.
  • the compounds of any one of Formulae (I), (II) and (III) are selected from those wherein R 3 is independently selected from: Ci to Ce alkyl, Ci to Ce alkoxy, Ci to C 6 alkyloxy, and -OH, preferably -CH 3 , -CH 2 OH, or -CH 2 OCH 3 .
  • each R 6 group of compounds (II) and/or (III) is independently selected from: -H, -OH, Ci to C 2 o alkyl, C 3 to C 2 o cycloalkyl, C 3 to C 2 o heterocycloalkyl, C 2 to C 2 o alkenyl, C 2 to C 2 o alkynyl, Ci to C 2 o alkyloxy, Ci to C 2 o alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R 6 is optionally substituted with one or more R 7 groups; wherein R 7 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C 3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR 1
  • the compounds of any one of Formulae (II) and (III) are selected from those wherein R 6 is independently selected from: -H, -OH, Ci to C20 alkyl, C 3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R 6 is optionally substituted with one or more R 7 groups; wherein R 7 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR 1 , - NH
  • the compounds of any one of Formulae (II) and (III) are selected from those wherein R 6 is independently selected from: H, -OH, Ci to C10 alkyl, C3 to C10 cycloalkyl, C 3 to C heterocycloalkyl, C 2 to C alkenyl, C 2 to C alkynyl, Ci to C alkyloxy, Ci to C10 alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R 6 is optionally substituted with one or more R 7 groups; wherein R 7 is independently selected from: Ci to Cw alkyl, Ci to Cw haloalkyl, C3 to Cw cycloalkyl, C3 to Cw heterocycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, Ci to Cw alkyloxy, Ci to Cw alkylamino, -OH, -OR 1 , - NH 2 , -N
  • the compounds of any one of Formulae (II) and (III) are selected from those wherein R 6 is independently selected from: H, -OH, Ci to C20 alkyl, C3 to C20 cycloalkyl, C 3 to C20 heterocycloalkyl, C 2 to C20 alkenyl, C 2 to C20 alkynyl, Ci to C20 alkyloxy, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R 6 is optionally substituted with one or more R 7 groups; wherein R 7 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C 20 alkyloxy, -OH, -OR 1 , -NR 1 2 , -C(O)OR 1 , -C(O)NH 2
  • the compounds of any one of Formulae (II) and (III) are selected from those wherein R 6 is independently selected from: -H, -OH, Ci to C10 alkyl, C3 to C10 cycloalkyl, C3 to C10 heterocycloalkyl, C2 to C10 alkenyl, C2 to C10 alkynyl, Ci to C10 alkyloxy, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R 6 is optionally substituted with one or more R 7 groups; wherein R 7 is independently selected from: Ci to C10 alkyl, Ci to C10 haloalkyl, C3 to C10 cycloalkyl, C3 to C10 heterocycloalkyl, C2 to C10 alkenyl, C2 to C10 alkynyl, Ci to C10 alkyloxy, -OH, -OR 1 , -NR 1 2 , -C(O)OR 1 , -C(O)NH
  • the compounds of any one of Formulae (II) and (III) are selected from those wherein R 6 is independently selected from: H, -OH, Ci to C20 alkyl, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R 6 is optionally substituted with one or more R 7 groups; wherein R 7 is independently selected from: Ci to C20 alkyl, -OH, -OR 1 , -NR 1 2 , - NO 2 , -CN, -F, -Cl, -Br, and -I.
  • the compounds of any one of Formulae (II) and (III) are selected from those wherein R 6 is independently selected from: -H, Ci to C10 alkyl, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R 6 is optionally substituted with one or more R 7 groups; wherein R 7 is independently selected from: Ci to C10 alkyl, -OH, -OR 1 , -NR 1 2 , -NO2, -CN, -F, -Cl, -Br, and -I.
  • the compounds of any one of Formulae (II) and (III) are selected from those wherein, R 6 is a phenyl group.
  • the compounds of any one of Formulae (II) and (III) are selected from those wherein, both R 6 groups are the same. In other embodiments, the compounds of any one of Formulae (II) and (III) are selected from those wherein, both R 6 groups are the different.
  • the present invention also provides processes for synthesising the compounds of formulae (I), (II) and (III).
  • Each of the one or more phenolic compounds has an unsubstituted position ortho to the phenolic -OH and at least one other unsubstituted position.
  • R 4 When R 4 is hydrogen, the R 4 may be said other unsubstituted position. In this case, when R 4 is hydrogen 3 other positions are available for substitution and thus x may be 0, 1 , 2 or 3.
  • R 4 When R 4 is other than hydrogen, another position must be said other unsubstituted position. In this case, when R 4 is other than hydrogen 2 other positions are available for substitution and thus x may be 0, 1 or 2.
  • a combination of two or more phenolic compounds may be used to form an asymmetric difunctional benzoxazine, or a single phenolic compound may be used to form a symmetrical difunctional benzoxazine.
  • At least one phenolic compound must be orthosubstituted, i.e. , have an R 4 group other than hydrogen at the ortho position relative to the phenolic -OH group.
  • each of the one or more phenolic compounds has an R 4 group other than hydrogen at the ortho position relative to the phenolic -OH group, and is unsubstituted at one or more of the 3-, 4- or 5-positions relative to the phenolic -OH group.
  • a single phenolic compound is used, wherein the single phenolic compound has an R 4 group other than hydrogen at the ortho position relative to the phenolic -OH group, and is unsubstituted at one or more of the 3-, 4- or 5-position relative to the phenolic -OH group.
  • the exact ratio of diamine to phenolic compound to furfuraldehyde used in this process is 1 :2:4, differing molar ratios of these precursors may be utilised in some embodiments.
  • the molar ratio of the diamine to the at least one furfuraldehyde is from 1 :2 to 1 :20, preferably from 1 :3 to 1 :10, more preferably from 1 :4 to 1 :8; and/or wherein the molar ratio of the diamine to the at least one phenolic compound is from 1 :1 to 1 :5, preferably from 1 :1.5 to 1 :4, more preferably from 1 :2 to 1 :3.
  • the diamine is contacted with the at least one furfuraldehyde prior to the addition of the at least one phenolic compound.
  • the diamine is contacted with a portion of the at least one furfuraldehyde prior to the addition of the at least one phenolic compound, wherein the remaining furfuraldehyde is added after and/or simultaneously to addition of the at least one phenolic compound.
  • the diamine is contacted with the at least one phenolic compound and the at least one furfuraldehyde simultaneously.
  • two different phenolic compounds are added separately. This embodiment is suited to the preparation of asymmetrical benzoxazines.
  • only one phenolic compound is added. This embodiment is suited to the preparation of symmetrical benzoxazines.
  • Each benzene ring of the bisphenol compound has an unsubstituted position ortho to the phenolic -OH and at least one other unsubstituted position.
  • R 4 When R 4 is hydrogen, the R 4 may be said other unsubstituted position. In this case, when R 4 is hydrogen, or when R 4 is a direct bond to L 2 , 2 other positions are available for substitution and thus y may be 0, 1 or 2.
  • R 4 is other than hydrogen, another position must be said other unsubstituted position. In this case, when R 4 is other than hydrogen or a direct bond to L 2 , 1 other position is available for substitution and thus y may be 0 or 1 .
  • the bisphenol compound is substituted with one R 4 group other than hydrogen at an ortho-position relative to the phenolic -OH on each benzene ring of the bisphenol compound, more preferably both, R 4 group(s) is/are the same.
  • this process yields a compound of formula (II) when a bisphenol compound precursor is used, a compound of formula (III) when a 1 ,3-benzene-diol is used.
  • the primary amine has one substituent defined herein as R 6 .
  • the primary amine becomes incorporated into the benzoxazine ring to provide the benzoxazine nitrogen substituted with R 6 .
  • a single primary amine may be used so that both R 6 groups are the same, or multiple primary amines may be used so that both R 6 groups are different from each other.
  • the molar ratio of the bisphenol compound or benzenediol to the at least one furfuraldehyde is from 1 :2 to 1 :20, preferably from 1 :3 to 1 :10, more preferably from 1 :4 to 1 :8; and/or wherein the molar ratio of the bisphenol compound or benzenediol to the at least one primary amine is from 1 :1 to 1 :5, preferably from 1 :1 .5 to 1 :4, more preferably from 1 :2 to 1 :3.
  • the at least one primary amine is contacted with the at least one furfuraldehyde prior to the addition of the bisphenol compound or benzenediol.
  • the at least one primary amine is contacted with a portion of the at least one furfuraldehyde prior to the addition of the bisphenol compound or benzenediol, wherein the remaining furfuraldehyde is added after and/or simultaneously to addition of the bisphenol compound or benzenediol, respectively.
  • the at least one primary amine is contacted with the bisphenol compound or benzenediol, and the at least one furfuraldehyde simultaneously.
  • two different primary amines are added separately. This embodiment is suited to the preparation of asymmetrical benzoxazines.
  • the compounds of the present invention may be prepared over a range of different temperatures that the skilled person would be familiar with from conventional Mannich chemistry and conventional benzoxazine preparations.
  • the compounds of the present invention may, for instance, be prepared at room temperature and the process may be accelerated by heating and/or the use of a catalyst.
  • the temperature of the reaction is between 25 °C and 150 °C, more preferably the temperature of the reaction is between 40 °C and 100 °C.
  • the reaction may optionally be catalysed wherein either: the catalyst is i) an acid catalyst, for example an acid catalyst selected from HCI, trifluoroacetic acid, methane sulphonic acid, p-toluenesulphonic acid, trifluoromethanesulphonic acid, benzoic acid and mixtures thereof; or ii) a basic catalyst, for example a basic catalyst selected from NaOH, Na 2 CO3, triethylamine, triethanolamine and mixtures thereof.
  • an acid catalyst for example an acid catalyst selected from HCI, trifluoroacetic acid, methane sulphonic acid, p-toluenesulphonic acid, trifluoromethanesulphonic acid, benzoic acid and mixtures thereof
  • a basic catalyst for example a basic catalyst selected from NaOH, Na 2 CO3, triethylamine, triethanolamine and mixtures thereof.
  • a broad range of organic solvents are suitable for use in the reaction, for example MeCN, benzene, methanol, ethanol, IPA, butanol, chloroform, DCM, diethyl ether, DMF, dioxane, ethyl acetate, petroleum ether, kerosine, pentane, hexane, heptane, MTBE, NMP, THF, toluene, xylene and mixtures thereof.
  • Toluene is the most preferred solvent for use in the reaction.
  • the Mannich reaction and benzoxazine cyclisation reaction produce water.
  • the skilled person is capable of employing methods of removing water produced during the reaction along with any solvent used, in order to yield the final product, such as boiling, distillation, vacuum distillation, azeotroping, dean stark, precipitation etc.
  • the present invention comprises a resin composition comprising a benzoxazine compound of formula (I), (II) or (III), as described herein.
  • Any suitable organic solvent may be used as a solvent or diluent in a resin composition of the present invention, for example MeCN, benzene, methanol, ethanol, IPA, butanol, chloroform, DCM, diethyl ether, DMF, dioxane, ethyl acetate, petroleum ether, kerosine, pentane, hexane, heptane, MTBE, NMP, THF, toluene, xylene and mixtures thereof.
  • Toluene is a particularly suitable solvent or diluent for ortho-substituted difunctional benzoxazine compounds and resins thereof of the present invention.
  • solvent or diluent for ortho-substituted difunctional benzoxazine compounds and resins thereof of the present invention.
  • thermoset polymer matrixes such as fibre-reinforced plastic, comprising fibrous materials, for example aramid fibre, basalt, wood fibre, glass fibre, carbon fibre or flax.
  • the material to be reinforced is contacted with an ortho-substituted difunctional benzoxazine compound of the present invention, or resin thereof, to form a pre-preg, followed by curing of the ortho-substituted difunctional benzoxazine compound by self-polymerisation to form cross-linkages, to thereby reinforce the material.
  • a coating may be formed on a material by contacting the surface of the material with an ortho-substituted difunctional benzoxazine compound of the present invention, or resin thereof, followed by allowing self-polymerisation of the ortho-substituted difunctional benzoxazine compound.
  • Selfpolymerisation of the ortho-substituted difunctional benzoxazine compound can occur at ambient temperature or elevated temperature, with or without a catalyst or co-reactant.
  • Self-polymerisation of the ortho-substituted difunctional benzoxazine also allows the compounds of the invention to be used for the purpose of liquid moulding, film adhesives, composite construction, material bonding and repair, as in the case of conventional benzoxazines.
  • the properties of the ortho-substituted difunctional benzoxazine compounds also find particular utility in resin formation, resin polymerisation, and formation of reinforced materials such as fibre-reinforced plastic.
  • the polymer formed by self-polymerisation of the ortho-substituted difunctional benzoxazine compounds of the present invention has exposed phenol groups, due to the benzoxazine ring opening reaction.
  • An epoxy-based resin may be applied to, or incorporated into, an ortho-substituted difunctional benzoxazine compound of the present invention, or resin composition thereof, or a pre-preg or reinforced material formed therefrom, in order to provide further curing, hardening, cross-linkage and reinforcement.
  • Hybridisation with epoxy-based resins may be used to increase the Tg of a benzoxazine thermoset, or material comprising or reinforced with the same.
  • epoxy-based resins suitable for use in the present invention include polyglycidyl ethers of polyhydric phenols, epoxidised novolacs or similar glycidated polyphenolic resins, glycidated bisphenols, such as glycidated bisphenol A or F, or halogenated (e.g. chlorinated or fluorinated) analogues thereof; polyglycidyl ethers of alcohols, glycols or polyglycols, and polyglycidyl esters of polycarboxylic acids.
  • Preferred examples of epoxy resins are polyglycidyl ethers of a polyhydric phenol.
  • Polyglycidyl ethers of polyhydric phenols can be produced, for example, by reacting an epihalohydrin with a polyhydric phenol in the presence of an alkali.
  • suitable polyhydric phenols include: 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A); 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane; 1 ,1-bis(4-hydroxyphenyl) ethane; 1 ,1- bis(4-hydroxyphenyl) isobutane; bis(2-hydroxy-1 -naphthyl) methane; 1 ,5- dihydroxynaphthalene; 1 ,1-bis(4-hydroxy-3-alkylphenyl) ethane and the like.
  • preferred epoxy resins that may be used include EPI LOK 60-600.
  • the reinforced material may be prepared by applying a layer of a resin as defined herein, onto a bottom film carrier layer. Glass fibres, carbon fibres, flax, or any other fibrous material as the reinforcement may then then be applied to the upper surface of the resin on the film carrier. A further layer of the resin is applied to sandwich the fibrous material between the layers. A top film may be applied to the upper layer. The resulting layered composition may subsequently be compressed as part of forming the reinforced material.
  • the reinforced material of the present invention may be formed from a sheet-molding compound (SMC) comprising a compound according to formula (I), (II) or (III), or resin thereof, and fibrous material as defined above.
  • SMC sheet-molding compound
  • Methods of preparing such SMC materials are known in the art and can be readily adapted for use in preparing reinforced materials as defined herein.
  • the SMC material may further include additives selected from hardeners, accelerators, fillers, pigments, fire retardants and/or any other components, as required.
  • the sheet-form polymeric material may also include melamine, which is useful as a fire retardant.
  • the SMC may include a further thermoplastic material.
  • the reinforced material of the present invention may comprise a number of layers, the layers may be joined together in a variety of ways. For instance, where air-tight sealing coating material comprising an elastomer is used, the same coating material may be used to bond the first insulating layer to one or more adjacent layers of the layered composite material panel.
  • SMC material comprising a compound according to formula (I), (II) or (III) may be bonded to one or more adjacent layers during curing of the reinforced material, for instance using heat and/or pressure.
  • a variety of known adhesives may be used to bond the individual layers of the layered composite material panel together.
  • pressure is applied to the layered composite material during the bonding step so as to ensure good adhesion of the layers.
  • one or more layers comprises a compound according to formula (I), (II) or (III), or resin thereof, (e.g. as part of an SMC material) the application of pressure may also assist in the curing of the compound according to formula (I), (II) or (III), or resin thereof.
  • the flask was heated to 85 °C and held 1 hour. It was then azeotroped up to 110 °C removing approximately 72 grams water formed during the reaction. The flask was then reconfigured for vacuum distillation and distilled under vacuum to 120 °C recovering the toluene [182 grams recovered] to yield Compound C in a liquid form.
  • R 8 is independently selected from a -C15H31 straight chain alkyl group, -C15H29 straight chain alkenyl group, -C15H27 straight chain alkenyl group, and -C15H25 straight chain alkenyl group.
  • Example 5 Comparison of physical properties against known benzoxazines Table 4. Comparison of the properties of Compounds A to D with those of a conventional benzoxazine (Cardarez R111)
  • Furan derived benzoxazines also have advantageously low viscosities which provides for easier handling during preparation, storge and use, as well as reducing the need for diluents or solvents in a resin composition.
  • Conventional benzoxazine, Cardarez R111 (RTM) is a solid, and as such no directly comparable viscosity measurement can be taken at 25 °C.
  • Figure 1 demonstrates the viscosity (mPa s) v temperature (°C) of Cardarez R111 (RTM), using ASTM D4287-00(2019). Due to the solid nature of Cardarez R111 (RTM) viscosity measurements must be taken at high temperatures in order to melt the Cardarez R111 (RTM).
  • Figure 2 demonstrates viscosity (mPa s) development over time (hours) of Cardarez R111 (RTM) at 100 °C, 120 °C and 140 °C.
  • Cardarez R111 (RTM) is a thermoset and reactivity rate [devoid of catalysis or co-polymer] is temperature dependent and depicted in Figure 2.
  • Cardarez R111 (RTM) stability evaluation undertaken with a 50 gram mass in all cases. Viscosity figures quoted are evaluated and detailed at the temperature that the material was held. Viscosity evaluation was undertaken using a cone and plate viscometer [CPV] and the test temperature for viscosity evaluation is the same as the designated stability test temperature[s].
  • CPV cone and plate viscometer
  • each of the furan derived benzoxazines exhibits a significantly shorter gel time (as measured by ASTM D3056-14(2018)) in comparison to conventional benzoxazine, Cardarez R111. Relatively slow curing times are a known deficiency associated with conventional benzoxazines.
  • Furan derived benzoxazines provide surprising improvements in gel time, indicating that furan derived benzoxazines exhibit greater reactivity, leading to improvements in process efficiency in applications where benzoxazines are employed.
  • Figure 3 and Figure 4 compare the gel-time reactivity (gel time I minutes) undertaken with a 1 gram mass of Cardarez R111 (RTM) and Compound A, respectively. Cure determination by plate gel at specified temperatures (°C). The gel time is representative of the progress of curing by self-polymerisation. No catalyst or co-reactant was used.
  • Figures 3 and 4 are in contrast to the plate gel data (ASTM D3056-14(2018)) shown in Table 4.
  • the ASTM D3056-14(2018) method used in Table 4 uses a catalyst, whereas the experiments shown in Figures 3 and 4 were performed in the absence of a catalyst.
  • Cardarez R111 is less amenable to catalysis as compared to the furan derived benzoxazines which are particularly well suited to catalysed curing.
  • the addition of the catalyst to furan derived benzoxazines provides for a much greater reduction in gel time. Without being bound to any particular theory, it is expected that the furan groups on the benzoxazine ring assist in co-ordinating the catalyst to bring it into closer proximity with the benzoxazine ring to stimulate ring opening.
  • Figure 5 demonstrates the Tg development (°C) of thermosets cured at 180 °C vs time (minutes) for a Compound A thermoset and a comparative Cardarez R111 (RTM) thermoset.
  • Compound A provides superior Tg development over time and thus is able to produce thermosets of a higher Tg once sufficient cure time is applied.
  • cure times of 90 minutes or greater are commonly used in the art for various applications.
  • Figure 7 demonstrates the Compound A viscosity build (Pa- s) vs time (minutes) at 60 °C and 100 °C, with 5% ferric chloride catalyst.
  • the 5% ferric chloride allows for curing to take place at significantly lower temperatures.
  • Cardarez R111 (RTM) is a solid and so must be heated to a high temperature and melted before a catalyst may be mixed with the Cardarez R111 (RTM).
  • This means that the catalysis of a solid benzoxazine such as Cardarez R111 (RTM) requires addition of the catalyst at high temperature followed by mixing before it can be applied in the desired use. This risks premature curing and causes difficulty in handling and storage.
  • the furan derived benzoxazines are liquids at room temperature (e.g. 25 °C) and so may be mixed with a catalyst at comparatively low temperature without the risk of premature curing.
  • the viscosity build is very slow at 60 °C, which demonstrates the utility for storage and handling of Compound A pre-mixed with catalyst at low temperature. Additionally, rapid curing can nevertheless be achieved, once desired, by heating to a higher temperature, e.g. 100 °C. This is not possible for a solid benzoxazine which cannot be pre-mixed with a catalyst prior to melting at high temperature.
  • a prepreg composite material in which a reinforcement fibre is preimpregnated with a resin composition comprising Compound A.
  • Compound A is a viscous liquid and can be commercially processed via hot-melt or solvated and processed through conventional methods.
  • the material was used to make a composite part produced by a standard prepreg stage and pressing at a consolidation pressure 80 bar/cm 2 .
  • Each composite part was generated using glass fabric with fibre density - binder ratio of 60:40 by weight: E-glass fabric, Style 7628 Finish phenolic compatible.
  • the cure schedule employed was heating at a rate of 8 °C/minute from RT up to 180 °C, followed by holding at 180 °C for 3 hours under a consolidation pressure of 80 bar/cm 2 .
  • the resultant composite panel had excellent surface appearance, free from defects such as porosity.
  • the resultant product is suitable for use with a variety of reinforcements finding application in numerous areas including but not limited to, aircraft interiors and flooring, aerospace components, cargo liners, automotive parts, ballistic components, electrical laminates, fire resistant laminates and panels, sporting goods, train components, and tooling.
  • Example 7 Sample laminate properties The physical properties, and chemical resistance properties of a reinforced material according to Example 6 were measured and compared to a comparative reinforced material produced by the same method of Example 6 using a known benzoxazine (Cardarez R111 (RTM))
  • the reinforced material made with compound A has comparable strength and flexibility to that of a reinforced material produced with Cardarez R111 (RTM).
  • the reinforced material made with Compound A is also shown to have a high degree of fire resistance.
  • the reinforced material made with Compound A also has comparable chemical resistance to that of a reinforced material produced with Cardarez R111 (RTM).
  • a very similar degree of weight change is generally observed as a result of chemical exposure.
  • the present invention thus allows for the provision of reinforced materials comprising a high degree of bio-carbon from renewable stocks without negatively impacting the physical properties or chemical resistance.
  • a solution of BCI3 octyl dimethylamine complex in ethanol was added to the solution of Compound A and mixed for 5 minutes with a slow rate agitator to form a homogenous solution without introducing air.
  • the combined material had a viscosity of 1180 mPa s at 25 °C.
  • the gel times of Compound A in combination with concentrations of 1 , 1.5 and 2 PHR of BCI3 octyl dimethylamine complex at 160 °C were found to be approximately 320 seconds, 180 seconds, and 60 seconds, respectively. As would be expected, increasing the concentration of catalyst decreases the gel time, and these results are shown graphically in Figure 8.
  • a combined solution of 90% Compound A and 10% acetone combined with 1 PHR of BCh octyl dimethylamine complex was used to prepare a prepreg material.
  • the combined solution was applied via a conventional process of impregnation of an E-glass fabric cloth (Style 7628 - finish phenolic compatible) having a fibre density of 70 % by weight, with the solution followed by driving off the solvent and partially advancing the resin to form a partially cured state or state of advancement/cure that allows the sheets to have sufficient strength so that they can be laid up as a laminate (prepreg layer stack), but not so advanced that they are rigid or fail to flow when pressed under heat and pressure.
  • E-glass fabric cloth Style 7628 - finish phenolic compatible
  • the sheets were cut and then aligned so they can be consolidated, and the cure schedule employed was heating at a rate of 8 °C/minute up to 170 °C, followed by heating at 170 °C for two hours, followed by heating at a rate of 8 °C/minute up to 190 °C under a consolidation pressure of 80 bar/cm 2 .
  • the resulting laminate had the following properties:
  • Flammability 5mm VO** UL 94 * (d 25mm) denotes that both electrodes have a 25 mm diameter.
  • ** VO Burning stops within 10 seconds after two applications of ten seconds each of a flame/vertical bum to a test bar. No flaming drips are observed.
  • furan derived benzoxazines are highly compatible with curing catalysts and may readily provide reinforced materials having desirable properties derived from furan derived benzoxazines, prepared with the assistance of a curing catalyst.
  • An ortho-substituted benzoxazine compound was prepared in order to establish that an ortho-substituted benzoxazine can provide suitable polymerisation properties.

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Abstract

The invention relates to a class of ortho-substituted difunctional benzoxazine compounds useful as curatives, as well as methods of preparation, and uses thereof. The ortho-substituted difunctional benzoxazine compounds comprise two benzoxazine rings, each disubstituted with two furfuryl groups. The two benzoxazine rings may be attached via a hydrocarbyl linker or two benzoxazine moieties may share a common benzene group. The ortho-substituted difunctional benzoxazine compounds are capable of self-polymerisation via a ring opening reaction which allows them to act as a curative. In one aspect, the present invention provides a compound of formula (I) below.

Description

ORTHO-SUBSTITUTED DIFUNCTIONAL BIO-BENZOXAZINE COMPOUNDS, PREPARATION METHODS AND USES THEREOF
The invention relates to a class of ortho-substituted benzoxazine compounds useful as a curative and having a high degree of biological based carbon content. In particular the invention is directed to a class of ortho-substituted difunctional benzoxazine compounds comprising two benzoxazine rings, each di-substituted with furfuryl groups, a resin curative composition comprising the benzoxazine compound, processes for preparing the benzoxazines and uses thereof.
BACKGROUND OF THE INVENTION
A benzoxazine is chemical compound comprising a bicyclic ring system containing an oxygen atom and a nitrogen atom within a heterocyclic oxazine ring that is directly fused to a benzene ring. There are several isomers of benzoxazine with the nitrogen and oxygen at differing positions that may be generically referred to as “benzoxazines”, in addition to compounds having differing levels of saturation in the oxazine ring that may also go by the name “benzoxazine”. In this application, the term “benzoxazine” refers to 3,4-dihydro-2/-/-1 ,3-benzoxazine, which is the benzoxazine monomer most useful in the production of benzoxazine based polymers, the structure of which is shown below.
Figure imgf000002_0001
3,4-dihydro-2/-/-1 ,3-benzoxazine structure
In this application, the term “ortho-substituted” or any variation thereof, in the context of an ortho-substituted benzoxazine refers to the position adjacent to the carbon atom bonded to the benzoxazine oxygen, the structure of which is shown below with the ortho-substituent denoted as R4.
Figure imgf000003_0001
Ortho-substituted benzoxazine structure
Benzoxazines are capable of undergoing ring opening on heating without the need of catalysts and without emitting volatiles, leading to self-polymerisation, which is useful for both providing thermosets and also in curing to reinforce other materials. The benzoxazine polymers formed therefrom are the products of interest for providing suitable molecular weight structures that confer desirable protective properties once fully cured.
The synthesis of benzoxazine dates back over 60 years although the low molecular weight species at that time could not offer the performance characteristics now attributed to, and associated with, the polymeric benzoxazines that form the basis of the coating and matrix systems employed today. Commercially available benzoxazines are generally provided by reaction of i) a phenolic compound, which may be phenol, bisphenol, or a substituted derivative thereof, ii) formaldehyde which comes in different concentrations as an aqueous solution of the gas or in polymerized form as paraformaldehyde, and iii) a primary amine which contains one or multiple primary amine groups, but may contain additional secondary or tertiary amine groups and/or other functional groups.
The process to synthesise the benzoxazine structure is a Mannich reaction between the primary amine and the aldehyde liberating water to form an iminium ion, followed by cyclisation with the phenolic compound and a second equivalent of aldehyde to form the oxazine ring. The Mannich reaction to form a benzoxazine ring, followed by selfpolymerisation, is shown in Scheme 1 below.
Scheme 1 : Mannich Synthesis and Self-Polymerisation of Generic Benzoxazine
Figure imgf000004_0001
The most desirable benzoxazine polymers for coating and matrix applications are derived from difunctional benzoxazines. The resultant products have repeating units of a higher molecular weight and form polymers with a higher degree of cross-linkage. A difunctional benzoxazine may also comprise only one benzene ring that is fused to two separate oxazine rings, providing two benzoxazine moieties on a shared benzene ring.
For this reason, bisphenol A is a well-known choice of phenolic compound for this purpose as it comprises two phenol groups capable of transformation into benzoxazines. Cardarez R111 (RTM), depicted below, is a known bisphenol A based benzoxazine useful for providing polymers with a high glass transition temperature (Tg), low water absorption, excellent physical electrical performance, along with excellent fire resistance properties. Like other conventional benzoxazines, Cardarez R111 (RTM) forms a solid resin when prepared.
Figure imgf000004_0002
Cardarez R111 (RTM)
However, a disadvantage of conventional benzoxazines, is that the formaldehyde from which they are prepared is a highly toxic and carcinogenic chemical that is synthesised by energy intensive industrial processes. Furthermore, as mentioned above, benzoxazines formed by these methods tend to be solid resins. The process temperature and the melting point of the product also results in increased viscosity and subsequent difficulty in management or the process. In particular, increased viscosity can also generate problems when processing as a solvent free matrix or coating system. Furthermore, conventional benzoxazine resins often suffer from slow gel times, reducing the efficiency of processes such as the formation of matrixes or coatings. The present invention is based on the surprising discovery of a new class of orthosubstituted difunctional benzoxazine compounds that are liquids under standard conditions (e.g. at 25 °C and 100 KPa), but provide thermosets with comparable properties, such as viscosity and Tg, whilst also providing greatly increased bio-carbon content and obviating the need for synthesis from formaldehyde. Resin compositions formed from the new class of ortho-substituted difunctional benzoxazine compounds of the present invention also present superior gel times, converting to a solid material more rapidly than conventional benzoxazine resins.
The bio-carbon content of the benzoxazines of the present invention is greatly increased by replacing the formaldehyde precursor with furfuraldehyde, also known as furfural. Furfural is an inexpensive, renewable and naturally occurring feedstock derived from the dehydration of sugars, and occurs in a variety of agricultural by-products, including corncobs, oats, wheat bran, and sawdust.
Furfural has been used in the synthesis of aryloxazines in the pharmaceutical industry, in particular, napthoxazines have been investigated for potential medicinal properties. See M. S. Al Ajely and A M Noori, Synthesis of New Oxazin Compounds Derived from Furfural. Chalcons and Schiff base, LOJ pharmacol., 2019, 1(3), 66-71. and S. A. Ozturkcan and T Zuhal, Synthesis and Characterizations of New 1,3-Oxazine Derivatives, J. Chem. Soc. Pak., 2011 , 33(6), 939-944.
D. R. de Oliveira, et al, Synthesis and Polymerization of Naphthoxazines Containing Furan Groups: An Approach to Novel Biobased and Flame-Resistant Thermosets, Int. J. Polym. Sci., 2018, 2018, 1-13, describe the use of solid furfuryl substituted napthoxazines, prepared from furfurylamine or furaldehyde precursors, as monomers for the production of polymeric materials. However, the polymer repeating unit of this disclosure is formed from a single napthoxazine ring.
The ortho-substituted difunctional benzoxazine of the present invention is useful in forming a polymer comprising repeating units formed from an ortho-substituted difunctional benzoxazine to provide a high degree of cross-linkage and a high biocarbon based content. Surprisingly, the new class of furfural derived ortho-substituted difunctional benzoxazines of the present invention have also been found to typically be in liquid form at standard conditions (e.g. 25 °C and 100 kPa), which provides numerous advantages in handling, application and use in resin compositions over conventional solid benzoxazine resins. For example, liquid benzoxazines may be combined with a curing catalyst at low temperature (below which reaction of the benzoxazine can be expected) without the risk of unwanted or premature self-polymerisation. In contrast, a solid benzoxazine compound such as Cardarez R111 (RTM) must be melted before mixing with a catalyst is possible, thus risking undesired self-polymerisation due to the high temperature required for melting.
SUMMARY OF THE INVENTION
In one aspect, the present invention provides a compound of formula (I):
Figure imgf000006_0001
wherein each R group is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- C3 to C20 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1, -NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, - C(O)NHR1, -C(O)NR12, -O(CO)H, -O(CO)R1, -NH(CO)H, -NH(CO)R1, -NR1(CO)H, - NR1(CO)R1, -SH, -SR1, -SO2H, -SO2R1, -SO3R1, -SO3H, -SiR1 3, -NO2, -ON, -F, -Cl, -Br, - I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein each R1 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-C6 to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- C3 to C10 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkoxy, Ci to C20 alkylamino, C6 to C14 aryl, and C2 to C9 heteroaryl; wherein R2 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, -OH, -NH2, -OC1 to C20 alkyl, -NHC1 to C20 alkyl, -N(Ci to C20 alkyl)2, -NO2, -ON, -F, -Cl, -Br, and -I; wherein R3 is independently selected from: Ci to Ce alkyl, Ci to Ce alkenyl, Ci to Ce alkoxy, Ci to Ce alkyloxy, -C(O)OH, -C(O)O-Ci to Ce alkyl, Ci to Ce alkyl-(O)O-H, Ci to Ce alkyl-(O)O-Ci to Ce alkyl, and -OH; wherein R4 is independently either hydrogen or is selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-Cs to C20 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1 , -NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, - C(O)NHR1, -C(O)NR1 2, -O(CO)H, -O(CO)R1 , -NH(CO)H, -NH(CO)R1 , -NR1(CO)H, - NR1(CO)R1 , -SH, -SR1 , -SO2H, -SO2R1, -SO3R1, -SO3H, -SiR1 3, -NO2, -CN, -F, -Cl, -Br, - I, C6 to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; with the proviso that at least one R4 group is other than hydrogen; wherein L1 is a divalent hydrocarbyl linker comprising 1 to 50 carbon atoms; wherein x is independently 0, 1 , 2 or 3 when R4 is hydrogen, and x is independently 0, 1 or 2 when R4 is other than hydrogen; and wherein n is independently 0, 1 , 2 or 3.
In another aspect, the present invention provides a compound of formula (II):
Figure imgf000007_0001
(H) wherein each R group is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- C3 to C20 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1 , -NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, - C(O)NHR1, -C(O)NR12, -O(CO)H, -O(CO)R1 , -NH(CO)H, -NH(CO)R1 , -NR1(CO)H, - NR1(CO)R1 , -SH, -SR1 , -SO2H, -SO2R1, -SO3R1, -SO3H, -SiR1 3, -NO2, -ON, -F, -Cl, -Br, - I, C6 to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein each R1 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- Cs to C10 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkoxy, Ci to C20 alkylamino, C6 to C14 aryl, and C2 to C9 heteroaryl; wherein R2 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, -OH, -NH2, -OC1 to C20 alkyl, -NHC1 to C20 alkyl, -N(Ci to C20 alkyl)2, -NO2, -CN, -F, -Cl, -Br, and -I; wherein R3 is independently selected from: Ci to Ce alkyl, Ci to Ce alkenyl, Ci to Ce alkoxy, Ci to Ce alkyloxy, -C(O)OH, -C(O)O-Ci to Ce alkyl, Ci to Ce alkyl-(O)O-H, Ci to C6 alkyl-(O)O-Ci to C6 alkyl, and -OH; wherein R4 is a direct bond to L2; or R4 is independently either hydrogen or is selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-Cs to C20 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1, - NR1 2, -C(O)OH, -C(O)OR1 , -C(O)NH2, -C(O)NHR1, -C(O)NR12, -O(CO)H, -O(CO)R1, - NH(CO)H, -NH(CO)R1 , -NR1(CO)H, -NR1(CO)R1, -SH, -SR1 , -SO2H, -SO2R1, -SO3R1 , - SO3H, -SiR1 3, -NO2, -CN, -F, -Cl, -Br, -I, C6 to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; with the proviso that at least one R4 group is other than hydrogen; wherein R6 is independently a monovalent group selected from -H, -OH, or a hydrocarbyl group comprising 1 to 50 carbon atoms; wherein L2 is a direct bond, a divalent group selected from: C(O), O, S, S(O), S(O)2, or a hydrocarbyl linker comprising 1 to 50 carbon atoms; wherein y is independently 0, 1 , or 2 when R4 is hydrogen or is a direct bond to L2, and y is independently 0 or 1 when R4 is other than hydrogen or a direct bond to L2; and wherein n is independently 0, 1 , 2 or 3.
In yet another aspect, the present invention provides a compound of formula (III):
Figure imgf000009_0001
wherein R is selected from: Ci to C2o alkyl, Ci to C2o haloalkyl, C3 to C20 cycloalkyl, C3 to C2o heterocycloalkyl, C2 to C2o alkenyl, C2 to C2o alkynyl, Ci to C2o alkyl- Ce to Cu aryl, Ci to C2o alkyl-C2 to C9 heteroaryl, Ci to C2o alkyl-C3 to C2o cycloalkyl, Ci to C20 alkyl-C3 to C heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, - OR1, -NH2, -NHR1, -NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, -C(O)NHR1, -C(O)NR1 2, - O(CO)H, -O(CO)R1, -NH(CO)H, -NH(CO)R1, -NR1(CO)H, -NR1(CO)R1, -SH, -SR1, - SO2H, -SO2R1, -SO3R1, -SO3H, -SiR1 3, -NO2, -ON, -F, -Cl, -Br, -I, C6 to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein each R1 is independently selected from: Ci to C2o alkyl, Ci to C2o haloalkyl, C3 to C2o cycloalkyl, C3 to C2o heterocycloalkyl, C2 to C2o alkenyl, C2 to C2o alkynyl, Ci to C2o alkyl-Ce to C14 aryl, Ci to C2o alkyl-C2 to C9 heteroaryl, Ci to C2o alkyl- C3 to C10 cycloalkyl, Ci to C2o alkyl-C3 to C10 heterocycloalkyl, Ci to C2o alkoxy, Ci to C2o alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R2 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, -OH, -NH2, -OC1 to C20 alkyl, -NHC1 to C20 alkyl, -N(Ci to C20 alkyl)2, -NO2, -ON, -F, -Cl, -Br, and -I; wherein R3 is independently selected from: Ci to Ce alkyl, Ci to Ce alkenyl, Ci to Ce alkoxy, Ci to Ce alkyloxy, -C(O)OH, -C(O)O-Ci to Ce alkyl, Ci to Ce alkyl-(O)O-H, Ci to Ce alkyl-(O)O-Ci to Ce alkyl, and -OH; wherein R6 is independently a monovalent group selected from -H, -OH, or a hydrocarbyl group comprising 1 to 50 carbon atoms; and wherein n is independently 0, 1 , 2 or 3.
In still another aspect, the present invention provides a process for preparing a compound of formula (I) as described herein, said method comprising: i) providing a diamine NH2-L1-NH2 wherein L1 is as described herein; ii) adding at least one furfuraldehyde substituted with n R3 groups, and one or more phenolic compounds independently substituted by R4 at one ortho position relative to the phenolic -OH group and independently substituted with x R groups, with the proviso that each of the one or more phenolic compounds has an unsubstituted position ortho to the phenolic -OH and at least one other unsubstituted position, wherein R, R3, R4 and n are as described herein, and x = 0, 1 , 2, or 3, and wherein R4 in at least one of the one or more phenolic compounds is other than hydrogen; and iii) forming a compound of formula (I).
In a further aspect, the present invention provides a process for preparing a compound of formula (II) or (III) as described herein, said method comprising: i) providing: A) a bisphenol compound substituted with y R groups on each benzene ring and comprising a linker L2, and wherein the bisphenol compound is substituted with one R4 group which is other than hydrogen at an ortho-position relative to the phenolic -OH on one or each benzene ring of the bisphenol compound, with the proviso that each benzene ring of the bisphenol compound has an unsubstituted position ortho to the phenolic - OH and at least one other unsubstituted position; or B) a benzene-1 ,3-diol substituted with 1 R group at the 2-position; wherein R, R4, and L2 are as described herein, and y = 0, 1 or 2; ii) contacting the compound from step i) with at least one furfuraldehyde substituted with n R3 groups, and at least one primary amine substituted with one R6 group, wherein n, R3 and R6 are as described herein; and iii) forming a compound of formula (II) or (III).
In a yet further aspect, the present invention comprises a resin composition comprising a benzoxazine compound of formula (I), (II) or (III), as described herein.
In a still further aspect, the present invention provides the use of a benzoxazine compound of formula (I), (II) or (III), or a resin composition thereof, as described herein, to reinforce a material.
In another aspect, the present invention provides a method for preparing a reinforced material, said method comprising: a) contacting a material to be reinforced with a compound of formula (I), (II) or (III), or a resin composition thereof; and b) allowing said compound to self-polymerise to form a reinforced material.
In another aspect, the present invention provides a reinforced material prepared, or preparable, by the methods described herein.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 demonstrates the viscosity vs temperature of the comparative Cardarez R111 (RTM) benzoxazine;
Figure 2 demonstrates the viscosity development over time of comparative Cardarez R111 (RTM) benzoxazine at 100 °C, 120 °C and 140 °C;
Figure 3 demonstrates the gel-time reactivity vs temperature of comparative Cardarez R111 (RTM);
Figure 4 demonstrates the gel-time reactivity vs temperature of Compound A; Figure 5 demonstrates the Tg development of thermosets cured at 180 °C vs time for a compound A thermoset and a comparative Cardarez R111 (RTM) thermoset;
Figure 6 demonstrates the Tg development of Compound A during curing at 140 °C over 1 hour with 3%, 4% or 5% of a ferric chloride catalyst;
Figure 7 demonstrates the Compound A viscosity build vs time at 60 °C and 100 °C, with 5% ferric chloride catalyst; and
Figure 8 demonstrates the gel times of Compound A in combination with concentrations of 1 , 1.5 and 2 PHR of BCh octyl dimethylamine complex at 160 °C.
DETAILED DESCRIPTION
Definition of terms
For the purposes of the present invention, the following terms as used herein shall, unless otherwise indicated, be understood to have the following meanings. Other terms that are not as defined below are to be understood as their normal meaning in the art.
The term "hydrocarbyl" as used herein, refers to a monovalent or divalent group, comprising hydrogen and carbon atoms, such as a major proportion (i.e., more than 50 %) of hydrogen and carbon atoms, preferably consisting exclusively of hydrogen and carbon atoms. The hydrocarbyl group may be aromatic, saturated aliphatic or unsaturated aliphatic. The hydrocarbyl group may be entirely aliphatic or a combination of aliphatic and aromatic portions. In some examples, the hydrocarbyl group includes a branched aliphatic chain which is substituted by one or more aromatic groups. Examples of hydrocarbyl groups therefore include acyclic groups, as well as groups that combine one or more acyclic portions and one or more cyclic portions, which may be selected from carbocyclic, aryl and heterocyclyl groups. The hydrocarbyl group includes monovalent groups and polyvalent groups as specified and may, for example, include one or more groups selected from alkyl, alkenyl, alkynyl, carbocyclyl (e.g. cycloalkyl or cycloalkenyl), aryl and heterocyclyl. The hydrocarbyl group may contain one or more heteroatoms, such as oxygen, nitrogen, sulphur, silicon or halogen which may be part of a functional group such as an alcohol, ether, carbonyl, ester, carboxylic acid, carbonate, amide, amine, carbamate, urea, thiol, thioether, thioester, thioacid, thioamide, silane organic halide or heterocycle, the hydrocarbyl linker may contain any combination of the above insofar as it is chemically stable. Furthermore, in some embodiments, halogens may entirely replace the hydrogen component of the hydrocarbyl group (i.e. the carbon- bonded hydrogens) to give the corresponding halo-substituted analogue.
The term "alkyl" as used herein refers to a monovalent straight- or branched-chain alkyl moiety. Unless specifically indicated otherwise, the term “alkyl” does not include optional substituents. The term "haloalkyl" as used herein refers to an alkyl group substituted with one or more halogen atoms. The term "halogen" as used herein refers to any of fluorine, chlorine, bromine, or iodine.
The term "alkyloxy" as used herein refers to an alkyl group substituted with one or more hydroxy groups. The term "alkylamino" as used herein refers to an alkyl group substituted with one or more primary, secondary, or tertiary amine groups.
The term "cycloalkyl" as used herein refers to a monovalent saturated aliphatic hydrocarbyl moiety containing at least one ring, wherein said ring has at least 3 ring carbon atoms. The cycloalkyl groups mentioned herein may optionally have alkyl groups attached thereto. Examples of cycloalkyl groups include groups that are monocyclic, polycyclic (e.g., bicyclic) or bridged ring system. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. The term "heterocycloalkyl" as used herein refers to a cycloalkyl group wherein the ring contains at least one heteroatom selected from oxygen, nitrogen, and sulphur. Examples of heterocycloalkyl groups include morpholine, piperidine, piperazine and the like.
The term "alkenyl" as used herein refers to a monovalent straight- or branched-chain alkyl group containing at least one carbon-carbon double bond, of either E or Z configuration unless specified. The term "alkynyl" as used herein refers to a monovalent straight- or branched-chain alkyl group containing at least one carbon-carbon triple bond. Examples of alkenyl groups include ethenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3- butenyl, 1 -pentenyl, 2-pentenyl, 3-pentenyl, 1 -hexenyl, 2-hexenyl, 3-hexenyl and the like. The term "aryl" as used herein refers to an aromatic carbocyclic ring system. An example of an aryl group includes a group that is a monocyclic aromatic ring system or a polycyclic ring system containing two or more rings, at least one of which is aromatic. Examples of aryl groups include aryl groups that comprise from 1 to 6 exocyclic carbon atoms in addition to ring carbon atoms. Examples of aryl groups include aryl groups that are monovalent or polyvalent as appropriate. Examples of monovalent aryl groups include phenyl, benzyl, naphthyl, fluorenyl, azulenyl, indenyl, anthryl and the like. An example of a divalent aryl group is 1 ,4-phenylene.
The term "heteroaryl" as used herein refers to an aromatic heterocyclic ring system wherein said ring atoms include at least one ring carbon atom and at least one ring heteroatom selected from nitrogen, oxygen and sulphur. Examples of heteroaryl groups include heteroaryl groups that are a monocyclic ring system or a polycyclic (e.g. bicyclic) ring system, containing two or more rings, at least one of which is aromatic. Examples of heteroaryl groups include those that, in addition to ring carbon atoms, comprise from 1 to 6 exocyclic carbon atoms. Examples of heteroaryl groups include those that are monovalent or polyvalent as appropriate. Examples of heteroaryl groups include pyridyl, pyrimidyl, thiopheneyl, isoxazolyl and benzo[b]furanyl groups.
The terms “furfural”, “furfuraldehyde”, “furfuryl” and “furan” are herein intended to optionally include any of the possible R3 substituents defined herein, unless explicitly stated otherwise. In the present invention, furfural is the aldehyde used in the Mannich reaction to form the benzoxazine rings. The resulting benzoxazine rings are substituted with furan at the 2- and 4-positions of the oxazine ring. Nevertheless, in the present invention a substituted furfural may be used instead of, or in combination with, unsubstituted furfural. In formulae (I), (II) and (III) the optional furfural substituents are defined by R3.
The term “phenolic compound” as used herein refers to phenol, optionally substituted with one or more R groups, wherein the R groups are as defined herein.
The term “bisphenol compound” as used herein refers to an organic compound comprising phenol moieties conjoined by a linker attached at any one of the 3-, 4-, or 5- positions, independently, relative to the phenol oxygen, wherein the linker is L2 as defined herein. The phenol moieties are optionally substituted with one or more R groups at one or more of the 3-, 4-, and/or 5- positions relative to the phenol oxygen that are not occupied by L2, wherein the R groups are as defined herein.
The present invention relates to a hitherto unknown class of ortho-substituted difunctional benzoxazine compounds comprising two benzoxazine rings di-substituted with furfuryl groups. Two benzoxazine groups may be conjoined by a linker attached to the oxazine nitrogen atoms, or attached to the benzoxazine benzene rings, or the two benzoxazine groups may share a single benzene ring.
The, benzoxazine compounds of the present invention comprise at least one unsubstituted position on the benzene ring to allow for self-polymerisation of the orthosubstituted difunctional benzoxazine compound. As will be appreciated, “unsubstituted” herein refers to substitution by a hydrogen atom.
The self-polymerisation takes place by thermal ring-opening polymerisation with or without catalyst or co-reactant. Whilst a wide range of Lewis acid catalysts (for example, including titanium isopropoxide, aluminium trichloride, Dichloro(methyl)aluminium, aluminium tribromide, iron tribromide, titanium tetrachloride, tin tetrachloride, yttrium trichloride, boron trifluoride (optionally in the form of boron trifluoride complexes, such as BF3 etherate, BF3 THF complex, or BF3 amine complexes such as BF3 methyl ethyl amine, BF3 ethyl amine, BF3 triethyl amine, or BF3 dimethyl octyl amine, preferably BF3 methyl ethyl amine), boron trichloride (optionally in the form of boron trichloride complexes, such as BCI3 methyl ethyl amine, BCI3 etherate, BCI3 THF complex, or BCI3 amine complexes such as BCI3 ethyl amine, BCI3 triethyl amine, or BCI3 dimethyl octyl amine, preferably BCI3 dimethyl octyl amine), zinc dichloride and trimethyl borane) may be used to catalyse self-polymerisation, it has been found that ferric chloride is particularly suitable for catalysing the self-polymerisation reaction. The result of the selfpolymerisation is a high molecular weight thermoset polymer matrix with a high degree of cross-linkage. Resins comprising the ortho-substituted difunctional benzoxazine compounds of the present invention are therefore useful precursors to poly-benzoxazine polymers. Advantageously, whilst the ortho-substituted difunctional benzoxazine compounds of the present invention are liquids at standard conditions, it may not be necessary to include a solvent or diluent in such a resin. Nevertheless, solvents or diluents may be used to adjust the properties of the resin as is required. The class of benzoxazines of the present invention may be synthesised by a Mannich reaction between an ortho-substituted phenolic compound, a primary amine, and furfural. As would be appreciated, two equivalents of furfural are required for every one equivalent of ortho-substituted phenolic compound and primary amine. As the present class of benzoxazines are difunctional, two equivalents of ortho-substituted phenolic compound and two equivalents of primary amine must be reacted with four equivalents of furfural to provide one equivalent of difunctional benzoxazine. However, two equivalents of the ortho-substituted phenolic compound or two equivalents of the primary amine may be comprised within a single difunctional molecule. For example, one equivalent of an ortho-substituted difunctional phenolic compound or of a difunctional primary amine, may be reacted with two equivalents of a primary amine or ortho-substituted phenolic compound, respectively, as well as four equivalents of furfural. The resulting benzoxazine will be difunctional as two benzoxazine rings are formed within the same single molecule. Therefore, the class of ortho-substituted difunctional benzoxazine compounds of the present invention all share the feature of two benzoxazine rings, each substituted with two furan groups and at least one benzoxazine ortho-substituent.
In one aspect, the benzoxazine compounds of the present invention have the general formula (I), shown below.
Figure imgf000016_0001
wherein each R group is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- C3 to C20 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C2o alkylamino, -OH, -OR1, -NH2, -NHR1 , -NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, - C(O)NHR1, -C(O)NR1 2, -O(CO)H, -O(CO)R1 , -NH(CO)H, -NH(CO)R1 , -NR1(CO)H, - NR1(CO)R1 , -SH, -SR1 , -SO2H, -SO2R1, -SO3R1, -SO3H, -SiR1 3, -NO2, -ON, -F, -Cl, -Br, - I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein each R1 is independently selected from: Ci to C2o alkyl, Ci to C2o haloalkyl, C3 to C2o cycloalkyl, C3 to C2o heterocycloalkyl, C2 to C2o alkenyl, C2 to C2o alkynyl, Ci to C2o alkyl-Ce to C14 aryl, Ci to C2o alkyl-C2 to C9 heteroaryl, Ci to C2o alkyl- C3 to C10 cycloalkyl, Ci to C2o alkyl-C3 to C10 heterocycloalkyl, Ci to C2o alkoxy, Ci to C2o alkylamino, C6 to C14 aryl, and C2 to C9 heteroaryl; wherein R2 is independently selected from: Ci to C2o alkyl, Ci to C2o haloalkyl, C3 to C2o cycloalkyl, C2 to C2o alkenyl, C2 to C2o alkynyl, -OH, -NH2, -OC1 to C2o alkyl, -NHC1 to C20 alkyl, -N(Ci to C20 alkyl)2, -NO2, -CN, -F, -Cl, -Br, and -I; wherein R3 is independently selected from: Ci to Ce alkyl, Ci to Ce alkenyl, Ci to Ce alkoxy, Ci to Ce alkyloxy, -C(O)OH, -C(O)O-Ci to Ce alkyl, Ci to Ce alkyl-(O)O-H, Ci to C6 alkyl-(O)O-Ci to C6 alkyl, and -OH; wherein R4 is independently either hydrogen, or is selected from: Ci to C2o alkyl, Ci to C2o haloalkyl, C3 to C2o cycloalkyl, C3 to C2o heterocycloalkyl, C2 to C2o alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-C3 to C2o cycloalkyl, Ci to C2o alkyl-C3 to C10 heterocycloalkyl, Ci to C2o alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1 , -NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, - C(O)NHR1, -C(O)NR1 2, -O(CO)H, -O(CO)R1 , -NH(CO)H, -NH(CO)R1 , -NR1(CO)H, - NR1(CO)R1 , -SH, -SR1 , -SO2H, -SO2R1, -SO3R1, -SO3H, -SiR1 3, -NO2, -CN, -F, -Cl, -Br, - I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; with the proviso that at least one R4 group is other than hydrogen; wherein L1 is a divalent hydrocarbyl linker comprising 1 to 50 carbon atoms; wherein x is independently 0, 1 , 2 or 3 when R4 is hydrogen, and x is independently 0, 1 or 2 when R4 is other than hydrogen; wherein n is independently 0, 1 , 2 or 3.
In preferred embodiment, both R4 groups are other than hydrogen, i.e. both R4 groups are independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C2o heterocycloalkyl, C2 to C2o alkenyl, C2 to C2o alkynyl, Ci to C2o alkyl-Ce to C14 aryl, Ci to C2o alkyl-C2 to C9 heteroaryl, Ci to C2o alkyl-C3 to C2o cycloalkyl, Ci to C2o alkyl-Cs to C heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, - NH2, -NHR1, -N 12, -C(O)OH, -C(O)OR1, -C(O)NH2, -C(O)NHR1, -C(O)NR12, -O(CO)H, - O(CO)R1, -NH(CO)H, -NH(CO)R1, -NR1(CO)H, -NR1(CO)R1, -SH, -SR1, -SO2H, -SO2R1, -SO3R1, -SO3H, -SiR13, -NO2, -ON, -F, -Cl, -Br, -I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group. In such an embodiment, both values of x are independently 0, 1 or 2. More preferably, both R4 groups are the same.
In a preferred embodiment, one, and more preferably both, R4 group(s) is/are activating groups.
In a preferred embodiment, one, and more preferably both, R4 group(s) is/are -OMe. A compound according to formula (I), wherein one or both R4 groups are -OMe may be prepared from guaiacol, also known as 2-Methoxy phenol. Guaiacol is a naturally occurring organic compound biosynthesized by a variety of organisms, such as guaiacum or wood creosote. It is also found in essential oils from celery seeds, tobacco leaves, orange leaves, and lemon peels. Guaiacol is also an innocuous compound often used as an expectorant, antiseptic, and local anaesthetic. Replacement of highly toxic, environmentally polluting and hydrocarbon derived chemicals such as phenol, with safe and bio-based alternatives provides significant advantage. The use of bio-based feedstocks such as guaiacol also significantly increases the percentage of bio-based carbon in the resulting benzoxazine.
In some embodiments one or both benzene rings of the benzoxazines are substituted with R groups at the 3-position and/or the 5-position, relative to the oxygen of the benzoxazine ring.
In some embodiments both x values < 2, preferably wherein both x values < 1 , and preferably wherein both x values are the same, and/or wherein both benzene rings of the benzoxazines are substituted with the same R group(s), more preferably wherein both x values = 0.
Formula (I) comprises two benzoxazine moieties attached at the benzoxazine nitrogen atoms though a divalent hydrocarbyl linker group L1. The ortho-substituted difunctional benzoxazine may be derived from a difunctional primary amine, comprising the linker group L1, wherein the difunctional primary amine undergoes a Mannich reaction with four equivalents of the furfural and two equivalents of a phenolic compound to form the compound of formula (I). In some embodiments L1 comprises 2 to 50 carbon atoms, 3 to 50 carbon atoms, 5 to 50 carbon atoms, 2 to 40 carbon atoms, 3 to 40 carbon atoms, 5 to 40 carbon atoms, 2 to 30 carbon atoms, 3 to 30 carbon atoms, 5 to 30 carbon atoms, 2 to 20 carbon atoms, 3 to 20 carbon atoms, or 5 to 20 carbon atoms. Preferably, L1 comprises at least one of: i) a heteroatom selected from nitrogen, oxygen, sulphur and silicon; ii) a double or triple carbon-carbon bond; or iii) an aromatic ring, heteroaromatic ring, and/or non-aromatic ring.
A list of preferred L1 groups is provided in Table 1 below, along with their corresponding difunctional primary amines.
Table 1. Exemplary list diamines useful in the present invention and their corresponding L1 linkers.
Diamine Name Diamine Structure Corresponding L1 Structure
Figure imgf000019_0001
2,2,4-trimethyl hexamethylene
Figure imgf000019_0002
diamine 2,4,4-trimethyl hexamethylene
Figure imgf000020_0001
diamine
Jeffamine
Figure imgf000020_0002
metaxylylene diamine
Figure imgf000020_0003
1 ,3-bis(aminomethyl) cyclohexane
Figure imgf000020_0004
benzene-1 ,4-diamine
Figure imgf000020_0005
isophorone diamine
Figure imgf000020_0006
diaminocyclohexane
Figure imgf000020_0007
Figure imgf000020_0008
Figure imgf000020_0009
bis-(p- aminocyclohexyl) methane
Figure imgf000021_0001
methylene dianiline
Figure imgf000021_0002
Bis-(p-aminocyclohexyl) methane and methylene dianiline, as well as derivatives thereof are particularly preferred difunctional amines. In some embodiments, L1 is a divalent hydrocarbyl linker comprising two rings conjoined by a divalent Ci to Cw alkyl group. The two rings may independently be carbocycles or heterocycles, but are both preferably carbocycles. The two rings may independently be 3- to 14-membered, but are preferably both 6-membered. The two rings may independently be aromatic, saturated or partially saturated, but are preferably saturated. Therefore, the two rings are most preferably cyclohexane.
In a preferred embodiment, the compound of formula (I) has the general formula (la), shown below.
Figure imgf000021_0003
wherein ring A and ring B are independently either aromatic or saturated 6 membered carbon rings, preferably wherein rings A and B are both saturated rings (e.g. both a cyclohexane group); wherein R5 is a divalent Ci to C alkyl group, preferably wherein R5 is a methylene group; with the proviso that at least one R4 group is other than hydrogen; and wherein R, R3, R4, x, and n are independently as defined hereinabove, preferably where both x values = 0 and/or wherein all n values = 0.
As can be seen from formula (I), one or two ortho-substituted phenols are used to provide the corresponding ortho-substituted benzoxazine, or phenols bearing further optional substitution may be used to provide corresponding further optional substitution in the resulting benzoxazine. In formula (I) the optional benzoxazine substituents are defined by group R.
However, one position ortho to the phenolic -OH group, i.e. either the 2-position or 6- position, must be unsubstituted (i.e. substituted by hydrogen), as well as at least one other position. This is because an unsubstituted ortho position, is required for the Mannich reaction to take place to form the benzoxazine ring, and the second unsubstituted position is required for the benzoxazine self-polymerisation to take place. Thus, the phenolic precursor must be 2- or 6-unsubsituted in relation to the phenolic oxygen, and must also be unsubstituted at at least one other position, in order to provide a benzoxazine with at least one unsubstituted position for polymerisation.
In formula (I), the ortho-position is defined by R4, wherein at least one R4 group, preferably both R4 groups, is/are an ortho-substituent independently selected from: Ci to C2o alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-C3 to C20 cycloalkyl, Ci to C20 alkyl-C3 to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1 , -NH2, -NHR1, -NR1 2, -C(O)OH, - C(O)OR1, -C(O)NH2, -C(O)NHR1, -C(O)NR12, -O(CO)H, -O(CO)R1 , -NH(CO)H, - NH(CO)R1, -NR1(CO)H, -NR1(CO)R1 , -SH, -SR1 , -SO2H, -SO2R1, -SO3R1, -SO3H, -SiR1 3, -NO2, -ON, -F, -Cl, -Br, -I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group.
This leaves 3 positions available for substitution with an R group when R4 is hydrogen, and 2 positions available for substitution with an R group when R4 is other than hydrogen, such that 0 to 3 R groups may exist on one benzoxazine ring, and 0 to 2 on the other, preferably neither R4 group is hydrogen and 0 to 2 R groups may exist on each benzoxazine ring. The number of possible R groups on each benzoxazine ring is shown in formula (I) as x. Two identical ortho-substituted phenolic compounds may be used to form a symmetrical ortho-substituted difunctional benzoxazine, or two different phenolic compounds may be used to form an asymmetrical difunctional benzoxazine, where one or both phenol compounds are ortho-substituted as long as both phenolic compounds are unsubstituted at one of the 2- or 6- positions, and at least one other position, in relation to the phenolic oxygen.
Preferably, naturally derived phenolic compounds may be used in order to further increase the content of bio-carbon in the resulting benzoxazine. One such example of bio derivable phenolic compound is guaiacol. Preferably guaiacol is used as one of the phenolic compounds, more preferably both of the phenolic compounds, giving a compound of formula (I) wherein one, preferably both, R4 group(s) is/are methoxy.
In another aspect, the benzoxazine compounds of the present invention have the general formula (II), shown below.
Figure imgf000023_0001
wherein each R group is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-C6 to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- C3 to C20 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1, -NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, - C(O)NHR1, -C(O)NR12, -O(CO)H, -O(CO)R1, -NH(CO)H, -NH(CO)R1, -NR1(CO)H, - NR1(CO)R1, -SH, -SR1, -SO2H, -SO2R1, -SO3R1, -SO3H, -SiR1 3, -NO2, -ON, -F, -Cl, -Br, - I, Ce to Cu aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein each R1 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- C3 to C10 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkoxy, Ci to C20 alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R2 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, -OH, -NH2, -OC1 to C20 alkyl, -NHC1 to C20 alkyl, -N(Ci to C20 alkyl)2, -NO2, -CN, -F, -Cl, -Br, and -I; wherein R3 is independently selected from: Ci to Ce alkyl, Ci to Ce alkenyl, Ci to Ce alkoxy, Ci to Ce alkyloxy, -C(O)OH, -C(O)O-Ci to Ce alkyl, Ci to Ce alkyl-(O)O-H, Ci to C6 alkyl-(O)O-Ci to C6 alkyl, and -OH; wherein R4 a direct bond to L2; or R4 is independently either hydrogen, or is selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-Cs to C20 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1, - NR1 2, -C(O)OH, -C(O)OR1 , -C(O)NH2, -C(O)NHR1, -C(O)NR12, -O(CO)H, -O(CO)R1, - NH(CO)H, -NH(CO)R1 , -NR1(CO)H, -NR1(CO)R1, -SH, -SR1 , -SO2H, -SO2R1, -SO3R1 , - SO3H, -SiR13, -NO2, -CN, -F, -Cl, -Br, -I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; with the proviso that at least one R4 group is other than hydrogen; wherein R6 is independently a monovalent group selected from -H, -OH, or a hydrocarbyl group comprising 1 to 50 carbon atoms; wherein L2 is a direct bond, a divalent group selected from: C(O), O, S, S(O), S(O)2, or a hydrocarbyl linker comprising 1 to 50 carbon atoms; wherein y is independently 0, 1 , or 2 when R4 is hydrogen or is a direct bond to L2, and y is independently 0 or 1 when R4 is other than hydrogen or a direct bond to L2; and wherein n is independently 0, 1 , 2 or 3.
In a preferred embodiment, both R4 groups are other than hydrogen or a direct bond to L2, i.e. both R4 groups are independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- C3 to C20 cycloalkyl, Ci to C20 alkyl-C3 to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1, -NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, - C(O)NHR1, -C(O)NR12, -O(CO)H, -O(CO)R1, -NH(CO)H, -NH(CO)R1, -NR1(CO)H, - NR1(CO)R1, -SH, -SR1, -SO2H, -SO2R1, -SO3R1, -SO3H, -SiR1 3, -NO2, -ON, -F, -Cl, -Br, - I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group. In such an embodiment, both values of y are independently 0 or 1 . More preferably, both R4 groups are the same.
In a preferred embodiment, one, and more preferably both, R4 group(s) is/are activating groups.
In a preferred embodiment, one, and more preferably both, R4 group(s) is/are -OMe. A compound according to formula (I), wherein both R4 groups are -OMe may be prepared from bisguiacol F. Bisguiacol F is a bisphenol compound substituted with a methoxy group at the ortho position of both benzene rings, i.e. two guaiacol groups connected at their 4-positions by a methylene bridge. Bisguiacol F has reduced endocrine disrupting activity compared to bisphenol A and other bisphenol compounds. Bisguiacol F may also be easily prepared from naturally derived guaiacol and vanillyl alcohol, which is derivable from vanilla extract. The use of bisguiacol F thus allows for the replacement of toxic, endocrine disrupting, and hydrocarbon derived chemicals, such as bisphenol A, with innocuous bio-based alternatives. The use of bio-based feedstocks such as bisguaiacol F also significantly increases the percentage of bio-based carbon in the resulting benzoxazine.
In some embodiments both y values < 1 , and preferably wherein both y values are the same, and/or wherein both benzene rings of the benzoxazine are substituted with the same R group(s), more preferably wherein both y values = 0.
Formula (II) comprises two benzoxazine moieties linked by a linker L2 attached to the benzene ring of each benzoxazine. As will be appreciated, this ortho-substituted difunctional benzoxazine may be derived from an ortho-substituted bisphenol compound. For the purpose of the present invention, the linker L2 may be independently attached to each benzene ring at any of the 2-, 3-, 4-, 5- or 6-positions relative to the phenolic oxygen. One of the two ortho (i.e. 2- and 6-positions) must remain unsubstituted, i.e. substituted by hydrogen in order for the Mannich reaction to proceed to form the benzoxazine ring.
In formula (II), L2 is a direct bond, or a divalent group selected from C(O), O, S, S(O), S(O)2 or a hydrocarbyl linker comprising 1 to 50 carbon atoms. In some embodiments L2 is attached at the 4-position, relative to the benzoxazine oxygen. In some embodiments L2 is selected from S(O)2, CH2, C(CH3)2, or a divalent benzene ring.
In some embodiments, L2 comprises 2 to 50 carbon atoms, 3 to 50 carbon atoms, 5 to 50 carbon atoms, 2 to 40 carbon atoms, 3 to 40 carbon atoms, 5 to 40 carbon atoms, 2 to 30 carbon atoms, 3 to 30 carbon atoms, 5 to 30 carbon atoms, 2 to 20 carbon atoms, 3 to 20 carbon atoms, or 5 to 20 carbon atoms.
The linker L2 may be attached to the resulting benzoxazine benzene ring at any available position, including via R4 when R4 is a direct bond. As will be appreciated, where R4 and L2 are both direct bonds, then this is equivalent to a single direct bond between the benzoxazine benzene rings. It is preferred that L2 is attached at the -3, -4, or 5-position, more preferably the 4-position, relative to the benzoxazine oxygen. Many widely commercially available bisphenol compounds comprise linkers L2 attached at both of the 4-positions relative to the phenolic oxygens, these are generally known as 4,4- bisphenols. Examples of 4,4-bisphenols with the ortho-positions substituted by R4, suitable for use in the present invention are listed in Table 2 below. Many orthosubstituted bisphenol compounds are commercially available. Additionally, orthosubstituted bisphenol compounds may be readily prepared from the corresponding unsubstituted bisphenol compounds. Addition of desired functional groups into an unsubstituted bisphenol compound at the ortho-position would be within the capabilities of the skilled person.
Table 2. Exemplary list of ortho-substituted bisphenols useful in the present invention and their corresponding L2 linkers.
Corresponding Corresponding ortho-substituted L2 structure unsubstituted Bisphenol structure
Bisphenol compound Bisphenol A -C(CH3)2-
Figure imgf000027_0001
Bisphenol AF -C(CF3)2-
Figure imgf000027_0002
Bisphenol AP -C(CH3)Ph-
Figure imgf000027_0003
Bisphenol B -C(CH3)(CH2CH3)-
Figure imgf000027_0004
Bisphenol BP -CPh2-
Figure imgf000027_0005
Bisphenol C -C=CCI2-
Figure imgf000027_0006
Bisphenol CP
Figure imgf000027_0007
Bisphenol E -C(CH3)H-
Figure imgf000027_0008
Bisphenol F -CH2-
Figure imgf000028_0001
Bisphenol FL
Figure imgf000028_0002
Bisphenol M
Figure imgf000028_0003
Bisphenol P
Figure imgf000028_0004
Bisphenol S -S(O)2-
Figure imgf000028_0005
Bisphenol TMC
Figure imgf000028_0006
Bisphenol Z
Figure imgf000028_0007
4,4'-Thiodiphenol -S-
Figure imgf000028_0008
Figure imgf000029_0001
Figure imgf000029_0004
Figure imgf000029_0005
1 ,4-Bis(4- hydroxybenzyl)benzol
Figure imgf000029_0002
4,4'-Biphenol Direct bond
Figure imgf000029_0003
As would be appreciated, the L2 groups would be conserved during a Mannich reaction and would thus be present in the compound of formula (II) when derived from the corresponding bisphenol compound precursor. Whilst the bisphenol compounds listed in Table 2 are all 4,4-bisphenols, the scope of the invention also includes any isomers of these bisphenol compounds wherein the L2 linker is attached at any combination of the 2-, 3-, 4-, 5- and -6 positions, so long as at least one ortho position, i.e. either the 2- or 6-position remains unsubstituted.
At least one unsubstituted position must remain on the resulting benzoxazine for polymerisation to take place. This leaves two positions available for substitution with an R group where R4 is hydrogen or is direct bond to L2, such that 0 to 2 R groups may exist on the benzoxazine ring, and leaves one position available for substitution with an R group where R4 is other than hydrogen or a direct bond to L2, such that 0 or 1 R groups may be present on the benzoxazine ring. Preferably, both R4 groups are other than hydrogen or a direct bond to L2 and 0 or 1 R groups are present on the benzoxazine ring. The number of possible R groups on each benzoxazine ring is shown in formula (II) as y. A symmetrical bisphenol compound, with the same on each phenol group may be used to form a symmetrical ortho-substituted difunctional benzoxazine, or an asymmetrical bisphenol compound, with differing substituents on each phenol group may be used may be used to form an asymmetrical difunctional benzoxazine, as long as both phenol groups are unsubstituted at one of the 2-or 6-position and at least one other position, in relation to the phenolic oxygen, in both cases the total number of R groups is y + y.
In another aspect, the benzoxazine compounds of the present invention have the general formula (III), shown below.
Figure imgf000030_0001
wherein R is selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl- Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-Cs to C20 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, - OR1 , -NH2, -NHR1 , -NR12, -C(O)OH, -C(O)OR1 , -C(O)NH2, -C(O)NHR1, -C(O)NR12, - O(CO)H, -O(CO)R1 , -NH(CO)H, -NH(CO)R1 , -NR1(CO)H, -NR1(CO)R1, -SH, -SR1, - SO2H, -SO2R1 , -SO3R1, -SO3H, -SiR1 3, -NO2, -ON, -F, -Cl, -Br, -I, C6 to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein each R1 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- Cs to C10 cycloalkyl, Ci to C20 alkyl-C3 to C heterocycloalkyl, Ci to C20 alkoxy, Ci to C20 alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R2 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, -OH, -NH2, -OC1 to C20 alkyl, -NHC1 to C20 alkyl, -N(Ci to C20 alkyl)2, -NO2, -CN, -F, -Cl, -Br, and -I; wherein R3 is independently selected from: Ci to Ce alkyl, Ci to Ce alkenyl, Ci to C6 alkoxy, Ci to C6 alkyloxy, -C(O)OH, -C(O)O-Ci to C6 alkyl, Ci to C6 alkyl-(O)O-H, Ci to Ce alkyl-(O)O-Ci to Ce alkyl, and -OH; wherein R6 is independently a monovalent group selected from -H, -OH, or a hydrocarbyl group comprising 1 to 50 carbon atoms; wherein n is independently 0, 1 , 2 or 3.
In this aspect, the ortho-substituted difunctional benzoxazine may be derived from a 2- subsitututed 1 ,3-benzene-diol. Two oxazine rings are formed on the shared benzene ring, giving an ortho-substituted difunctional benzoxazine with a shared benzene ring and a shared ortho-substituent. The compound of formula (III) may not be substituted at the 5-position of the benzene ring relative to the benzoxazine oxygens which are considered to occupy the 1 - and 3-positions, so that self-polymerisation of the resulting benzoxazine may take place at this position. The corresponding 4- and 6-positions of the benzene ring are occupied carbon atoms that form part of the benzoxazine ring. The compound of formula (III) is substituted at the 2-position, relative to the benzoxazine oxygens which are considered to occupy the 1 - and 3-positions. The 2-position is occupied by R in formula (III), wherein R is selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-C6 to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- C3 to C20 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1, -NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, - C(O)NHR1, -C(O)NR12, -O(CO)H, -O(CO)R1, -NH(CO)H, -NH(CO)R1, -NR1(CO)H, - NR1(CO)R1, -SH, -SR1, -SO2H, -SO2R1, -SO3R1, -SO3H, -SiR1 3, -NO2, -ON, -F, -Cl, -Br, - I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group. Therefore, the 1 ,3-benzene-diol precursor must be unsubstituted at the 4- and 6-positions in order to allow the oxazine rings to be formed at these positions, and the 5-position must be unsubstituted to allow for self-polymerisation of the resulting benzoxazine compound.
This leaves no further positions available for optional substitution on the benzoxazine ring. The corresponding precursor with hydroxy substitution at the 2-position, i.e. 1 ,2,3- benzene-triol, is known as pyrogallol. Pyrogallol is derivable by de-carboxylation of gallic acid, which is found in gallnuts, sumac, witch hazel, tea leaves, oak bark, and other plants.
In some embodiments, the compounds of any one of Formulae (I), (II) and (III) are selected from those wherein R is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl- C6 to C14 aryl, Ci to C29 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-C3 to C10 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, - OR1, -NH2, -NHR1, -NR1 2, -O(CO)H, -O(CO)R1, -NH(CO)H, -NH(CO)R1, -NR1(CO)H, - NR1(CO)R1, -SH, -SR1, -SiR13, -F, -Cl, -Br, -I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein R1 is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C29 alkyl-C3 to C29 cycloalkyl, Ci to C20 alkyl-C3 to C10, heterocycloalkyl, Ci to C20 alkoxy, Ci to C20 alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; and wherein R2 is independently selected from: Ci to C29 alkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, -OH, -NH2, -OC1 to C20 alkyl, -NHC1 to C20 alkyl, -N(Ci to C20 alkyl)2, -F, -Cl, -Br, or -I. In some embodiments, the compounds of any one of Formulae (I), (II) and (III) are selected from those wherein R is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1, -NR1 2, Ce to C14 aryl optionally substituted with one or more R2 group, or C2 to C9 heteroaryl optionally substituted with one or more R2 group; preferably -OH; wherein R1 is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl or C2 to C20 alkenyl; wherein R2 is independently selected from: Ci to C20 alkyl, -OH, -NH2, -OC1 to C20 alkyl, -NHC1 to C20 alkyl or -N(Ci to C20 alkyl)2, preferably -OH.
In some embodiments, the compounds of any one of Formulae (I), (II) and (III) are selected from those wherein R is independently selected from: Ci to C10 alkyl, Ci to C10 haloalkyl, C3 to Cw cycloalkyl, C3 to C10 heterocycloalkyl, C2 to Cw alkenyl, C2 to C10 alkynyl, Ci to C alkyl-C6 to C14 aryl, Ci to C alkyl-C2 to C9 heteroaryl, Ci to C alkyl- C3 to C10 cycloalkyl, Ci to C10 alkyl-Cs to Cw heterocycloalkyl, Ci to Cw alkyloxy, Ci to Cw alkylamino, -OH, -OR1, -NH2, -NHR1, -NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, - C(O)NHR1, -C(O)NR1 2, -O(CO)H, -O(CO)R1, -NH(CO)H, -NH(CO)R1, -NR1(CO)H, - NR1(CO)R1, -SH, -SR1, -SO2H, -SO2R1, -SO3R1, -SO3H, -SiR1 3, -NO2, -CN, -F, -Cl, -Br, - I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein each R1 is independently selected from: Ci to Cw alkyl, Ci to Cw haloalkyl, C3 to Cw cycloalkyl, C3 to Cw heterocycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, Ci to Cw alkyl-Ce to C14 aryl, Ci to Cw alkyl-C2 to C9 heteroaryl, Ci to Cw alkyl- Cs to Cw cycloalkyl, Ci to Cw alkyl-Cs to Cw heterocycloalkyl, Ci to Cw alkoxy, Ci to Cw alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R2 is independently selected from: Ci to Cw alkyl, Ci to Cw haloalkyl, C3 to Cw cycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, -OH, -NH2, -OC1 to Cw alkyl, -NHC1 to Cw alkyl, -N(Ci to Cw alkyl)2, -NO2, -CN, -F, -Cl, -Br, and -I.
In some embodiments, the compounds of any one of Formulae (I), (II) and (III) are selected from those wherein R is independently selected from: Ci to Cw alkyl, C3 to Cw cycloalkyl, C3 to Cw heterocycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, Ci to Cw alkyl- Ce to C14 aryl, Ci to Cw alkyl-C2 to C9 heteroaryl, Ci to Cw alkyl-Cs to Cw cycloalkyl, Ci to Cw alkyl-C3 to Cw heterocycloalkyl, Ci to Cw alkyloxy, Ci to Cw alkylamino, -OH, - OR1, -NH2, -NHR1, -NR1 2, -O(CO)H, -O(CO)R1, -NH(CO)H, -NH(CO)R1, -NR1(CO)H, - NR1(CO)R1, -SH, -SR1, -SiR1 3, -F, -Cl, -Br, -I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein R1 is independently selected from: Ci to Cw alkyl, C3 to Cw cycloalkyl, C3 to Cw heterocycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, Ci to Cw alkyl-Ce to C14 aryl, Ci to Cw alkyl-C2 to C9 heteroaryl, Ci to Cw alkyl-C3 to Cw cycloalkyl, Ci to Cw alkyl-C3 to Cw, heterocycloalkyl, Ci to Cw alkoxy, Ci to Cw alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; and wherein R2 is independently selected from: Ci to Cw alkyl, C3 to Cw cycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, -OH, -NH2, -OC1 to Cw alkyl, -NHC1 to Cw alkyl, -N(Ci to Cw alkyl)2, -F, -Cl, -Br, or -I.
In some embodiments, the compounds of any one of Formulae (I), (II) and (III) are selected from those wherein R is independently selected from: Ci to C alkyl, C3 to C cycloalkyl, C3 to Cw heterocycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, Ci to Cw alkyloxy, Ci to Cw alkylamino, -OH, -OR1, -NH2, -NHR1, -NR1 2, Ce to C14 aryl optionally substituted with one or more R2 group, or C2 to C9 heteroaryl optionally substituted with one or more R2 group; preferably -OH; wherein R1 is independently selected from: Ci to Cw alkyl, C3 to Cw cycloalkyl or C2 to Cw alkenyl; wherein R2 is independently selected from: Ci to Cw alkyl, -OH, -NH2, -OC1 to Cw alkyl, -NHC1 to Cw alkyl or -N(Ci to Cw alkyl)2, preferably -OH.
In some embodiments, the compounds of any one of Formulae (I) and (II) are selected from those wherein R4 is independently either hydrogen or selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-C3 to Cw cycloalkyl, Ci to C20 alkyl-C3 to Cw heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1, -NR1 2, -O(CO)H, -O(CO)R1, -NH(CO)H, - NH(CO)R1, -NR1(CO)H, -NR1(CO)R1, -SH, -SR1, -SiR1 3, -F, -Cl, -Br, -I, C6 to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein R1 is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-Cs to C20 cycloalkyl, Ci to C20 alkyl-Cs to Cw, heterocycloalkyl, Ci to C20 alkoxy, Ci to C20 alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; and wherein R2 is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, -OH, -NH2, -OC1 to C20 alkyl, -NHC1 to C20 alkyl, -N(Ci to C20 alkyl)2, -F, -Cl, -Br, or -I.
In some embodiments, the compounds of any one of Formulae (I) and (II) are selected from those wherein R4 is independently either hydrogen or selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1, -NR1 2, C6 to C14 aryl optionally substituted with one or more R2 group, or C2 to C9 heteroaryl optionally substituted with one or more R2 group; preferably -OH; wherein R1 is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl or C2 to C20 alkenyl; wherein R2 is independently selected from: Ci to C20 alkyl, -OH, -NH2, -OC1 to C20 alkyl, -NHC1 to C20 alkyl or -N(Ci to C20 alkyl)2, preferably -OH.
In some embodiments, the compounds of any one of Formulae (I) and (II) are selected from those wherein R4 is independently either hydrogen or selected from: Ci to C alkyl, Ci to C10 haloalkyl, C3 to C10 cycloalkyl, C3 to Cw heterocycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, Ci to Cw alkyl-Ce to C14 aryl, Ci to Cw alkyl-C2 to C9 heteroaryl, Ci to Cw alkyl-Cs to Cw cycloalkyl, Ci to Cw alkyl-Cs to Cw heterocycloalkyl, Ci to Cw alkyloxy, Ci to Cw alkylamino, -OH, -OR1, -NH2, -NHR1, -NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, - C(O)NHR1, -C(O)NR1 2, -O(CO)H, -O(CO)R1, -NH(CO)H, -NH(CO)R1, -NR1(CO)H, - NR1(CO)R1, -SH, -SR1, -SO2H, -SO2R1, -SO3R1, -SO3H, -SiR1 3, -NO2, -CN, -F, -Cl, -Br, - I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein each R1 is independently selected from: Ci to Cw alkyl, Ci to Cw haloalkyl, C3 to Cw cycloalkyl, C3 to Cw heterocycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, Ci to Cw alkyl-Ce to C14 aryl, Ci to Cw alkyl-C2 to C9 heteroaryl, Ci to Cw alkyl- Cs to Cw cycloalkyl, Ci to Cw alkyl-Cs to Cw heterocycloalkyl, Ci to Cw alkoxy, Ci to Cw alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R2 is independently selected from: Ci to Cw alkyl, Ci to Cw haloalkyl, C3 to Cw cycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, -OH, -NH2, -OC1 to Cw alkyl, -NHC1 to Cw alkyl, -N(Ci to Cw alkyl)2, -NO2, -CN, -F, -Cl, -Br, and -I.
In some embodiments, the compounds of any one of Formulae (I) and (II) are selected from those wherein R4 is independently either hydrogen or selected from: Ci to Cw alkyl, C3 to Cw cycloalkyl, C3 to Cw heterocycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, Ci to Cw alkyl-Ce to C14 aryl, Ci to Cw alkyl-C2 to C9 heteroaryl, Ci to Cw alkyl-Cs to Cw cycloalkyl, Ci to Cw alkyl-Cs to Cw heterocycloalkyl, Ci to Cw alkyloxy, Ci to Cw alkylamino, -OH, -OR1, -NH2, -NHR1, -NR1 2, -O(CO)H, -O(CO)R1, -NH(CO)H, - NH(CO)R1, -NR1(CO)H, -NR1(CO)R1, -SH, -SR1, -SiR1 3, -F, -Cl, -Br, -I, C6 to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein R1 is independently selected from: Ci to Cw alkyl, C3 to Cw cycloalkyl, C3 to Cw heterocycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, Ci to Cw alkyl-Ce to C14 aryl, Ci to Cw alkyl-C2 to C9 heteroaryl, Ci to Cw alkyl-C3 to Cw cycloalkyl, Ci to Cw alkyl-C3 to Cw, heterocycloalkyl, Ci to Cw alkoxy, Ci to Cw alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; and wherein R2 is independently selected from: Ci to Cw alkyl, C3 to Cw cycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, -OH, -NH2, -OC1 to Cw alkyl, -NHC1 to Cw alkyl, -N(Ci to Cw alkyl)2, -F, -Cl, -Br, or -I.
In some embodiments, the compounds of any one of Formulae (I) and (II) are selected from those wherein R4 is independently either hydrogen or selected from: Ci to C alkyl, C3 to C10 cycloalkyl, C3 to C10 heterocycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, Ci to Cw alkyloxy, Ci to Cw alkylamino, -OH, -OR1, -NH2, -NHR1, -NR1 2, Ce to C14 aryl optionally substituted with one or more R2 group, or C2 to C9 heteroaryl optionally substituted with one or more R2 group; preferably -OH; wherein R1 is independently selected from: Ci to Cw alkyl, C3 to Cw cycloalkyl or C2 to Cw alkenyl; wherein R2 is independently selected from: Ci to Cw alkyl, -OH, -NH2, -OC1 to Cw alkyl, -NHC1 to Cw alkyl or -N(Ci to Cw alkyl)2, preferably -OH.
In some embodiments, the compounds of any one of Formulae (I) and (II) are selected from those wherein R4 is independently either hydrogen or -OMe. It is preferred that the R group(s) and/or the R4 groups(s) where they are other than hydrogen present on the benzoxazine ring(s) of compounds of any of Formulae (I), (II) and/or (III) are activating groups. The activating properties of an activating group derive from their ability to donate electrons into an aromatic system, thus enhancing its affinity towards electrophiles, i.e. activating groups are electron donating groups. The degree of electron donation of an electron donating group is proportional to its strength as an activating group. These properties can be determined in relation to a specific substituent using the Hammett equation: a = log Kx - log KH
K is the ionisation constant for benzoic acid in water at 25 °C and Kx is the ionisation constant in water at 25 °C for a benzoic acid substituted with the electron donating group in question, o is the Hammett substituent constant, the more negative the Hammett substituent constant is, the more electron donating the substituent is, and therefore the stronger an activating group the substituent is. The Hammett substituent constant can thus be used to measure the strength of an activating group.
The Hammett substituent constant of a substituent will differ depending on its position on the benzoic acid (e.g. -para, -meta or -ortho), the -para, -meta and -ortho Hammett substituent constants thus represent the activating effect the substituent has on the position -para, -meta or -ortho to the substituent, respectively. Hammett substituent constants for substituents at the -ortho position cannot be accurately experimentally calculated due to the interference of steric effects. However, -ortho Hammett substituent constants can be estimated using density functional theory and are found to closely correspond to the -para Hammett substituent constants. Hammett substituent constants of an electron donating group at the -meta position tend to be significantly smaller than those at the -para and -ortho positions, which gives rise to the preferentially -ortho and - para regioselective directing effects of activating groups. -Meta Hammett substituent constants are thus of little relevance to electrophilic aromatic substitution.
The Hammett substituent constant (a) herein refers to the Hammett substituent constant of the substituent in question at the -para position, which is approximately equivalent to the Hammett substituent constant at the -ortho position and corresponds to the increase in reactivity of the aromatic ring with regard to electrophilic aromatic substitution at both the -para and -ortho positions. As would be appreciated, a more negative Hammett substituent constant corresponds to an increase in reactivity.
Literature values of Hammett substituent constants for common substituents would be known to the skilled person and can be found by reference to textbooks, for example, Hansch. C, Leo. A, Substituent constants for correlation analysis in chemistry and biology, New York NY: Wiley, 1979. Hammett substituent constants could also be easily measured by the skilled person by methods known in the art, see Hammett. P, The Effect of Structure upon the Reactions of Organic Compounds. Benzene Derivatives, J. Am. Chem. Soc., 1937, 59, 1, 96-103 and Hansch. C et al A Survey of Hammett Substituent Constants and Resonance and Field Parameters, Chem. Rev., 1991 , 91, 165-195.
Table 3 provides examples of Hammett substituent constants, as reported by Hammett. P, The Effect of Structure upon the Reactions of Organic Compounds. Benzene Derivatives, J. Am. Chem. Soc., 1937, 59, 1, 96-103 and Hansch. C et al A Survey of Hammett Substituent Constants and Resonance and Field Parameters, Chem. Rev., 1991 , 91, 165-195, as well as Hansch. C, Leo. A, Substituent constants for correlation analysis in chemistry and biology, New York NY: Wiley, 1979. As described hereinabove, Hammett Substituent constants reported in Table 3 are the para Hammett Substituent Constants.
Table 3. Hammett substituent constants
Group Structure Hammett Substituent
Constant (a)
Dimethyl amine -NMe2 -0.830
Primary amine -NH2 -0.660
Hydroxy -OH -0.370
Methoxy -OMe -0.268
Ethoxy -OEt -0.250
Methyl -CH3 -0.170
Benzyl -CH2C6H5 -0.090 Trimethyl silyl -SiMe3 -0.070
Phenyl -C6H6 -0.010
In some embodiments, the compounds of any one of Formulae (I), (II) and (III) are selected from those wherein R is selected from a substituent having a Hammett substituent constant (a) of less than zero, more preferably less than -0.050, even more preferably less than -0.100, most preferably less than -0.200.
In some embodiments, the compounds of any one of Formulae (I) and (II) are selected from those wherein one, and preferably both, R4 group(s) is/are selected from a substituent having a Hammett substituent constant (a) of less than zero, more preferably less than -0.050, even more preferably less than -0.100, most preferably less than - 0.200.
Unsubstituted furfural is a particularly desirable feedstock due to its low toxicity and abundant availability from natural sources. Related furan 2-carbaldehydes are also derivable from natural sources and thus also desirable chemical feedstocks, in particular 5-(Hydroxymethyl)-2-furaldehyde, 5-(methoxymethyl)-2-furaldehyde, and 5-methy-2- furfuraldehyde are preferred furfuraldehydes useful in the present invention. Unsubstituted furfural is the most preferred.
In some embodiments, the compounds of any one of Formulae (I), (II) and (III) are selected from those wherein R3 is independently selected from: Ci to Ce alkyl, Ci to Ce alkoxy, Ci to C6 alkyloxy, and -OH, preferably -CH3, -CH2OH, or -CH2OCH3.
In some embodiments, the compounds of any one of Formulae (I), (II) and (III) are selected from those wherein all n values < 1 , and preferably wherein all n values are the same, and/or wherein all R3 groups are the same, and/or wherein all R3 groups are attached at the position ortho to the furan oxygen; more preferably wherein all n values = 0.
In some embodiments, each R6 group of compounds (II) and/or (III) is independently selected from: -H, -OH, Ci to C2o alkyl, C3 to C2o cycloalkyl, C3 to C2o heterocycloalkyl, C2 to C2o alkenyl, C2 to C2o alkynyl, Ci to C2o alkyloxy, Ci to C2o alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R6 is optionally substituted with one or more R7 groups; wherein R7 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1 , -NH2, -NHR1 , -NR1 2, -C(O)OH, -C(O)OR1 , - C(O)NH2, -C(O)NHR1 , -C(O)NR12, -O(CO)H, -O(CO)R1 , -NH(CO)H, -NH(CO)R1 , - NR1(CO)H, -NR1(CO)R1 , -SH, -SR1, -SO2H, -SO2R1 , -SO3R1, -SO3H, -SiR1 3, -NO2, -ON, - F, -Cl, -Br, -I, Ce to C14 aryl, and C2 to C9 heteroaryl.
In some embodiments, the compounds of any one of Formulae (II) and (III) are selected from those wherein R6 is independently selected from: -H, -OH, Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R6 is optionally substituted with one or more R7 groups; wherein R7 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, - NH2, -NHR1, -NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, -C(O)NHR1 , -C(O)NR1 2, -O(CO)H, - O(CO)R1, -NH(CO)H, -NH(CO)R1 , -NR1(CO)H, -NR1(CO)R1, -SH, -SR1 , -SO2H, -SO2R1, -SO3R1 , -SO3H, -SiR13, -NO2, -CN, -F, -Cl, -Br, -I, Ce to C14 aryl, and C2 to C9 heteroaryl.
In some embodiments, the compounds of any one of Formulae (II) and (III) are selected from those wherein R6 is independently selected from: H, -OH, Ci to C10 alkyl, C3 to C10 cycloalkyl, C3 to C heterocycloalkyl, C2 to C alkenyl, C2 to C alkynyl, Ci to C alkyloxy, Ci to C10 alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R6 is optionally substituted with one or more R7 groups; wherein R7 is independently selected from: Ci to Cw alkyl, Ci to Cw haloalkyl, C3 to Cw cycloalkyl, C3 to Cw heterocycloalkyl, C2 to Cw alkenyl, C2 to Cw alkynyl, Ci to Cw alkyloxy, Ci to Cw alkylamino, -OH, -OR1, - NH2, -NHR1, -NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, -C(O)NHR1 , -C(O)NR1 2, -O(CO)H, - O(CO)R1, -NH(CO)H, -NH(CO)R1 , -NR1(CO)H, -NR1(CO)R1, -SH, -SR1 , -SO2H, -SO2R1, -SO3R1 , -SO3H, -SiR13, -NO2, -CN, -F, -Cl, -Br, -I, Ce to C14 aryl, and C2 to C9 heteroaryl.
In some embodiments, the compounds of any one of Formulae (II) and (III) are selected from those wherein R6 is independently selected from: H, -OH, Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyloxy, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R6 is optionally substituted with one or more R7 groups; wherein R7 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyloxy, -OH, -OR1 , -NR1 2, -C(O)OR1 , -C(O)NH2, -C(O)NHR1, - C(O)NR12, -O(CO)R1 , -NH(CO)H, -NH(CO)R1 , -NR1(CO)H, -NR1(CO)R1, -SH, -SR1, - SiR13, -NO2, -ON, -F, -Cl, -Br, -I, Ce to C14 aryl, and C2 to C9 heteroaryl.
In some embodiments, the compounds of any one of Formulae (II) and (III) are selected from those wherein R6 is independently selected from: -H, -OH, Ci to C10 alkyl, C3 to C10 cycloalkyl, C3 to C10 heterocycloalkyl, C2 to C10 alkenyl, C2 to C10 alkynyl, Ci to C10 alkyloxy, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R6 is optionally substituted with one or more R7 groups; wherein R7 is independently selected from: Ci to C10 alkyl, Ci to C10 haloalkyl, C3 to C10 cycloalkyl, C3 to C10 heterocycloalkyl, C2 to C10 alkenyl, C2 to C10 alkynyl, Ci to C10 alkyloxy, -OH, -OR1 , -NR1 2, -C(O)OR1 , -C(O)NH2, -C(O)NHR1, - C(O)NR1 2, -O(CO)R1 , -NH(CO)H, -NH(CO)R1 , -NR1(CO)H, -NR1(CO)R1, -SH, -SR1, - SiR13, -NO2, -CN, -F, -Cl, -Br, -I, Ce to C14 aryl, and C2 to C9 heteroaryl.
In some embodiments, the compounds of any one of Formulae (II) and (III) are selected from those wherein R6 is independently selected from: H, -OH, Ci to C20 alkyl, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R6 is optionally substituted with one or more R7 groups; wherein R7 is independently selected from: Ci to C20 alkyl, -OH, -OR1, -NR1 2, - NO2, -CN, -F, -Cl, -Br, and -I.
In some embodiments, the compounds of any one of Formulae (II) and (III) are selected from those wherein R6 is independently selected from: -H, Ci to C10 alkyl, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R6 is optionally substituted with one or more R7 groups; wherein R7 is independently selected from: Ci to C10 alkyl, -OH, -OR1, -NR1 2, -NO2, -CN, -F, -Cl, -Br, and -I. In preferred embodiments, the compounds of any one of Formulae (II) and (III) are selected from those wherein, R6 is a phenyl group.
In some embodiments, the compounds of any one of Formulae (II) and (III) are selected from those wherein, both R6 groups are the same. In other embodiments, the compounds of any one of Formulae (II) and (III) are selected from those wherein, both R6 groups are the different.
The present invention also provides processes for synthesising the compounds of formulae (I), (II) and (III). In one aspect the present invention also provides a process for preparing a compound of formula (I) comprising the steps of: i) providing a diamine NH2-L1-NH2 wherein L1 is as defined herein; ii) adding at least one furfuraldehyde substituted with n R3 groups, and one or more phenolic compounds independently substituted by R4 at one ortho position relative to the phenolic -OH group and independently substituted with x R groups, with the proviso that each of the one or more phenolic compounds has an unsubstituted position ortho to the phenolic -OH and at least one other unsubstituted position, wherein R, R3, R4 and n are as defined herein, and x = 0, 1 , 2 or 3, and wherein R4 in at least one of the one or more phenolic compounds is other than hydrogen; and iii) forming a compound of formula (I).
Each of the one or more phenolic compounds has an unsubstituted position ortho to the phenolic -OH and at least one other unsubstituted position. When R4 is hydrogen, the R4 may be said other unsubstituted position. In this case, when R4 is hydrogen 3 other positions are available for substitution and thus x may be 0, 1 , 2 or 3. When R4 is other than hydrogen, another position must be said other unsubstituted position. In this case, when R4 is other than hydrogen 2 other positions are available for substitution and thus x may be 0, 1 or 2.
A combination of two or more phenolic compounds may be used to form an asymmetric difunctional benzoxazine, or a single phenolic compound may be used to form a symmetrical difunctional benzoxazine. At least one phenolic compound must be orthosubstituted, i.e. , have an R4 group other than hydrogen at the ortho position relative to the phenolic -OH group. In a preferred embodiment each of the one or more phenolic compounds has an R4 group other than hydrogen at the ortho position relative to the phenolic -OH group, and is unsubstituted at one or more of the 3-, 4- or 5-positions relative to the phenolic -OH group. More preferably, a single phenolic compound is used, wherein the single phenolic compound has an R4 group other than hydrogen at the ortho position relative to the phenolic -OH group, and is unsubstituted at one or more of the 3-, 4- or 5-position relative to the phenolic -OH group. Whilst the exact ratio of diamine to phenolic compound to furfuraldehyde used in this process is 1 :2:4, differing molar ratios of these precursors may be utilised in some embodiments. Optionally, the molar ratio of the diamine to the at least one furfuraldehyde is from 1 :2 to 1 :20, preferably from 1 :3 to 1 :10, more preferably from 1 :4 to 1 :8; and/or wherein the molar ratio of the diamine to the at least one phenolic compound is from 1 :1 to 1 :5, preferably from 1 :1.5 to 1 :4, more preferably from 1 :2 to 1 :3.
There exists a wide range of orders of addition that fall within the scope of the processes for synthesising the compound of formula (I). Different orders of addition of the reactants may be used to favour specific products.
In one embodiment the diamine is contacted with the at least one furfuraldehyde prior to the addition of the at least one phenolic compound.
In one embodiment the diamine is contacted with a portion of the at least one furfuraldehyde prior to the addition of the at least one phenolic compound, wherein the remaining furfuraldehyde is added after and/or simultaneously to addition of the at least one phenolic compound.
In one embodiment the diamine is contacted with the at least one phenolic compound and the at least one furfuraldehyde simultaneously.
In one embodiment, two different phenolic compounds are added separately. This embodiment is suited to the preparation of asymmetrical benzoxazines.
In one embodiment, only one phenolic compound is added. This embodiment is suited to the preparation of symmetrical benzoxazines.
In another aspect, the present invention provides a process for preparing a compound of formula (II) or (III) comprising the steps of: i) providing A) a bisphenol compound substituted with y R groups on each benzene ring and comprising a linker L2, and wherein the bisphenol compound is substituted with one R4 group other than hydrogen at an orthoposition relative to the phenolic -OH on one or each benzene ring of the bisphenol compound, with the proviso that each benzene ring of the bisphenol compound has an unsubstituted position ortho to the phenolic - OH and at least one other unsubstituted position; or B) a benzene-1 ,3-diol substituted with 1 R group at the 2-position; wherein R, R4, and L2 are as defined herein, and y = 0, 1 or 2; ii) contacting the compound from step i) with at least one furfuraldehyde substituted with n R3 groups, and at least one primary amine substituted with one R6 group, wherein n, R3 and R6 are as defined herein; and iii) forming a compound of formula (II) or (III).
Each benzene ring of the bisphenol compound has an unsubstituted position ortho to the phenolic -OH and at least one other unsubstituted position. When R4 is hydrogen, the R4 may be said other unsubstituted position. In this case, when R4 is hydrogen, or when R4 is a direct bond to L2, 2 other positions are available for substitution and thus y may be 0, 1 or 2. When R4 is other than hydrogen, another position must be said other unsubstituted position. In this case, when R4 is other than hydrogen or a direct bond to L2, 1 other position is available for substitution and thus y may be 0 or 1 .
In a preferred embodiment, the bisphenol compound is substituted with one R4 group other than hydrogen at an ortho-position relative to the phenolic -OH on each benzene ring of the bisphenol compound, more preferably both, R4 group(s) is/are the same.
As described above, this process yields a compound of formula (II) when a bisphenol compound precursor is used, a compound of formula (III) when a 1 ,3-benzene-diol is used. In the aspects relating to formula (II) and (III), two equivalents of primary amine are used in the preparation of the benzoxazine compound, the primary amine has one substituent defined herein as R6. The primary amine becomes incorporated into the benzoxazine ring to provide the benzoxazine nitrogen substituted with R6. A single primary amine may be used so that both R6 groups are the same, or multiple primary amines may be used so that both R6 groups are different from each other.
Whilst the exact ratio of phenolic compound or benzene-diol, to primary amine to furfuraldehyde used in this process is 1 :2:4, differing molar ratios of these precursors may be utilised in some embodiments. Optionally, the molar ratio of the bisphenol compound or benzenediol to the at least one furfuraldehyde is from 1 :2 to 1 :20, preferably from 1 :3 to 1 :10, more preferably from 1 :4 to 1 :8; and/or wherein the molar ratio of the bisphenol compound or benzenediol to the at least one primary amine is from 1 :1 to 1 :5, preferably from 1 :1 .5 to 1 :4, more preferably from 1 :2 to 1 :3.
There exists a wide range of orders of addition that fall within the scope of the processes for synthesising the compounds of formulae (II) and (III). Different orders of addition of the reactants may be used to favour specific products.
In one embodiment the at least one primary amine, is contacted with the at least one furfuraldehyde prior to the addition of the bisphenol compound or benzenediol.
In one embodiment the at least one primary amine, is contacted with a portion of the at least one furfuraldehyde prior to the addition of the bisphenol compound or benzenediol, wherein the remaining furfuraldehyde is added after and/or simultaneously to addition of the bisphenol compound or benzenediol, respectively.
In one embodiment the at least one primary amine, is contacted with the bisphenol compound or benzenediol, and the at least one furfuraldehyde simultaneously.
In one embodiment two different primary amines are added separately. This embodiment is suited to the preparation of asymmetrical benzoxazines.
In one embodiment only one primary amine is added. This embodiment is suited to the preparation of symmetrical benzoxazines.
The compounds of the present invention may be prepared over a range of different temperatures that the skilled person would be familiar with from conventional Mannich chemistry and conventional benzoxazine preparations. The compounds of the present invention may, for instance, be prepared at room temperature and the process may be accelerated by heating and/or the use of a catalyst. Preferably, the temperature of the reaction is between 25 °C and 150 °C, more preferably the temperature of the reaction is between 40 °C and 100 °C. The reaction may optionally be catalysed wherein either: the catalyst is i) an acid catalyst, for example an acid catalyst selected from HCI, trifluoroacetic acid, methane sulphonic acid, p-toluenesulphonic acid, trifluoromethanesulphonic acid, benzoic acid and mixtures thereof; or ii) a basic catalyst, for example a basic catalyst selected from NaOH, Na2CO3, triethylamine, triethanolamine and mixtures thereof. A broad range of organic solvents are suitable for use in the reaction, for example MeCN, benzene, methanol, ethanol, IPA, butanol, chloroform, DCM, diethyl ether, DMF, dioxane, ethyl acetate, petroleum ether, kerosine, pentane, hexane, heptane, MTBE, NMP, THF, toluene, xylene and mixtures thereof. Toluene is the most preferred solvent for use in the reaction.
As would be appreciated, the Mannich reaction and benzoxazine cyclisation reaction produce water. The skilled person is capable of employing methods of removing water produced during the reaction along with any solvent used, in order to yield the final product, such as boiling, distillation, vacuum distillation, azeotroping, dean stark, precipitation etc.
In a yet further aspect, the present invention comprises a resin composition comprising a benzoxazine compound of formula (I), (II) or (III), as described herein. Any suitable organic solvent may be used as a solvent or diluent in a resin composition of the present invention, for example MeCN, benzene, methanol, ethanol, IPA, butanol, chloroform, DCM, diethyl ether, DMF, dioxane, ethyl acetate, petroleum ether, kerosine, pentane, hexane, heptane, MTBE, NMP, THF, toluene, xylene and mixtures thereof. Toluene is a particularly suitable solvent or diluent for ortho-substituted difunctional benzoxazine compounds and resins thereof of the present invention. As would be appreciated, methods of forming and handling a resin composition from a given monomeric compound would be known by the skilled person.
Reinforced materials
The benzoxazine compounds of the present invention, or resins thereof are particularly useful in the manufacture of reinforced materials. In particular, thermoset polymer matrixes, such as fibre-reinforced plastic, comprising fibrous materials, for example aramid fibre, basalt, wood fibre, glass fibre, carbon fibre or flax. The material to be reinforced is contacted with an ortho-substituted difunctional benzoxazine compound of the present invention, or resin thereof, to form a pre-preg, followed by curing of the ortho-substituted difunctional benzoxazine compound by self-polymerisation to form cross-linkages, to thereby reinforce the material. A coating may be formed on a material by contacting the surface of the material with an ortho-substituted difunctional benzoxazine compound of the present invention, or resin thereof, followed by allowing self-polymerisation of the ortho-substituted difunctional benzoxazine compound. Selfpolymerisation of the ortho-substituted difunctional benzoxazine compound can occur at ambient temperature or elevated temperature, with or without a catalyst or co-reactant.
Self-polymerisation of the ortho-substituted difunctional benzoxazine also allows the compounds of the invention to be used for the purpose of liquid moulding, film adhesives, composite construction, material bonding and repair, as in the case of conventional benzoxazines. As the skilled person will appreciate from the present disclosure, the properties of the ortho-substituted difunctional benzoxazine compounds also find particular utility in resin formation, resin polymerisation, and formation of reinforced materials such as fibre-reinforced plastic.
The polymer formed by self-polymerisation of the ortho-substituted difunctional benzoxazine compounds of the present invention has exposed phenol groups, due to the benzoxazine ring opening reaction. This means that further cross-linkage or curing can be achieved using epoxy resin, the epoxide groups of which are capable of reacting with the exposed phenol groups. An epoxy-based resin may be applied to, or incorporated into, an ortho-substituted difunctional benzoxazine compound of the present invention, or resin composition thereof, or a pre-preg or reinforced material formed therefrom, in order to provide further curing, hardening, cross-linkage and reinforcement. Hybridisation with epoxy-based resins may be used to increase the Tg of a benzoxazine thermoset, or material comprising or reinforced with the same.
Examples of epoxy-based resins suitable for use in the present invention include polyglycidyl ethers of polyhydric phenols, epoxidised novolacs or similar glycidated polyphenolic resins, glycidated bisphenols, such as glycidated bisphenol A or F, or halogenated (e.g. chlorinated or fluorinated) analogues thereof; polyglycidyl ethers of alcohols, glycols or polyglycols, and polyglycidyl esters of polycarboxylic acids. Preferred examples of epoxy resins are polyglycidyl ethers of a polyhydric phenol. Polyglycidyl ethers of polyhydric phenols can be produced, for example, by reacting an epihalohydrin with a polyhydric phenol in the presence of an alkali. Examples of suitable polyhydric phenols include: 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A); 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane; 1 ,1-bis(4-hydroxyphenyl) ethane; 1 ,1- bis(4-hydroxyphenyl) isobutane; bis(2-hydroxy-1 -naphthyl) methane; 1 ,5- dihydroxynaphthalene; 1 ,1-bis(4-hydroxy-3-alkylphenyl) ethane and the like. Commercial examples of preferred epoxy resins that may be used include EPI LOK 60-600.
The reinforced material may be prepared by applying a layer of a resin as defined herein, onto a bottom film carrier layer. Glass fibres, carbon fibres, flax, or any other fibrous material as the reinforcement may then then be applied to the upper surface of the resin on the film carrier. A further layer of the resin is applied to sandwich the fibrous material between the layers. A top film may be applied to the upper layer. The resulting layered composition may subsequently be compressed as part of forming the reinforced material.
As will be appreciated, in some embodiments, the reinforced material of the present invention may be formed from a sheet-molding compound (SMC) comprising a compound according to formula (I), (II) or (III), or resin thereof, and fibrous material as defined above. Methods of preparing such SMC materials are known in the art and can be readily adapted for use in preparing reinforced materials as defined herein. The SMC material may further include additives selected from hardeners, accelerators, fillers, pigments, fire retardants and/or any other components, as required. For example, the sheet-form polymeric material may also include melamine, which is useful as a fire retardant. The SMC may include a further thermoplastic material.
In some embodiments, the reinforced material of the present invention may comprise a number of layers, the layers may be joined together in a variety of ways. For instance, where air-tight sealing coating material comprising an elastomer is used, the same coating material may be used to bond the first insulating layer to one or more adjacent layers of the layered composite material panel. Alternatively, or in addition, SMC material comprising a compound according to formula (I), (II) or (III) may be bonded to one or more adjacent layers during curing of the reinforced material, for instance using heat and/or pressure. In addition, a variety of known adhesives may be used to bond the individual layers of the layered composite material panel together. Preferably, pressure is applied to the layered composite material during the bonding step so as to ensure good adhesion of the layers. As noted above, where one or more layers comprises a compound according to formula (I), (II) or (III), or resin thereof, (e.g. as part of an SMC material) the application of pressure may also assist in the curing of the compound according to formula (I), (II) or (III), or resin thereof. The invention will now be described by reference to the following non-limiting Examples and the Figures.
EXAMPLES
EXAMPLE 1 - Preparation of Compound A
Figure imgf000049_0001
184 grams of toluene was added to a 1 litre, round-bottomed flask equipped with a condenser, mechanical stirrer, addition funnel and thermometer. 384 grams [4 Mols] of unsubstituted furfuraldehyde was added and the agitator started. 210 grams [1 Mol] of 4,4-Diaminodicyclohexylmethane, was added to the flask over a 60-minute period controlling the temperature below 60 °C throughout the addition.
188 grams of phenol [2 Mols] was added in 8 aliquots maintaining the temperature below 50 °C throughout the 30-minute period. The mixture was held for a further 30 minutes before being heated to azeotrope up to 120 °C removing approximately 72 grams of water formed during the reaction.
The flask was then reconfigured for vacuum distillation and distilled under vacuum to 120 °C recovering the toluene [182 grams recovered] to yield Compound A in a liquid form. EXAMPLE 2 - Preparation of Compound B
Figure imgf000050_0001
Compound B
184 grams toluene was added to a 1 litre, round-bottomed flask equipped with a dean and stark separator, condenser, mechanical stirrer, addition funnel and thermometer.
228 grams of bisphenol A [1 Mole] was added to the flask along with 384 grams [4 Mols] of unsubstituted furfuraldehyde and the agitator started. A nitrogen atmosphere was applied and aniline 186 grams [2 Moles] added in 4 aliquots over a period of 60 minutes. The temperature was maintained between 43 - 47 °C throughout the addition.
Following the addition of the aniline the flask was heated to 85 °C and held 1 hour. It was then azeotroped up to 110 °C removing approximately 71 grams water formed during the reaction. The Flask was then reconfigured for vacuum distillation and distilled under vacuum to 120 °C recovering the toluene [181 grams recovered] to yield Compound B in a liquid form.
EXAMPLE 3 - Preparation of Compound C
Figure imgf000050_0002
Compound C 184 grams of toluene was added to a 1 litre, round-bottomed flask equipped with a dean and stark separator, condenser, mechanical stirrer, addition funnel and thermometer. 110 grams of resorcinol [1 Mole] was added to the flask along with 384 grams [4 Mols] of unsubstituted furfuraldehyde and the agitator started. A nitrogen atmosphere was applied and aniline 186 grams [2 Moles] added in 4 aliquots over a period of 60 minutes. The temperature was maintained between 45 - 50 °C throughout the addition.
Following the addition of the aniline the flask was heated to 85 °C and held 1 hour. It was then azeotroped up to 110 °C removing approximately 72 grams water formed during the reaction. The flask was then reconfigured for vacuum distillation and distilled under vacuum to 120 °C recovering the toluene [182 grams recovered] to yield Compound C in a liquid form.
Figure imgf000051_0001
Wherein R8 is independently selected from a -C15H31 straight chain alkyl group, -C15H29 straight chain alkenyl group, -C15H27 straight chain alkenyl group, and -C15H25 straight chain alkenyl group.
184 grams of toluene was added to a 1 litre, round-bottomed flask equipped with a dean and stark separator, condenser, mechanical stirrer, addition funnel and thermometer. 230 grams of Jeffamine D230 (RTM) [1 Mole] was added to the flask along with 384 grams [4 Mols] of unsubstituted furfuraldehyde and the agitator started. A nitrogen atmosphere was applied and 660 grams [2 Moles] of cardanol added. The temperature was maintained <75 °C throughout the additions. Following the addition of the cardanol the flask was heated to 85 °C and held 1 hour. It was then azeotroped up to 110 °C removing approximately 71 grams of water formed during the reaction. The flask was then reconfigured for vacuum distillation and distilled under vacuum to 120 °C recovering the toluene [180 grams recovered] to yield Compound D in a liquid form.
Example 5 - Comparison of physical properties against known benzoxazines Table 4. Comparison of the properties of Compounds A to D with those of a conventional benzoxazine (Cardarez R111)
Compound Colour Plate gel at Viscosity at Tg / °C Bio- (ASTM 200 °C / 25 °C / Pa S (cured at carbon D1544- minutes (ASTM 180 °C for content 04(2018)) (ASTM D2556- 2 hours, / % D3056- 14(2018)) and then 14(2018)) 200 °C for 4 hours)
Compound A 18 (black) 6:55 115 190 44
Compound B 18 (black) 7:22 215.7 128 43
Compound C 18 (black) 7:18 345.2 114 53
Compound D 18 (black) 9:18 11.8 123 ~85
Cardarez R111 18 (black) 12:00 3* 160 0
(RTM)
* Solution viscosity is undertaken as a 50% weight/weight solution in toluene as Cardarez R111 (RTM) is a solid.
The results in Table 4 demonstrate the advantages of furan derived di-functional benzoxazine compounds. Furan derived benzoxazines provide a significant bio-carbon contents, exceeding 40% in each case, meaning that the furan derived benzoxazine compounds of the present invention can help meet environmental targets in the applications in which they are deployed and are produced using renewal feedstocks.
Furan derived benzoxazines also have advantageously low viscosities which provides for easier handling during preparation, storge and use, as well as reducing the need for diluents or solvents in a resin composition. Conventional benzoxazine, Cardarez R111 (RTM), is a solid, and as such no directly comparable viscosity measurement can be taken at 25 °C. However, Figure 1 demonstrates the viscosity (mPa s) v temperature (°C) of Cardarez R111 (RTM), using ASTM D4287-00(2019). Due to the solid nature of Cardarez R111 (RTM) viscosity measurements must be taken at high temperatures in order to melt the Cardarez R111 (RTM). It can be seen from Figure 1 that temperatures as high as 120 °C to 140 °C are required before the viscosity of Cardarez R111 (RTM) is at a comparable order of magnitude to the viscosities of compounds A to D at 25 °C.
Figure 2 demonstrates viscosity (mPa s) development over time (hours) of Cardarez R111 (RTM) at 100 °C, 120 °C and 140 °C. Cardarez R111 (RTM) is a thermoset and reactivity rate [devoid of catalysis or co-polymer] is temperature dependent and depicted in Figure 2. Cardarez R111 (RTM) stability evaluation undertaken with a 50 gram mass in all cases. Viscosity figures quoted are evaluated and detailed at the temperature that the material was held. Viscosity evaluation was undertaken using a cone and plate viscometer [CPV] and the test temperature for viscosity evaluation is the same as the designated stability test temperature[s].
As will be appreciated, each of the furan derived benzoxazines exhibits a significantly shorter gel time (as measured by ASTM D3056-14(2018)) in comparison to conventional benzoxazine, Cardarez R111. Relatively slow curing times are a known deficiency associated with conventional benzoxazines. Furan derived benzoxazines provide surprising improvements in gel time, indicating that furan derived benzoxazines exhibit greater reactivity, leading to improvements in process efficiency in applications where benzoxazines are employed.
Figure 3 and Figure 4 compare the gel-time reactivity (gel time I minutes) undertaken with a 1 gram mass of Cardarez R111 (RTM) and Compound A, respectively. Cure determination by plate gel at specified temperatures (°C). The gel time is representative of the progress of curing by self-polymerisation. No catalyst or co-reactant was used. Figures 3 and 4 are in contrast to the plate gel data (ASTM D3056-14(2018)) shown in Table 4. The ASTM D3056-14(2018) method used in Table 4 uses a catalyst, whereas the experiments shown in Figures 3 and 4 were performed in the absence of a catalyst. As can be seen, Cardarez R111 (RTM) is less amenable to catalysis as compared to the furan derived benzoxazines which are particularly well suited to catalysed curing. The addition of the catalyst to furan derived benzoxazines provides for a much greater reduction in gel time. Without being bound to any particular theory, it is expected that the furan groups on the benzoxazine ring assist in co-ordinating the catalyst to bring it into closer proximity with the benzoxazine ring to stimulate ring opening.
The results in Table 4 also show that glass transition temperatures compare favourably with the conventional benzoxazine (Cardarez R111) or, in the case of Compound A, are improved over the conventional benzoxazine.
Figure 5 demonstrates the Tg development (°C) of thermosets cured at 180 °C vs time (minutes) for a Compound A thermoset and a comparative Cardarez R111 (RTM) thermoset. As can be seen, Compound A provides superior Tg development over time and thus is able to produce thermosets of a higher Tg once sufficient cure time is applied. As would be appreciated, cure times of 90 minutes or greater are commonly used in the art for various applications.
It has also been demonstrated that the furan derived benzoxazines are particularly well suited to curing with a ferric chloride catalyst, although any suitable Lewis acid catalyst may also be used. Figure 6 demonstrates the Tg development (°C) of Compound A during curing at 140 °C over 1 hour with 3%, 4% or 5% by weight of a ferric chloride catalyst. Increased concentration of catalyst can clearly be seen to accelerate curing in order to rapidly provide thermosets of higher Tg.
Similarly, Figure 7 demonstrates the Compound A viscosity build (Pa- s) vs time (minutes) at 60 °C and 100 °C, with 5% ferric chloride catalyst. The 5% ferric chloride allows for curing to take place at significantly lower temperatures. Cardarez R111 (RTM) is a solid and so must be heated to a high temperature and melted before a catalyst may be mixed with the Cardarez R111 (RTM). This means that the catalysis of a solid benzoxazine such as Cardarez R111 (RTM) requires addition of the catalyst at high temperature followed by mixing before it can be applied in the desired use. This risks premature curing and causes difficulty in handling and storage. The furan derived benzoxazines, however, are liquids at room temperature (e.g. 25 °C) and so may be mixed with a catalyst at comparatively low temperature without the risk of premature curing.
As can be seen from Figure 7, the viscosity build is very slow at 60 °C, which demonstrates the utility for storage and handling of Compound A pre-mixed with catalyst at low temperature. Additionally, rapid curing can nevertheless be achieved, once desired, by heating to a higher temperature, e.g. 100 °C. This is not possible for a solid benzoxazine which cannot be pre-mixed with a catalyst prior to melting at high temperature.
Example 6 - Preparation of reinforced material
A prepreg composite material was provided, in which a reinforcement fibre is preimpregnated with a resin composition comprising Compound A. Compound A is a viscous liquid and can be commercially processed via hot-melt or solvated and processed through conventional methods.
The material was used to make a composite part produced by a standard prepreg stage and pressing at a consolidation pressure 80 bar/cm2. Each composite part was generated using glass fabric with fibre density - binder ratio of 60:40 by weight: E-glass fabric, Style 7628 Finish phenolic compatible.
The cure schedule employed was heating at a rate of 8 °C/minute from RT up to 180 °C, followed by holding at 180 °C for 3 hours under a consolidation pressure of 80 bar/cm2.
The resultant composite panel had excellent surface appearance, free from defects such as porosity. The resultant product is suitable for use with a variety of reinforcements finding application in numerous areas including but not limited to, aircraft interiors and flooring, aerospace components, cargo liners, automotive parts, ballistic components, electrical laminates, fire resistant laminates and panels, sporting goods, train components, and tooling.
Example 7 - Sample laminate properties The physical properties, and chemical resistance properties of a reinforced material according to Example 6 were measured and compared to a comparative reinforced material produced by the same method of Example 6 using a known benzoxazine (Cardarez R111 (RTM))
Table 5 - Reinforced material physical properties comparison
Physical Property Cardarez R111 (RTM) Compound A
Tg / °C 160 190
Flexural strength / MPa 580 550
Flexural modulus / GPa 27 25
Impact strength / KJ M2 48 50
UL 94 evaluation VO Chemical resistance of the reinforced material derived from a furan derived benzoxazine vs a comparative reinforced material was determined by weight change following submersion of the materials. The samples were submerged in the given chemical for 4 weeks at 25 °C.
Table 6 - Reinforced material chemical resistance comparison
Chemical submersion Cardarez R111 (RTM) Compound A Weight gain/loss / %
Weight gain/loss / %
Acetone -7.00 +4.58
Butyl acetate -1.23 +3.36
Ethylene diamine Destroyed Destroyed
Methanol -0.64 +5.61 Nitric acid 20 % -0.74 +0.47
Sulphuric acid 50 % -3.08 +1 .24
Xylene -0.42 +1.39
As can be seen from Table 5, the reinforced material made with compound A, has comparable strength and flexibility to that of a reinforced material produced with Cardarez R111 (RTM). The reinforced material made with Compound A is also shown to have a high degree of fire resistance. As can be seen from Table 6, the reinforced material made with Compound A, also has comparable chemical resistance to that of a reinforced material produced with Cardarez R111 (RTM). A very similar degree of weight change (indicative of chemical degradation) is generally observed as a result of chemical exposure.
The present invention thus allows for the provision of reinforced materials comprising a high degree of bio-carbon from renewable stocks without negatively impacting the physical properties or chemical resistance.
Example 8 - Effects of catalysis
Effect of Catalyst on Gel Time
The effects of catalysis on gel time were investigated by measuring the gel time of a solution of 90% Compound A and 10% acetone with various concentrations of a curing catalyst at 160 °C. The catalyst used was BCh octyl dimethylamine complex and its relative concentration was measured in parts per hundred (PHR) with respect to Compound A.
A solution of BCI3 octyl dimethylamine complex in ethanol was added to the solution of Compound A and mixed for 5 minutes with a slow rate agitator to form a homogenous solution without introducing air. The combined material had a viscosity of 1180 mPa s at 25 °C. The gel times of Compound A in combination with concentrations of 1 , 1.5 and 2 PHR of BCI3 octyl dimethylamine complex at 160 °C were found to be approximately 320 seconds, 180 seconds, and 60 seconds, respectively. As would be expected, increasing the concentration of catalyst decreases the gel time, and these results are shown graphically in Figure 8.
Preparation of Reinforced Material Using a Catalyst
A combined solution of 90% Compound A and 10% acetone combined with 1 PHR of BCh octyl dimethylamine complex was used to prepare a prepreg material. The combined solution was applied via a conventional process of impregnation of an E-glass fabric cloth (Style 7628 - finish phenolic compatible) having a fibre density of 70 % by weight, with the solution followed by driving off the solvent and partially advancing the resin to form a partially cured state or state of advancement/cure that allows the sheets to have sufficient strength so that they can be laid up as a laminate (prepreg layer stack), but not so advanced that they are rigid or fail to flow when pressed under heat and pressure. The sheets were cut and then aligned so they can be consolidated, and the cure schedule employed was heating at a rate of 8 °C/minute up to 170 °C, followed by heating at 170 °C for two hours, followed by heating at a rate of 8 °C/minute up to 190 °C under a consolidation pressure of 80 bar/cm2. The resulting laminate had the following properties:
Table 7 - Catalysed reinforced material physical properties
Physical Property Compound A (1 PHR Testing Method
Catalyst)
Density / g/cm3 1.95 ISO 1183
Flexural strength / MPa 500 ISO 178
E-modulus (flexural strength) / 35 ISO 178
GPa
Tensile strength / MPa 400 ISO 527
Compression strength 500 ISO 604 perpendicular to lamination I MPa
Breakdown voltage / KV 75 I EC 60243-1
(d=25mm)*
Flammability 5mm VO** UL 94 * (d=25mm) denotes that both electrodes have a 25 mm diameter.
** VO = Burning stops within 10 seconds after two applications of ten seconds each of a flame/vertical bum to a test bar. No flaming drips are observed.
Thus, furan derived benzoxazines are highly compatible with curing catalysts and may readily provide reinforced materials having desirable properties derived from furan derived benzoxazines, prepared with the assistance of a curing catalyst.
Example 9 - Preparation of compound E - ortho-substituted benzoxazine
Figure imgf000059_0001
Compound E
An ortho-substituted benzoxazine compound was prepared in order to establish that an ortho-substituted benzoxazine can provide suitable polymerisation properties.
184 grams toluene were added to a 1 litre, round-bottomed flask equipped with a condenser, mechanical stirrer, addition funnel and thermometer.
328 grams [4 Mols] of a 36.5% aqueous formaldehyde solution was added next and the agitator started. 210 grams [1 Mol] PACM, bis-(p-aminocyclohexyl) methane was added to the flask over a 60-minute period controlling the temperature below 60°C throughout the addition.
248 grams [2Mols] of 2-M ethoxy phenol [guaiacol] was added in 8 aliquots maintaining the temperature below 50C throughout the 30-minute period. The mixture was held for a further 30 minutes before being heated to azeotrope up to 120°C removing water. Once at 120°C the flask was reconfigured for vacuum distillation and distilled under vacuum to 120°C recovering the toluene. The material was then discharged directly from the flask as a brittle solid having the following properties.
Table 8 - Compound E properties
Figure imgf000060_0002
As can be seen by comparison of Examples 5 and 9, whilst compound E is not within the scope of the present invention, compound E nevertheless demonstrates that orthosubstituted di-functional benzoxazine compounds are capable of polymerisation at a comparable rate to conventional di-functional benzoxazines, as well as analogous non- ortho-substituted furan derived di-functional benzoxazines.
EXAMPLE 10 - Preparation of Compound F
Figure imgf000060_0001
102 grams (1 mols) of cadaverine was added to a 1 litre, round-bottomed flask equipped with a condenser, mechanical stirrer, addition funnel and thermometer.
The flask was set for atmospheric reflux, agitator started and gently heated to 20°C. A nitrogen blanket applied and 384 grams (4 mols) furfuraldehyde was slowly charged over a 60-minute period controlling the temperature [exotherm] below 45°C throughout the addition process. Once charged the contents were cooled back to 30°C and 248 grams (2 Mols) of guaiacol was added in 4 aliquots over 60 minutes maintaining the temperature at 50°C [No exotherm observed]. The contents were held for 30 minutes at 50°C before raising the temperature to 100°C for 30 minutes. The flask was configured for distillation and the temperature increased to 120°C receiving distillate during the temperature ramping. At 120°C the flask was reconfigured for vacuum distillation and distilled under 20” vacuum for 120 minutes. The product was then cooled and evaluated to yield compound F. Table 9 - Properties of Compound F
Figure imgf000061_0001
Cure 1 - 1 hour at 180°C plus 2 hours at 200°C.

Claims

CLAIMS:
1 . A compound of formula (I):
Figure imgf000062_0001
wherein each R group is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- C3 to C10 cycloalkyl, Ci to C20 alkyl-C3 to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1 , -NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, - C(O)NHR1, -C(0)NR12, -O(CO)H, -O(CO)R1 , -NH(CO)H, -NH(CO)R1 , -NR1(CO)H, - NR1(CO)R1 , -SH, -SR1 , -SO2H, -SO2R1, -SO3R1, -SO3H, -SiR1 3, -NO2, -ON, -F, -Cl, -Br, - I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein each R1 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- C3 to C10 cycloalkyl, Ci to C20 alkyl-C3 to C heterocycloalkyl, Ci to C20 alkoxy, Ci to C20 alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R2 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, -OH, -NH2, -OC1 to C20 alkyl, -NHC1 to C20 alkyl, -N(Ci to C20 alkyl)2, -NO2, -CN, -F, -Cl, -Br, and -I; wherein R3 is independently selected from: Ci to Ce alkyl, Ci to Ce alkenyl, Ci to Ce alkoxy, Ci to Ce alkyloxy, -C(O)OH, -C(O)O-Ci to Ce alkyl, Ci to Ce alkyl-(O)O-H, Ci to Ce alkyl-(O)O-Ci to Ce alkyl, and -OH; wherein R4 is independently either hydrogen or is selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-C3 to C20 cycloalkyl, Ci to C20 alkyl-C3 to C heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1 , -NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, - C(O)NHR1, -C(O)NR12, -O(CO)H, -O(CO)R1 , -NH(CO)H, -NH(CO)R1 , -NR1(CO)H, - NR1(CO)R1 , -SH, -SR1 , -SO2H, -SO2R1, -SO3R1, -SO3H, -SiR1 3, -NO2, -ON, -F, -Cl, -Br, -
1. Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; with the proviso that at least one R4 group is other than hydrogen; wherein L1 is a divalent hydrocarbyl linker comprising 1 to 50 carbon atoms; wherein x is independently 0, 1 , 2 or 3 when R4 is hydrogen, and x is independently 0, 1 or 2 when R4 is other than hydrogen; and wherein n is independently 0, 1 , 2 or 3.
2. The compound of Claim 1 , wherein one or both benzene rings of the benzoxazines are substituted with R groups at the 3-position and/or the 5-position, relative to the oxygen of the benzoxazine ring.
3. The compound of Claim 1 or Claim 2 wherein both x values < 1 , and preferably wherein both x values are the same, and/or wherein both benzene rings of the benzoxazines are substituted with the same R group(s), more preferably wherein both x values = 0.
4. The compound of any preceding claim, wherein L1 comprises 2 to 50 carbon atoms, 3 to 50 carbon atoms, 5 to 50 carbon atoms, 2 to 40 carbon atoms, 3 to 40 carbon atoms, 5 to 40 carbon atoms, 2 to 30 carbon atoms, 3 to 30 carbon atoms, 5 to 30 carbon atoms, 2 to 20 carbon atoms, 3 to 20 carbon atoms, or 5 to 20 carbon atoms.
5. The compound of any preceding claim, wherein L1 comprises at least one of: i) a heteroatom selected from nitrogen, oxygen, sulphur and silicon; ii) a double or triple carbon-carbon bond; or iii) an aromatic ring, heteroaromatic ring, and/or non-aromatic ring.
6. The compound of any preceding claim, wherein L1 is derived from the reaction of a diamine NH2-L1-NH2, when NH2-L1-NH2 is selected from: ethylene diamine, diethylene triamine, triethylene tetramine, hexamethylene diamine, 2,2,4-trimethyl hexamethylene diamine, 2,4,4-trimethyl hexamethylene diamine, a Jeffamine, metaxylylene diamine, 1 ,3-bis(aminomethyl) cyclohexane, benzene-1 ,4-diamine, isophorone diamine, diaminocyclohexane, 4-Cyclohexene-1 ,2-diamine, 3-Hexyne-1 ,6-diamine, bis-(p- aminocyclohexyl) methane or methylene dianiline; preferably when NH2-L1-NH2 is selected from: ethylene diamine, hexamethylene diamine, 2,2,4-trimethyl hexamethylene diamine, 2,4,4-trimethyl hexamethylene diamine, a Jeffamine, metaxylylene diamine, 1 ,3-bis(aminomethyl) cyclohexane, benzene-1 ,4-diamine, isophorone diamine, diaminocyclohexane, bis-(p-aminocyclohexyl) methane and methylene dianiline.
7. The compound of any preceding claim, wherein the compound has the structure:
Figure imgf000064_0001
wherein ring A and ring B are independently either aromatic or saturated 6 membered carbon rings, preferably wherein rings A and B are both saturated rings; wherein R5 is a divalent Ci to C alkyl group, preferably wherein R5 is a methylene group; and wherein R, R3, R4, x, and n are independently as defined in any one of Claims 1 to 6, preferably where both x values = 0 and/or wherein all n values = 0.
8. A compound of formula (II):
Figure imgf000065_0001
wherein each R group is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- C3 to C20 cycloalkyl, Ci to C20 alkyl-C3 to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1 , -NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, - C(O)NHR1, -C(0)NR12, -O(CO)H, -O(CO)R1 , -NH(CO)H, -NH(CO)R1 , -NR1(CO)H, - NR1(CO)R1 , -SH, -SR1 , -SO2H, -SO2R1, -SO3R1, -SO3H, -SiR1 3, -NO2, -ON, -F, -Cl, -Br, - I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein each R1 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- C3 to C10 cycloalkyl, Ci to C20 alkyl-C3 to C heterocycloalkyl, Ci to C20 alkoxy, Ci to C20 alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R2 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, -OH, -NH2, -OC1 to C20 alkyl, -NHC1 to C20 alkyl, -N(Ci to C20 alkyl)2, -NO2, -CN, -F, -Cl, -Br, and -I; wherein R3 is independently selected from: Ci to Ce alkyl, Ci to Ce alkenyl, Ci to C6 alkoxy, Ci to C6 alkyloxy, -C(O)OH, -C(O)O-Ci to C6 alkyl, Ci to C6 alkyl-(O)O-H, Ci to Ce alkyl-(O)O-Ci to Ce alkyl, and -OH; wherein R4 is a direct bond to L2, or R4 is independently either hydrogen or is selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-Cs to C20 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1, - NR1 2, -C(O)OH, -C(O)OR1, -C(O)NH2, -C(O)NHR1, -C(O)NR12, -O(CO)H, -O(CO)R1, - NH(CO)H, -NH(CO)R1, -NR1(CO)H, -NR1(CO)R1, -SH, -SR1, -SO2H, -SO2R1, -SO3R1, - SO3H, -SiR13, -NO2, -ON, -F, -Cl, -Br, -I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; with the proviso that at least one R4 group is other than hydrogen; wherein R6 is independently a monovalent group selected from -H, -OH, or a hydrocarbyl group comprising 1 to 50 carbon atoms; wherein L2 is a direct bond, a divalent group selected from: C(O), O, S, S(O), S(O)2, or a hydrocarbyl linker comprising 1 to 50 carbon atoms; wherein y is independently 0, 1 , or 2 when R4 is hydrogen or is a direct bond to L2, and y is independently 0 or 1 when R4 is other than hydrogen or a direct bond to L2; and wherein n is independently 0, 1 , 2 or 3.
9. The compound of Claim 8, wherein L2 is attached at the 4-position, relative to the benzoxazine oxygen; and/or wherein L2 is selected from S(O)2, CH2, C(CH3)2, or a divalent benzene ring.
10. The compound of Claim 8 or Claim 9, wherein both y values are the same, and/or wherein both benzene rings of the benzoxazines are substituted with the same R group(s), more preferably wherein both y values = 0.
11. The compound of any preceding claim wherein each R4 group is independently either hydrogen or is selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-Cs to C10 cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1, - NR1 2, -O(CO)H, -O(CO)R1, -NH(CO)H, -NH(CO)R1, -NR1(CO)H, -NR1(CO)R1, -SH, -SR1, -SiR13, -F, -Cl, -Br, -I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein R1 is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-Cs to C20 cycloalkyl, Ci to C20 alkyl-Cs to Cw, heterocycloalkyl, Ci to C20 alkoxy, Ci to C20 alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; and wherein R2 is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, -OH, -NH2, -OC1 to C20 alkyl, -NHC1 to C20 alkyl, -N(Ci to C20 alkyl)2, -F, -Cl, -Br, or -I; preferably wherein each R4 group is independently either hydrogen or is selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1 , -NH2, -NHR1 , -NR1 2, Ce to C14 aryl optionally substituted with one or more R2 group, or C2 to C9 heteroaryl optionally substituted with one or more R2 group; preferably -OH; wherein R1 is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl or C2 to C20 alkenyl; wherein R2 is independently selected from: Ci to C20 alkyl, -OH, -NH2, -OC1 to C20 alkyl, -NHC1 to C20 alkyl or -N(Ci to C20 alkyl)2, preferably -OH; more preferably wherein each R4 group is either hydrogen or -OMe.
12. The compound of any preceding claim wherein both R4 groups are other than hydrogen, more preferably wherein both R4 are other than hydrogen and are the same.
13. A compound of formula (III):
Figure imgf000067_0001
Wherein R is selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl- Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-C3 to Cw cycloalkyl, Ci to C20 alkyl-Cs to C10 heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, - OR1 , -NH2, -NHR1 , -NR12, -C(O)OH, -C(O)OR1 , -C(O)NH2, -C(O)NHR1, -C(0)NR12, - O(CO)H, -O(CO)R1 , -NH(CO)H, -NH(CO)R1 , -NR1(CO)H, -NR1(CO)R1, -SH, -SR1, - SO2H, -SO2R1 , -SO3R1, -SO3H, -SiR1 3, -NO2, -ON, -F, -Cl, -Br, -I, C6 to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein each R1 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl- Cs to C10 cycloalkyl, Ci to C20 alkyl-C3 to C heterocycloalkyl, Ci to C20 alkoxy, Ci to C20 alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R2 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, -OH, -NH2, -OC1 to C20 alkyl, -NHC1 to C20 alkyl, -N(Ci to C20 alkyl)2, -NO2, -CN, -F, -Cl, -Br, and -I; wherein R3 is independently selected from: Ci to Ce alkyl, Ci to Ce alkenyl, Ci to C6 alkoxy, Ci to C6 alkyloxy, -C(O)OH, -C(O)O-Ci to C6 alkyl, Ci to C6 alkyl-(O)O-H, Ci to Ce alkyl-(O)O-Ci to Ce alkyl, and -OH; wherein R6 is independently a monovalent group selected from -H, -OH, or a hydrocarbyl group comprising 1 to 50 carbon atoms; and wherein n is independently 0, 1 , 2 or 3.
14. The compound of any preceding claim, wherein each R group is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-Cs to C10 cycloalkyl, Ci to C20 alkyl-Cs to Cw heterocycloalkyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1 , -NH2, -NHR1, -NR1 2, -O(CO)H, - O(CO)R1, -NH(CO)H, -NH(CO)R1, -NR1(CO)H, -NR1(CO)R1, -SH, -SR1 , -SiR1 3, -F, -Cl, - Br, -I, Ce to C14 aryl optionally substituted with one or more R2 group, and C2 to C9 heteroaryl optionally substituted with one or more R2 group; wherein R1 is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyl-Ce to C14 aryl, Ci to C20 alkyl-C2 to C9 heteroaryl, Ci to C20 alkyl-Cs to C20 cycloalkyl, Ci to C20 alkyl-Cs to Cw, heterocycloalkyl, Ci to C20 alkoxy, Ci to C20 alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; and wherein R2 is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, -OH, -NH2, -OC1 to C20 alkyl, -NHC1 to C20 alkyl, -N(Ci to C20 alkyl)2, -F, -Cl, -Br, or -I; preferably wherein each R group is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1, -NH2, -NHR1, -NR1 2, Ce to C14 aryl optionally substituted with one or more R2 group, or C2 to C9 heteroaryl optionally substituted with one or more R2 group; preferably -OH; wherein R1 is independently selected from: Ci to C20 alkyl, C3 to C20 cycloalkyl or C2 to C20 alkenyl; wherein R2 is independently selected from: Ci to C20 alkyl, -OH, -NH2, -OC1 to C20 alkyl, -NHC1 to C20 alkyl or -N(Ci to C20 alkyl)2, preferably -OH.
15. The compound of any preceding claim, wherein R3 is independently selected from: Ci to Ce alkyl, Ci to Ce alkoxy, Ci to Ce alkyloxy, and -OH, preferably -CH3, -CH2OH, or - CH2OCH3.
16. The compound of any preceding claim, wherein all n values < 1 , and preferably wherein all n values are the same, and/or wherein all R3 groups are the same, and/or wherein all R3 groups are attached at the position ortho to the furan oxygen; more preferably wherein all n values = 0.
17. The compound of any one of Claims 8 to 16 wherein, wherein R6 is independently selected from: -H, -OH, Ci to C20 alkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, Ce to C14 aryl, and C2 to C9 heteroaryl; wherein R6 is optionally substituted with one or more R7 groups;
Wherein R7 is independently selected from: Ci to C20 alkyl, Ci to C20 haloalkyl, C3 to C20 cycloalkyl, C3 to C20 heterocycloalkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, Ci to C20 alkyloxy, Ci to C20 alkylamino, -OH, -OR1 , -NH2, -NHR1 , -NR1 2, -C(O)OH, -C(O)OR1 , - C(O)NH2, -C(O)NHR1 , -C(O)NR12, -O(CO)H, -O(CO)R1 , -NH(CO)H, -NH(CO)R1 , - NR1(CO)H, -NR1(CO)R1 , -SH, -SR1, -SO2H, -SO2R1 , -SO3R1, -SO3H, -SiR1 3, -NO2, -CN, - F, -Cl, -Br, -I, Ce to C14 aryl, and C2 to C9 heteroaryl.
18. A process for preparing a compound of formula (I) according to any one of Claims 1 to 7, said method comprising: i) providing a diamine NH2-L1-NH2 wherein L1 is as defined in any one of Claims 1 to 7; ii) adding at least one furfuraldehyde substituted with n R3 groups, and one or more phenolic compounds independently substituted by R4 at one ortho position relative to the phenolic -OH group and independently substituted with x R groups, with the proviso that each of the one or more phenolic compounds has an unsubstituted position ortho to the phenolic -OH and at least one other unsubstituted position, wherein R, R3, R4 and n are as defined in any one of Claims 1 to 7, 11 to 12 and 14 to 16, and x = 0, 1 , 2 or 3, and wherein R4 in at least one of the one or more phenolic compounds is other than hydrogen; and iii) forming a compound of formula (I).
19. The process of Claim 18 wherein the one or more phenolic compounds consists of one or more phenolic compounds wherein R4 is other than hydrogen, preferably wherein R4 is the same, more preferably wherein the one or more phenolic compounds consists of one phenolic compound wherein R4 is other than hydrogen, most preferably wherein R4 is -OMe.
20. The process of Claim 18 or Claim 19, wherein the molar ratio of the diamine to the at least one furfuraldehyde is from 1 :2 to 1 :20, preferably from 1 :3 to 1 :10, more preferably from 1 :4 to 1 :8; and/or wherein the molar ratio of the diamine to the one or more phenolic compound is from 1 :1 to 1 :5, preferably from 1 :1.5 to 1 :4, more preferably from 1 :2 to 1 :3.
21. A process for preparing a compound of formula (II) or (III) according to any one of Claims 8 to 17, said method comprising: i) providing: A) a bisphenol compound substituted with y R groups on each benzene ring and comprising a linker L2, and wherein the bisphenol compound is substituted with one R4 group other than hydrogen at an orthoposition relative to the phenolic -OH on one or each benzene ring of the bisphenol compound, with the proviso that each benzene ring of the bisphenol compound has an unsubstituted position ortho to the phenolic - OH and at least one other unsubstituted position; or B) a benzene-1 ,3-diol substituted with 1 R group at the 5-position; wherein R, R4, and L2 are as defined in any one of Claims 8 to 17, and y = 0, 1 or 2; ii) contacting the compound from step i) with at least one furfuraldehyde substituted with n R3 groups, and at least one primary amine substituted with one R6 group, wherein n, R3 and R6 are as defined in any one of Claims 8 to 17; and iii) forming a compound of formula (II) or (III).
22. The process of Claim 21 wherein the bisphenol compound is substituted with one R4 group at the ortho-position relative to the phenolic -OH on each benzene ring, preferably wherein both R4 groups are the same, more preferably wherein both R4 groups are - OMe.
23. The process of Claim 21 or Claim 22, wherein the molar ratio of the bisphenol compound or benzenediol to the at least one furfuraldehyde is from 1 :2 to 1 :20, preferably from 1 :3 to 1 :10, more preferably from 1 :4 to 1 :8; and/or wherein the molar ratio of the bisphenol compound or benzenediol to the at least one primary amine is from 1 :1 to 1 :5, preferably from 1 :1 .5 to 1 :4, more preferably from 1 :2 to 1 :3.
24. The process of any one of Claims 18 to 23, wherein either; the diamine or at least one primary amine, is contacted with the at least one furfuraldehyde prior to the addition of either; the one or more phenolic compound, or the bisphenol compound or benzenediol, respectively.
25. The process of any one of Claims 18 to 23, wherein either; the diamine or at least one primary amine, is contacted with a portion of the at least one furfuraldehyde prior to the addition of either; the one or more phenolic compound, or the bisphenol compound or benzenediol, respectively, wherein the remaining furfuraldehyde is added after and/or simultaneously to addition of either; the one or more phenolic compound, or the bisphenol compound or benzenediol, respectively.
26. The process of any one of Claims 18 to 23, wherein either; the diamine or at least one primary amine, is contacted with either; the one or more phenolic compound, or the bisphenol compound or benzenediol, respectively, and the at least one furfuraldehyde simultaneously.
27. The process of any one of Claims 18 to 26, wherein two different phenolic compounds or two different primary amines are added separately; or wherein only one primary amine is added.
28. A resin composition comprising the compound of any one of Claims 1 to 17.
29. Use of a compound according to any one of Claims 1 to 17 or a resin composition according to Claim 28 to reinforce a material, preferably a fibrous material, more preferably glass fibre, carbon fibre or flax.
30. The use according to Claim 29 wherein a catalyst or co-reactant is used to reduce the activation temperature of a polymerisation reaction of the compound of any one of Claims 1 to 17, preferably wherein the catalyst is ferric chloride.
31. A method for preparing a reinforced material, said method comprising: a) contacting a material to be reinforced with a compound as defined in any one of Claim 1 to 17, or with a resin composition as defined in Claim 28; and b) allowing said compound to self-polymerise to form a reinforced material, preferably wherein the material to be reinforced is a fibrous material, more preferably glass fibre, carbon fibre or flax.
32. A reinforced material prepared, or preparable, by the method of Claim 31.
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