WO2017098229A1

WO2017098229A1 - Novel porous materials

Info

Publication number: WO2017098229A1
Application number: PCT/GB2016/053838
Authority: WO
Inventors: Andrew Cooper; Buyi LI; Jose Antonio LOPEZ SANCHEZ
Original assignee: The University Of Liverpool
Priority date: 2015-12-08
Filing date: 2016-12-06
Publication date: 2017-06-15
Also published as: GB201521640D0

Abstract

The present invention relates to novel porous materials. More specifically, the present invention relates to functionalised hypercrosslinked porous polymeric materials. The present invention also relates to processes for the preparation of these materials and to the use of these materials in catalysis and in gas storage.

Description

NOVEL POROUS MATERIALS

INTRODUCTION

[0001] The present invention relates to functionalised hypercrosslinked porous polymeric materials. The present invention also relates to processes for the preparation of these materials and to the use of these materials in applications, such as, for example, catalysis, adsorption, separation and gas storage.

BACKGROUND OF THE INVENTION

[0002] There is a need for inexpensive, functionalised and highly porous materials for use in industrial applications such as gas storage, catalysis and sensing. The high operating costs, environmental impacts and health implications that are often associated with such industrial processes has fuelled demand for new functionalised materials that are more efficient and cheaper to produce and use.

[0003] In recent years, Metal Organic Frameworks (MOFs) have been investigated for use in such industrial processes. MOFs are a class of crystalline materials made from the coordination of metal ions to a variety of organic ligands. They are typically characterised by their structure, which comprises a network of metal-organic ligand coordination complexes that provide a rigid open framework comprising a multitude of well-defined pores. The properties of MOFs, namely their porosity, stability and low cost, have resulted in them finding applications in numerous fields such as gas storage, separation and catalysis.

[0004] Although MOFs have been shown to be useful in a number of industrial applications, there still remains a need for new and improved materials for application such as gas storage, separation and catalysis. In particular, there is a need for new materials that can be used to efficiently absorb toxic gases, especially gases in low concentrations (parts per million or below). For example, ammonia has a recommended CAL-OSHA permissible exposure limit of just 25 ppnr¹ and, like other small volatile amines with low recommended exposure limits, it has proven challenging to absorb ammonia through conventional means.

[0005] Although ammonia absorption by MOFs has been reported in the literature, in many cases the absorption is low and the inclusion of Lewis acidic moieties in the MOFs often result in them suffering from poor stability and high water sensitivity.^{1 2}

[0006] Thus, in one instance, there remains a need for new porous materials that are capable of absorbing and storing toxic gases such as ammonia and other small volatile amines. [0007] In addition to the need for new materials for gas absorption, there is also a need for new catalyst materials, including acid catalysts, base catalysts or mixed acid and base catalysts.

[0008]There is a particular need for new acid catalysts for use in the transformation of biomass (such as cellulose) into useful building blocks (such as glucose). The demand for renewable sources of energy has fuelled the need for cheap, stable, and efficient means for renewably producing energy, of which the hydrolysis of cellulose into fermentable sugars, such as glucose, has shown promise.^{3 4} Traditional homogeneous catalytic processes for hydrolysing cellulose using, for example, mineral acids such as H₂S0₄, HCI, and HF,^{5 7} suffer a series of problems, including problems with product separation from acid waste, poor catalyst recyclability, the corrosion of equipment, high energy consumption and environmental implications that arise due to the need to treat the hazardous waste sulphuric acid effluent.^{8 9} The use of MOFs and other solid acid based matrixes (such as carbon, zeolites and silicas)^10- ¹² as acidic catalysts in the hydrolysis of cellulose have been explored, however such materials often suffer from poor physiochemical stability, sensitivity to water, incompatible pore sizes and restrictive rigidity, which has rendered them incompatible for widespread use. Furthermore, the functionalisation of carbon with acidic groups, such as S0₃H groups, is mainly accomplished by hazardous processes that generate a large amount of waste, for instance, by heating carbon in large volumes of concentrated H₂S0₄, or by fuming in H₂S0₄ (ca. 20 ml per 1 g solid) above 150 Ό.

[0009] Accordingly, there also remains a need for new solid acid catalysts for the hydrolysis of cellulose that are cheap to produce, stable, efficient and recyclable.

[0010] The present invention was devised with the foregoing in mind.

SUMMARY OF THE INVENTION

[0011] According to a first aspect of the present invention there is provided a process for the preparation of a functionalised hypercrosslinked porous polymeric material, the process comprising the steps of:

i) providing a hypercrosslinked porous polymeric material comprising a plurality of aromatic monomer units, that are crosslinked by reacting the aromatic monomer units with a crosslinking molecule; and

ii) reacting the hypercrosslinked porous polymeric material of step (i) to

introduce one or more functional groups; with the proviso that the aromatic monomer of step (i) does not comprise a vinyl group.

[0012] According to a second aspect of the present invention, there is provided a process for the preparation of a functionalised hypercrosslinked porous polymeric material, the process comprising the steps of:

i) providing a hypercrosslinked porous polymeric material comprising a plurality of aromatic monomer units comprising one or more aromatic rings, formed by reacting, and subsequently crosslinking, the aromatic rings of adjacent aromatic monomer units with a crosslinking molecule; and

ii) reacting the hypercrosslinked porous polymeric material of step (i) to

introduce one or more functional groups.

[0013] According to another aspect of the present invention, there is provided a functionalised hypercrosslinked porous polymeric material obtainable by the process as defined herein.

[0014] According to another aspect of the present invention, there is provided the use of a functionalised hypercrosslinked porous polymeric material as defined herein in catalysis.

[0015] According to another aspect of the present invention, there is provided the use of a functionalised hypercrosslinked porous polymeric material as defined herein in gas adsorption.

[0016] According to another aspect of the present invention, there is provided the use of a functionalised hypercrosslinked porous polymeric material as defined herein as a solid acid catalyst.

[0017] According to another aspect of the present invention, there is provided the use of a functionalised hypercrosslinked porous polymeric material as defined herein as a solid base catalyst.

[0018] According to another aspect of the present invention, there is provided the use of a functionalised hypercrosslinked porous polymeric material as defined herein as an ion- exchange resin.

[0019] According to another aspect of the present invention, there is provided the use of a functionalised hypercrosslinked porous polymeric material as defined herein in the hydrolysis of oligo- and polysaccharides.

[0020] According to another aspect of the present invention, there is provided the use of a functionalised hypercrosslinked porous polymeric material as defined herein in the catalysis of base promoted organic reactions. [0021] According to another aspect of the present invention, there is provided the use of a functionalised hypercrosslinked porous polymeric material as defined herein in the catalytic conversion of glucose to 5-hydroxymethylfurfural.

[0022] According to another aspect of the present invention, there is provided the use of a functionalised hypercrosslinked porous polymeric material as defined herein in the absorption and/or storage of ammonia.

[0023] According to another aspect of the present invention, there is provided the use of a functionalised hypercrosslinked porous polymeric material as defined herein in the purification of water.

[0024] According to another aspect of the present invention, there is provided the use of a functionalised hypercrosslinked porous polymeric material, as defined herein, in the separation of alkanes from alkane/alkene mixtures.

[0025] According to another aspect of the present invention, there is provided the use of a functionalised hypercrosslinked porous polymeric material comprising fluorobenzene monomer units as a proton conductor.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

[0026] Throughout the description and claims of this specification, the words "comprise" and "contain" and variations of them mean "including but not limited to", and they are not intended to (and do not) exclude other moieties, additives, components, integers or steps. Throughout the description and claims of this specification, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.

[0027] Features, integers, characteristics, compounds, chemical moieties or groups described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. The invention is not restricted to the details of any foregoing embodiments. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

[0028] Unless otherwise stated, the following terms used in the specification and claims have the following meanings set out below.

[0029] In this specification the term "alkyl" includes both straight and branched chain alkyl groups. References to individual alkyl groups such as "propyl" are specific for the straight chain version only and references to individual branched chain alkyl groups such as "isopropyl" are specific for the branched chain version only. For example, "(1 -6C)alkyl" includes (1 - 4C)alkyl, (1 -3C)alkyl, propyl, isopropyl and f-butyl.

[0030] The term "(m-nC)" or "(m-nC) group" used alone or as a prefix, refers to any group having m to n carbon atoms.

[0031] Unless otherwise specified, the term "alkoxy" as used herein include reference to -O- alkyl, wherein alkyl is straight or branched chain and comprises 1 , 2, 3, 4, 5 or 6 carbon atoms. In one class of embodiments, alkoxy has 1 , 2, 3 or 4 carbon atoms. This term includes reference to groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentoxy, hexoxy and the like.

[0032] Unless otherwise specified, the term "aryl" as used herein includes reference to an aromatic ring system comprising 6, 7, 8, 9 or 10 ring carbon atoms. Aryl is often phenyl but may be a polycyclic ring system, having two or more rings, at least one of which is aromatic. This term includes reference to groups such as phenyl, naphthyl and the like.

[0033] Unless otherwise specified, the term "halogen" or "halo" as used herein includes reference to F, CI, Br or I. In a particular, halogen may be F or CI, of which CI is more common.

[0034] The term "heteroaryl" or "heteroaromatic" means an aromatic mono-, bi-, or polycyclic ring incorporating one or more (for example 1 -4, particularly 1 , 2 or 3) heteroatoms selected from nitrogen, oxygen or sulfur. The term heteroaryl includes both monovalent species and divalent species. Examples of heteroaryl groups are monocyclic and bicyclic groups containing from five to twelve ring members, and more usually from five to ten ring members. The heteroaryl group can be, for example, a 5- or 6-membered monocyclic ring or a 9- or 10- membered bicyclic ring, for example a bicyclic structure formed from fused five and six membered rings or two fused six membered rings. Each ring may contain up to about four heteroatoms typically selected from nitrogen, sulfur and oxygen. Typically the heteroaryl ring will contain up to 3 heteroatoms, more usually up to 2, for example a single heteroatom. In one embodiment, the heteroaryl ring contains at least one ring nitrogen atom. The nitrogen atoms in the heteroaryl rings can be basic, as in the case of an imidazole or pyridine, or essentially non-basic as in the case of an indole or pyrrole nitrogen. In general the number of basic nitrogen atoms present in the heteroaryl group, including any amino group substituents of the ring, will be less than five.

[0035] Examples of heteroaryl include furyl, pyrrolyl, thienyl, oxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1 ,3,5-triazenyl, benzofuranyl, indolyl, isoindolyl, benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzothiazolyl, indazolyl, purinyl, benzofurazanyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, pteridinyl, naphthyridinyl, carbazolyl, phenazinyl, benzisoquinolinyl, pyridopyrazinyl, thieno[2,3-b]furanyl, 2H-furo[3,2-b]-pyranyl, 5H-pyrido[2,3-d]-o-oxazinyl, 1 H-pyrazolo[4,3-d]-oxazolyl, 4H-imidazo[4,5-d]thiazolyl, pyrazino[2,3-d]pyridazinyl, imidazo[2,1 -b]thiazolyl, imidazo[1 ,2-b][1 ,2,4]triazinyl. "Heteroaryl" also covers partially aromatic bi- or polycyclic ring systems wherein at least one ring is an aromatic ring and one or more of the other ring(s) is a non-aromatic, saturated or partially saturated ring, provided at least one ring contains one or more heteroatoms selected from nitrogen, oxygen or sulfur. Examples of partially aromatic heteroaryl groups include for example, tetrahydroisoquinolinyl, tetrahydroquinolinyl, 2-oxo- 1 ,2,3,4-tetrahydroquinolinyl, dihydrobenzthienyl, dihydrobenzfuranyl, 2,3-dihydro- benzo[1 ,4]dioxinyl, benzo[1 ,3]dioxolyl, 2,2-dioxo-1 ,3-dihydro-2-benzothienyl, 4,5,6,7- tetrahydrobenzofuranyl, indolinyl, 1 ,2,3,4-tetrahydro-1 ,8-naphthyridinyl,

1 ,2,3,4-tetrahydropyrido[2,3-£>]pyrazinyl and 3,4-dihydro-2/- -pyrido[3,2-£>][1 ,4]oxazinyl.

[0036] Unless otherwise specified, the term "phosphate" means an organophosphorus compound of the formula -0-PO(OR)₂, wherein R may be a hydrogen or any suitable organic substituent, such as, for example, alkly, cycloalkyl or phenyl. Thus the term phosphate will be understood as referring to hydrogen sulfate, sulfuric acid, methyl sulfate, and the like.

[0037] Unless otherwise specified, the term "sulfate" means an organosulfur compound of the formula -0-S0₂(OR), wherein R may be a hydrogen or any suitable organic substituent, such as, for example, alkly, cycloalkyl or phenyl. Thus the term sulfate will be understood as referring to dihydrogen phosphate, hydrogen phosphate, dimethyl phosphate, and the like.

[0038] Unless otherwise specified, the term "substituted" as used herein in reference to a moiety means that one or more, especially up to 5, more especially 1 , 2 or 3, of the hydrogen atoms in said moiety are replaced independently of each other by the corresponding number of the described substituents. The term "optionally substituted" as used herein means substituted or unsubstituted.

[0039] It will, of course, be understood that substituents are only at positions where they are chemically possible, the person skilled in the art being able to decide (either experimentally or theoretically) without inappropriate effort whether a particular substitution is possible. For example, amino or hydroxy groups with free hydrogen may be unstable if bound to carbon atoms with unsaturated (e.g. olefinic) bonds. Additionally, it will of course be understood that the substituents described herein may themselves be substituted by any substituent, subject to the aforementioned restriction to appropriate substitutions as recognised by the skilled person.

[0040] Unless otherwise specified, the term "optionally substituted" refers to either groups, structures, or molecules that are substituted and those that are not substituted. The term "wherein a/any CH, CH₂, CH₃ group or heteroatom (i.e. NH) within a R¹ group is optionally substituted" suitably means that (any) one of the hydrogen radicals of the R¹ group is substituted by a relevant stipulated group.

[0041] Where optional substituents are chosen from "one or more" groups it is to be understood that this definition includes all substituents being chosen from one of the specified groups or the substituents being chosen from two or more of the specified groups.

[0042] Unless otherwise specified, the term "base promoted" refers to a reaction that is enhanced in the presence of a base. It will be understood that the term refers to both reactions that require a base to proceed and reactions that are improved or enhanced in the presence of a base. The base may be catalytic, and thus regenerated during the course of the reaction, or non-catalytic, and therefore consumed during the course of the reaction.

[0043] Unless otherwise specified, the term "hypercrosslinked" refers to the extensive crosslinking of several chemical entities (e.g. aromatic monomer units) with one another, mediated through multiple covalent bonds between the chemical entity and one or more suitable crosslinkers. It will be understood that hypercrosslinking differs to conventional crosslinking in regards to the degree of crosslinking, in which hypercrosslinked materials notably comprise a larger number of crosslinks. A person skilled in the art will be able to ascertain the difference between a conventional crosslinked material and hypercrosslinked material. However, typically, the term hypercrosslinked refers to a network of crosslinks wherein substantially all chemical entities (e.g. aromatic monomer units) are covalently bound to a least 2 other chemical entities (e.g. aromatic monomer units), mediated through reaction with a suitable crosslinker.

[0044] The phrase "compound of the invention" means those compounds which are disclosed herein, both generically and specifically. Processes of the present invention

[0045] As described hereinbefore, the present invention provides a process for the preparation of a functionalised hypercrosslinked porous polymeric material, the process comprising the steps of:

ii) reacting the hypercrosslinked porous polymeric material of step (i) to

introduce one or more functional groups;

with the proviso that the aromatic monomer of step (i) does not comprise a vinyl group.

[0046] In another aspect, the present invention provides a process for the preparation of a functionalised hypercrosslinked porous polymeric material, the process comprising the steps of:

ii) reacting the hypercrosslinked porous polymeric material of step (i) to

introduce one or more functional groups.

[0047] The processes of the present invention provides access to an array of novel functionalised materials. Furthermore, the novel functionalised materials provided by the processes of the present invention may be utilised in numerous applications, such as, for example, catalysis, adsorption, separation and gas storage. Accordingly, the process of the present invention may be utilised to provide novel materials for use in applications, such as catalysis and gas storage, wherein there remains a need new and improved materials.

[0048] In an embodiment, the hypercrosslinked porous polymeric material of step (i) of the process or the functionalised hypercrosslinked porous polymeric material of step (ii) of the process is impregnated with a metal ion and/or nanoparticle. In another embodiment, the functionalised hypercrosslinked porous polymeric material of step (ii) of the process is impregnated with a metal ion and/or nanoparticle. Suitably, the metal ion or nanoparticle is selected from Ru, Rh, Pd, Co, Au, Ag, Ni or Fe₃0₄. More suitably, the metal ion and/or nanoparticle is selected from Ru, Rh, Pd, Au or Ag. Yet more suitably, the metal ion and/or nanoparticle is selected from Ru, Rh, Ag or Pd. Most suitably, the metal ion and/or nanoparticle is Ru or Ag.

[0049] It will be understood that the material obtained through either step (i) or step (ii) of the process, as defined hereinabove, may be impregnated with a metal nanoparticle by any conventional technique known in the art. Suitably, the material obtained through either step (i) or step (ii) of the process is impregnated with a metal nanoparticle by stirring the material obtained from either step (i) or step (ii) of the process with a solution, or slurry, of metal nanoparticles, before removing the solvent from the solution, or slurry, and subsequently drying the remaining material.

Step ii)

[0050] Any suitable reaction conditions may be used in step (i) of the process defined herein.

[0051] The reaction conditions used in step (i) of the process will vary according to the aromatic monomer and / or crosslinker used. A person skilled in the art will be able to select suitable reaction conditions (e.g. temperature, pressures, reaction times, concentration etc.) to use in step (i) of the process.

[0052] In an embodiment, the reaction between the aromatic monomer units and the crosslinking molecule in step (i) of the process, as defined herein, is a Friedel-Crafts alkylation or Friedel-Crafts acylation. Suitably, the reaction between the aromatic monomer units and the crosslinking molecule in step (i) of the process, as defined herein, is a Friedel-Crafts alkylation.

[0053] In another embodiment, step (i) of the process of the present invention is conducted at a temperature of between 0 and 200 °C. Suitably, step (i) of the process of the present invention is conducted at a temperature of between 0 and 150 °C. More suitably, step (i) of the process of the present invention is conducted at a temperature of between 0 and 100 °C. Most suitably, step (i) of the process of the present invention is conducted at a temperature of between 25 and 100 °C.

[0054] Furthermore, step (i) of the process of the present invention may be carried out in the presence of any suitable solvent. The solvent may be used to solubilise the aromatic monomer units and crosslinking molecule and facilitate a reaction between them. Accordingly, it will be understood that the solvent selected will depend on the aromatic monomer units and crosslinking molecule selected. Moreover, certain aromatic monomer units (e.g. benzene) may themselves may act as a suitable solvent for the crosslinking molecule, and thus in certain embodiments of the present invention no solvent is required for step (i). [0055] In a particular embodiment, the solvent used in step (i) of the process is an organic solvent. More suitably, the solvent used in step (i) of the process is selected from 1 ,2- dichloroethane, dichloromethane, nitromethane, carbon disulphide, petroleum ether, nitrobenzene, tetrachloride, 1 ,1 ,2,2-tetrachioroethane. Most suitably, the solvent used in step (i) of the process is selected from 1 ,2-dichloroethane, nitromethane or carbon disulphide.

[0056] It will be appreciated that additional activating agents such as, for example, a Bronsted acid or Lewis acid may also be used together with the crosslinking molecule, as defined hereinabove, to further enhance reactivity between the aromatic monomer units and the crosslinking molecule in step (i) of the process.

[0057] Any suitable Bronsted or Lewis acid may be used as an activating agent. In an embodiment, the activating agent is selected from FeCI₃, FeBr₃, SnCU, AICI₃ or CF3CO2H. Suitably, the activating agent are FeCI₃, AICI3, and CF₃COOH.

[0058] In an embodiment, both a crosslinking molecule and an activating agent are used in step (i) of the process.

[0059] Examples of suitable processes for step (i) of the process of the present invention are described in CN104193969, the entire contents of which are incorporated herein by reference. It will be appreciated that any reaction conditions and/or embodiments disclosed in CN104193969 may be applied to step (i) of the process of the present invention.

Step (ii)

[0060] The inventors have advantageously found that functionalising the hypercrosslinked porous polymeric materials obtained from step (i) of the process with various functional groups allows access to a variety of novel porous and functionalised materials. Furthermore, the inventors have surprisingly found that the functionalisation described herein does not impede the porosity of the hypercrosslinked porous polymeric materials of step (i) of the process, and advantageously provides porous materials with properties suitable for use in applications such as, for example, catalysis, adsorption, separation and gas storage.

[0061] It will be understood that any suitable functional group may be introduced at step (ii) of the process. The functional group must be compatible with the functionality of the hypercrosslinked porous polymeric material of step (i) of the process (e.g. the functionality on the aromatic monomer units). The skilled person will be able to select suitable functional groups to be introduced in step (ii) of the process in accordance with any functionality appended to the aromatic monomer units of the hypercrosslinked porous polymeric material obtained through step (i) of the process. [0062] It will be understood that one or more functional groups may be introduced in step (ii) of the process of the present invention. Furthermore, it will be appreciated that certain functional groups introduced in step (ii) of the process may be introduced by subjecting the hypercrosslinked porous polymeric material, obtained through step (i) of the process, to one or more functionalisation reactions. Accordingly, it will be understood that the term "reacting" recited in step (ii) of the process, as defined herein, covers both a single functionalization reaction and two or more sequential functionalisation reactions.

[0063] In an embodiment, the functional groups introduced in step (ii) of the process of the present invention are introduced onto part of the hypercrosslinked porous polymeric material derived from the aromatic monomer units of step (i). In this regard, it will be appreciated that no functional groups are introduced onto the part of the hypercrosslinked porous polymeric material that is derived from the crosslinking molecule.

[0064] In an embodiment, the functional group introduced in step (ii) of the process is selected from an acid group, a basic group, a carbonyl, a nitro or a combination thereof. Suitably, the functional group introduced in step (ii) of the process is selected from S0₃H, C0₂H, PO(OH)₂, C(O), NH₂, N0₂ or a combination thereof. More suitably, the functional group introduced in step (ii) of the process is selected from S0₃H, C0₂H, PO(OH)₂, C(O), NH₂ or a combination thereof. Most suitably, the functional group introduced in step (ii) of the process is selected from SO3H, C(O), NH2 or a combination thereof.

[0065] In a particular embodiment, the functional group introduced in step (ii) of the process defined herein is an acid group. It will be understood that any suitable organic acid may be used. Suitably, the organic acid introduced in step (ii) of the process is selected from is selected from S0₃H, C0₂H or PO(OH)₂. Most suitably, the organic acid introduced in step (ii) of the process is S0₃H.

[0066] In another embodiment, the functional group introduced in step (ii) of the process, as defined herein, is an organic base. Again, it will be understood that any suitable organic base may be used. Suitably, the organic base introduced in step (ii) of the process is an amino group. Most suitably, the organic base introduced in step (ii) of the process is NH₂.

[0067] In another embodiment, the functional group introduced in step (ii) of the process, as defined herein, comprises one or more organic acid functional groups and one or more organic base functional groups. It will be appreciated that in such an embodiment one or more steps may be required to install both the organic acid functional group and the organic base functional group. Suitably, the organic acid and/or organic base may be introduced in any order.

[0068] In an embodiment, step (ii) of the process comprises the steps of: a) reacting the hypercrosslinked material of step (i) of the process to introduce one or more acidic functional groups; and

b) subsequently reacting the hypercrosslinked material of step (ii)(a) of the process to introduce one or more basic functional groups.

[0069] In another embodiment, the functional group introduced in step (ii) of the process, as defined hereinabove, comprises one or more organic acid functional groups selected from SO3H, CO2H or PO(OH)₂, and one or more amino groups. Suitably, the functional group introduced in step (ii) of the process, as defined hereinabove, comprises one or more S0₃H groups, and one or more NH₂ groups.

Hypercrosslinked polymers of the present invention

[0070] In another aspect, the present invention provides a functionalised hypercrosslinked porous polymeric material obtainable by, obtained by or directly obtained by any process of the present invention defined herein.

[0071] The functionalised hypercrosslinked porous polymeric material comprises a plurality of aromatic monomer units as defined herein that are crosslinked by reacting the aromatic monomer units with a crosslinking molecule as defined herein.

[0072] The process of the present invention advantageously provides functionalised hypercrosslinked porous polymeric material with a high surface area and pore volume.

[0073] In an embodiment, the hypercrosslinked porous polymeric materials of the present invention have a Brunauer-Emmett-Teller (BET) surface area of greater than or equal to 350 m² g ¹. Suitably, the hypercrosslinked porous polymeric materials of the present invention have a BET surface area of greater than or equal to 450 m² g ¹ , more suitably, greater than or equal to 500 m² g^~1 and most suitably greater than or equal to 550 m² g^~1.

[0074] In another embodiment, the hypercrosslinked porous polymeric materials of the present invention have a pore volume of greater than or equal 0.175 cm³ g^~1. Suitably, the hypercrosslinked porous polymeric materials of the present invention have a pore volume of greater than or equal to 0.25 cm³ g^~1 , more suitably, greater than or equal to 0.3 cm³ g^~1 and most suitably greater than or equal to 0.35 cm³ g^~1.

Aromatic monomer units

[0075] The aromatic monomer units of the present invention are organic molecules that comprise one or more aromatic rings. It will be understood by the person skilled in the art that the term "aromatic" refers to any molecule that satisfies Huckel's rule, whereby the number of delocalised electrons equals 4n+2, wherein n is zero or a positive integer. Suitably, the aromatic rings of the aromatic monomer units are electron rich, so as to facilitate better reaction with the crosslinking molecule of the present invention.

[0076] Furthermore, it will be understood that the aromatic monomer units of the present invention may comprise one or more aromatic monomer units, such that, for example, the aromatic monomer units comprise one species (e.g. benzene) or alternatively comprise a combination of two or more species (e.g. benzene and naphthalene). In the situation where the aromatic monomer units comprise two or more species, it will be understood that any suitable ratio of those species may be used.

[0077] In an embodiment, the aromatic monomer units of the present invention have a molecular weight of less than 750. Suitably, the aromatic monomer units have a molecular weight of less than 600. More suitably, the aromatic monomer units have a molecular weight of less than 500. Yet more suitably, the aromatic monomer units have a molecular weight of less than 400. Most suitably, the aromatic monomer units have a molecular weight of less than 350.

[0078] Particular aromatic monomer units of the invention may include any compound as defined hereinbefore or any compound as defined in any one of paragraphs (1 ) to (22) hereinafter:-

(1 ) the aromatic monomer units are selected from an aryl or heteroaryl, wherein each aryl or heteroaryl is optionally substituted with one or more substituents selected from (1 - 6C)alkyl, (1 -6C)alkoxy, halo, hydroxy, aryl, heteroaryl, phosphate, sulfate or NR_aRt_>, and wherein R_a and Rb are independently selected from H or (1 -4C)alkyl;

(2) the aromatic monomer units are selected from an aryl or heteroaryl, wherein each aryl or heteroaryl is optionally substituted with one or more substituents selected from (1 - 6C)alkyl, (1 -6C)alkoxy, halo, hydroxy, aryl or phosphate;

(3) the aromatic monomer units are selected from an aryl or heteroaryl, wherein each aryl or heteroaryl is optionally substituted with one or more substituents selected from (1 - 6C)alkyl, (1 -6C)alkoxy, halo, hydroxy, phenyl or phosphate;

(4) the aromatic monomer units are selected from an aryl or heteroaryl, wherein each aryl or heteroaryl is optionally substituted with one or more substituents selected from (1 - 2C)alkyl, (1 -2C)alkoxy, halo, hydroxy, phenyl or phosphate;

(5) the aromatic monomer units are selected from benzene, biphenyl, 1 ,3,5- triphenylbenzene, naphthalene, anthracene, pyrene, perylene, coronene, thiophene, pyrrole, furan, carbazole, 1 ,1 '-binaphthyl-2,2'-diyl hydrogen phosphate or 2,2'- biphenyldiol cyclic phosphate, wherein each of the aforementioned is optionally substituted with one or more substituent selected from (1 -6C)alkyl, (1 -6C)alkoxy, halo, hydroxy or NR_aRt_>, and wherein R_a and Rb are independently selected from H or (1 - 4C)alkyl;

(6) the aromatic monomer units are selected from benzene, fluorobenzene, biphenyl, 1 ,3,5-triphenylbenzene, naphthalene, anthracene, pyrene, perylene, coronene, thiophene, pyrrole, furan, 1 ,1 '-binaphthyl-2,2'-diyl hydrogen phosphate or 2,2'- biphenyldiol cyclic phosphate, wherein each of the aforementioned is optionally substituted with one or more substituent selected from (1 -6C)alkyl, (1 -6C)alkoxy, halo, hydroxy or NR_aRt_>, and wherein R_a and Rb are independently selected from H or (1 - 4C)alkyl;

(7) the aromatic monomer units are selected from benzene, biphenyl, 1 ,3,5- triphenylbenzene, naphthalene, anthracene, pyrene, perylene, coronene, thiophene, pyrrole, furan, carbazole, 1 ,1 '-binaphthyl-2,2'-diyl hydrogen phosphate or 2,2'- biphenyldiol cyclic phosphate, wherein each of the aforementioned is optionally substituted with one or more substituent selected from (1 -6C)alkyl, (1 -6C)alkoxy, halo, hydroxy;

(8) the aromatic monomer units are selected from benzene, , fluorobenzene, biphenyl, 1 ,3,5-triphenylbenzene, naphthalene, anthracene, pyrene, perylene, coronene, thiophene, pyrrole, furan, 1 ,1 '-binaphthyl-2,2'-diyl hydrogen phosphate or 2,2'- biphenyldiol cyclic phosphate, wherein each of the aforementioned is optionally substituted with one or more substituent selected from (1 -6C)alkyl, (1 -6C)alkoxy, halo, hydroxy;

(9) the aromatic monomer units are selected from benzene, biphenyl, 1 ,3,5- triphenylbenzene, naphthalene, anthracene, pyrene, perylene, coronene, thiophene, pyrrole, furan, carbazole, 1 ,1 '-binaphthyl-2,2'-diyl hydrogen phosphate or 2,2'- biphenyldiol cyclic phosphate, wherein each of the aforementioned is optionally substituted with one or more substituent selected from (1 -4C)alkyl, (1 -4C)alkoxy, halo or hydroxy;

(10) the aromatic monomer units are selected from benzene, fluorobenzene, biphenyl, 1 ,3,5-triphenylbenzene, naphthalene, anthracene, pyrene, perylene, coronene, thiophene, pyrrole, furan, 1 ,1 '-binaphthyl-2,2'-diyl hydrogen phosphate or 2,2'- biphenyldiol cyclic phosphate, wherein each of the aforementioned is optionally substituted with one or more substituent selected from (1 -4C)alkyl, (1 -4C)alkoxy, halo or hydroxy; (1 1 ) the aromatic monomer units are selected from benzene, biphenyl, 1 ,3,5- triphenylbenzene, naphthalene, anthracene, pyrene, perylene, coronene, thiophene, pyrrole, furan, carbazole, 1 ,1 '-binaphthyl-2,2'-diyl hydrogen phosphate or 2,2'- biphenyldiol cyclic phosphate, wherein each of the aforementioned is optionally substituted with one or more substituent selected from (1 -2C)alkyl, halo or hydroxy;

(12) the aromatic monomer units are selected from benzene, fluorobenzene, biphenyl, 1 ,3,5-triphenylbenzene, naphthalene, anthracene, pyrene, perylene, coronene, thiophene, pyrrole, furan, 1 ,1 '-binaphthyl-2,2'-diyl hydrogen phosphate or 2,2'- biphenyldiol cyclic phosphate, wherein each of the aforementioned is optionally substituted with one or more substituent selected from (1 -2C)alkyl, halo or hydroxy;

(13) the aromatic monomer units are selected from benzene, phenol, biphenyl, biphenol, 1 ,3,5-triphenylbenzene, naphthalene, anthracene, pyrene, perylene, coronene, thiophene, pyrrole, furan, carbazole, 1 ,1 '-binaphthyl-2,2'-diyl hydrogen phosphate or 2,2'-biphenyldiol cyclic phosphate;

(14) the aromatic monomer units are selected from benzene, fluorobenzene, phenol, biphenyl, biphenol, 1 ,3,5-triphenylbenzene, naphthalene, anthracene, pyrene, perylene, coronene, thiophene, pyrrole, furan, 1 ,1 '-binaphthyl-2,2'-diyl hydrogen phosphate or 2,2'-biphenyldiol cyclic phosphate;

(15) the aromatic monomer units are of the Formula (I), Formula (II) or Formula (III), shown below:

Formula (I) Formula (II)

Formula (III)

wherein:

q is an integer between 0 and 3; Ri is selected from (1 -6C)alkyl, (1 -6C)alkoxy, halo, hydroxy, aryl, heteroaryl or NR_aRb, wherein R_a and Rb are independently selected from H or (1 -4C)alkyl;

R₂ is selected from hydrogen or (1 -4C)alkyl;

Ring A is absent or phenyl; and

X is selected from O, NH or S;

(16) the aromatic monomer units are of the Formula (I), Formula (II) or Formula (III), shown below:

Formula (I) Formula (II)

Formula (III)

wherein:

q is an integer between 0 and 3;

Ri is selected from (1 -6C)alkyl, (1 -6C)alkoxy, halo, hydroxy or aryl; A is absent or phenyl; and

X is O, NH or S;

(17) the aromatic monomer units are of the Formula (I), Formula (II) or Formula (III), shown below:

Formula (I) Formula (II)

Formula (III)

wherein:

q is an integer between 0 and 3;

Ri is selected from (1 -4C)alkyl, (1 -4C)alkoxy, halo, hydroxy or aryl;

A is absent or phenyl; and

X is O or S;

(18) the aromatic monomer units are of the Formula (I), Formula (II) or Formula (III), shown below:

Formula (I) Formula (II)

Formula (III)

wherein:

q is an integer between 0 and 3;

Ri is selected from (1 -2C)alkyl, halo, hydroxy, phenol or phenyl; A is absent or phenyl; and

X is S;

(19) the aromatic monomer units are selected from:

wherein Ri is selected from (1 -4C)alkyl, (1 -2C)alkoxy, halo or hydroxy; (20) the aromatic monomer units are selected from:

wherein Ri is selected from (1 -2C)alkyl, halo or hydroxy;

(21 ) the aromatic monomer units are selected from benzene, fluorobenzene, biphenyl, 1 ,3,5-triphenylbenzene, naphthalene, thiophene or 1 ,1 '-binaphthyl-2,2'-diyl hydrogen phosphate.

(22) the aromatic monomer units are selected from benzene, biphenyl, 1 ,3,5- triphenylbenzene, naphthalene, thiophene or 1 ,1 '-binaphthyl-2,2'-diyl hydrogen phosphate.

[0079] The aromatic monomer units of the present invention are as defined in any one of paragraph (1 ) to (22). Suitably, the aromatic monomer units are as defined in any one of paragraphs (4) to (22). More suitably, the aromatic monomer units are as defined in any one of paragraphs (8) to (22). Yet more suitably, the aromatic monomer units are as defined in any one of paragraphs (14) to (22). Most suitably, the aromatic monomer units are as defined in any one of paragraphs (18) to (22).

Crosslinking molecule

[0080] The crosslinking molecule of the present invention reacts with the aromatic rings of one or more aromatic monomer units to covalently bind (crosslink) the two entities together. It will be understood that, in order to facilitate hypercrosslinking between the aromatic monomer units of the present invention, the crosslinking molecule needs to be capable of forming two or more covalent bonds with the aromatic rings of adjacent aromatic monomer units. Suitably, the crosslinking molecule is capable of forming two or more covalent bonds with the aromatic rings of the aromatic monomer units of the present invention. Most suitably, the crosslinking molecule is capable of forming two covalent bonds with the aromatic rings of the aromatic monomer units of the present invention. [0081] In an embodiment, the crosslinking molecule of the present invention is an electrophilic alkylating or acylating agent. It will be understood by a person skilled in the art that an electrophilic alkylating or acylating agent refers to a species capable of delivering the equivalent alkyl or acyl group (cation) to a particular substrate, notably an aromatic substrate. Suitably, the crosslinking molecule of the present invention is an alkylating or acylating agent capable of facilitating a Friedel-Crafts acylation or Friedel-Crafts alkylation with the aromatic monomer units of the present invention. Most suitably, the crosslinking molecule of the present invention is an alkylating agent capable of facilitating a Friedel-Crafts alkylation with the aromatic monomer units of the present invention.

[0082] In an embodiment, the crosslinking molecule is selected from formaldehyde, paraformaldehyde, chloromethyl methyl ether, dimethyl acetal, dichloromethane, p-xylylene dichloride, bis(chloromethyl)anthracene, 1 ,3,5-tris[4-chloromethyl)phenyl]benzene or a compound of the formula (II), shown below:

Formula (II)

wherein n is an integer between 1 and 4.

[0083] In another embodiment, the crosslinking molecule is selected from formaldehyde, paraformaldehyde, chloromethyl methyl ether, dimethyl acetal, dichloromethane, p-xylylene dichloride, 9,10-bis(chloromethyl)anthracene, 9,10- bis(bromomethyl)anthracene, 1 ,3,5-tris[4- (bromomethyl)phenyl]benzene or 1 ,3,5-tris[4-chloromethyl)phenyl]benzene. Suitably, the crosslinking molecule is selected from formaldehyde, dichloromethane, chloromethyl methyl ether or formaldehyde dimethyl acetal. Most suitably, the crosslinking molecule is formaldehyde dimethyl acetal.

[0084] The crosslinking molecule of the present invention may be present at any suitable concentration in the reaction mixture. In an embodiment, the concentration of the crosslinking molecule of the present invention is between 0.01 and 20 M. Suitably, the concentration of the crosslinking molecule of the present invention is between 0.1 and 10 M. More suitably, the concentration of the crosslinking molecule of the present invention is between 0.1 and 5 M. Yet more suitably, the concentration of the crosslinking molecule of the present invention is between 1 and 5 M.

[0085] In another embodiment, the molar ratio of the crosslinking molecule to the aromatic monomer unit is between 50:1 to 0.1 :1 . Suitably, the ratio of crosslinking molecule to the aromatic monomer unit is between 25:1 to 0.5:1 . More suitably, the ratio of crosslinking molecule to the aromatic monomer unit is between 10:1 to 1 :1 . Most suitably, the ratio of crosslinking molecule to the aromatic monomer unit is between 5:1 and 1 :1 .

[0086] It will be understood that the crosslinking molecule of the present invention may be present in the form of a solvate. Non-limiting examples of suitable solvates of the crosslinking molecule of the invention are, for example, a hydrate such as a hemi-hydrate, a mono-hydrate, a di-hydrate or a tri-hydrate or an alternative quantity thereof.

[0087] Additional activating agents such as, for example, a Bronsted acid or Lewis acid may also be used together with the crosslinking molecule, as defined hereinabove, to further enhance reactivity between the crosslinking molecule and the aromatic monomer units.

[0088] Any suitable Bronsted or Lewis acid may be used as an activating agent. In an embodiment, the activating agent is selected from FeCI₃, FeBr₃, SnCU, AICI₃ or CF3CO2H. Suitably, the activating agent is selected from FeCI₃, AICI3, and CF₃COOH. Most suitably, the activating agent is FeCI₃.

[0089] In an embodiment, both a crosslinking molecule and an activating agent are used in step (i) of the process, as defined hereinabove.

Particular embodiments

[0090] In an embodiment, the process of the present invention comprises the steps of:

i) providing a hypercrosslinked porous polymeric material comprising a plurality of aromatic monomer units, that are crosslinked by reacting the aromatic monomer units with a crosslinking molecule;

wherein the aromatic monomer unit is selected from an aryl or heteroaryl, wherein said aryl or heteroaryl is optionally substituted with one or more substituents selected from (1 -6C)alkyl, (1 -6C)alkoxy, halo, hydroxy, aryl, heteroaryl, phosphate, sulfate or NR_aRt>, and wherein R_a and Rb are independently selected from H or (1 -4C)alkyl; and

ii) reacting the hypercrosslinked porous polymeric material of step (i) to introduce one or more functional groups.

[0091] In an embodiment, the process of the present invention comprises the steps of:

i) providing a hypercrosslinked porous polymeric material comprising a plurality of aromatic monomer units, that are crosslinked by reacting the aromatic monomer units with a crosslinking molecule; wherein:

the aromatic monomer unit is selected from an aryl or heteroaryl, wherein said aryl or heteroaryl is optionally substituted with one or more substituents selected from (1 -6C)alkyl, (1 -6C)alkoxy, halo, hydroxy, aryl, heteroaryl, phosphate, sulfate or NR_aRt_>, and wherein R_a and Rb are independently selected from H or (1 -4C)alkyl; and

the crosslinking molecule is selected from formaldehyde, paraformaldehyde, chloromethyl methyl ether, dimethyl acetal, dichloromethane, p-xylylene dichloride, bis(chloromethyl)anthracene or 1 ,3,5-tris[4-chloromethyl)phenyl]benzene; and

[0092] In an embodiment, the process of the present invention comprises the steps of:

wherein:

the aromatic monomer unit is selected from an aryl or heteroaryl, wherein said aryl or heteroaryl is optionally substituted with one or more substituents selected from (1 -6C)alkyl, (1 -6C)alkoxy, halo, hydroxy, aryl, heteroaryl, phosphate or NR_aRt_>, and wherein R_a and Rb are independently selected from H or (1 -4C)alkyl; and the crosslinking molecule is selected from formaldehyde, paraformaldehyde, chloromethyl methyl ether, dimethyl acetal, dichloromethane, p-xylylene dichloride, bis(chloromethyl)anthracene or 1 ,3,5-tris[4-chloromethyl)phenyl]benzene; and

ii) reacting the hypercrosslinked porous polymeric material of step (i) to introduce one or more functional groups selected from an organic acid, an organic base, a carbonyl, a nitro or a combination thereof.

[0093] In an embodiment, the process of the present invention comprises the steps of:

the aromatic monomer unit is selected from an aryl or heteroaryl, wherein said aryl or heteroaryl is optionally substituted with one or more substituents selected from (1 -6C)alkyl, (1 -6C)alkoxy, halo, hydroxy, aryl, heteroaryl, phosphate or NR_aRt_>, and wherein R_a and Rb are independently selected from H or (1 -4C)alkyl; and the crosslinking molecule is selected from formaldehyde, paraformaldehyde, chloromethyl methyl ether or formaldehyde dimethyl acetal; and

[0094] In an embodiment, the process of the present invention comprises the steps of:

wherein:

ii) reacting the hypercrosslinked porous polymeric material of step (i) to introduce one or more functional groups selected from S0₃H, C0₂H, PO(OH)₂, C(O), NH₂, N0₂ or a combination thereof.

[0095] In an embodiment, the process of the present invention comprises the steps of:

wherein: the aromatic monomer unit is selected from

wherein Ri is selected from (1 -2C)alkyl, halo or hydroxy; and the crosslinking molecule is selected from formaldehyde, paraformaldehyde, chloromethyl methyl ether or formaldehyde dimethyl acetal; and

ii) reacting the hypercrosslinked porous polymeric material of step (i) to introduce one or more functional groups selected from S0₃H, C0₂H, PO(OH)₂, C(O), NH2, NO2 or a combination thereof.

In an embodiment, the process of the present invention comprises the steps of:

i) providing a hypercrosslinked porous polymeric material comprising a plurality of aromatic monomer units comprising one or more aromatic rings, formed by reacting, and subsequently crosslinking, the aromatic rings of adjacent aromatic monomer units with a crosslinking molecule;

wherein:

the crosslinking molecule is selected from formaldehyde, paraformaldehyde, chloromethyl methyl ether, dimethyl acetal, dichloromethane, p-xylylene dichloride, bis(chloromethyl)anthracene or 1 ,3,5-tris[4-chloromethyl)phenyl]benzene.

[0097] In an embodiment, the process of the present invention comprises the steps of:

wherein:

[0098] In an embodiment, the process of the present invention comprises the steps of:

wherein:

the aromatic monomer unit is selected from

wherein Ri is selected from (1 -2C)alkyl, halo or hydroxyl; and

the crosslinking molecule is selected from formaldehyde, paraformaldehyde, chloromethyl methyl ether or formaldehyde dimethyl acetal; and

Applications

[0099] The process of the present invention provides access to the novel functionalised materials that may be utilised in numerous applications, such as, for example, catalysis, adsorption, separation and gas storage. Accordingly, the process of the present invention may be utilised to provide novel materials for use in applications, such as, catalysis, adsorption, separation and gas storage, wherein there remains a need new and improved functionalised and porous materials.

[00100] Thus, in one aspect, there is provided the use of the functionalised hypercrosslinked porous polymeric material of the present invention in catalysis. [00101 ] It will be appreciated that catalytic reaction in which the functionalised hypercrosslinked porous polymeric material of the present invention is used in will vary depending on the functional group or groups introduced during step (ii) of the process. The person skilled in the art will be able to select suitable functional groups to introduce in step (ii) of the process of the present invention, in accordance with the intended use of the material. By way of example, a functionalised hypercrosslinked porous polymeric material comprising an organic acid functional group may be used in the catalysis of acid promoted reactions. Conversely, a functionalised hypercrosslinked porous polymeric material comprising an organic base functional group may be used in the catalysis of base promoted reactions.

[00102] In one aspect of the present invention, there is provided the use of a functionalised hypercrosslinked porous polymeric material comprising one or more organic acid functional groups, as defined herein, as a solid acid catalyst.

[00103] In another aspect, there is provided the use of a functionalised hypercrosslinked porous polymeric material comprising one or more organic acid functional groups, as defined herein, in the hydrolysis of oligo- and polysaccharides. Suitably, there is provided the use of a functionalised hypercrosslinked porous polymeric material comprising one or more organic acid functional groups, as defined herein, in the hydrolysis cellulose and/or cellulose oligomers (e.g. cellobiose, cellotriose and cellotetraose).

[00104] In another aspect, there is provided the use of a functionalised hypercrosslinked porous polymeric material, comprising one or more organic base functional groups, as defined herein, as a solid base catalyst.

[00105] In yet another aspect, there is provided the use of a functionalised hypercrosslinked porous polymeric material, comprising one or more organic base functional groups, as defined herein, in the catalysis of base promoted organic reactions (e.g. alkylation reactions).

[00106] Non-limiting examples of base promoted organic reactions that may be catalysed by the functionalised hypercrosslinked porous polymeric materials of the present invention nclude:

(i) the pre-concentration and recovery of Hg²⁺ from waste discharged from industries;

(ii) alkylation reactions;

(iii) isomerisation ;

(iv) dehydration/condensation reactions;

(v) esterifications;

(vi) the reduction of carboxylic acids to aldehydes; (vii) the synthesis of thiols from alcohols with H₂S;

(viii) the synthesis of mercaptane from alcohols with H₂S;

(ix) the cyclization of an imine with sulfur dioxide; or

(x) the synthesis of spirooxindoles.

[00107] In a further aspect, there is provided the use of a functionalised hypercrosslinked porous polymeric material, comprising one or more organic acid functional groups and one or more organic base functional groups, as an ion exchange resin. Suitably, the ion exchange resin is a strongly acidic cation-exchange resin.

[00108] It will be understood that the functionalised hypercrosslinked porous polymeric materials of the present invention, comprising one or more organic acid functional groups and one or more organic base functional groups, may be used as an ion exchange resin in any suitable application.

[00109] Non limiting examples of suitable applications for the functionalised hypercrosslinked porous polymeric materials of the present invention, comprising one or more organic acid functional groups and one or more organic base functional groups, (ion exchange resins), include the use of the functionalised hypercrosslinked porous polymeric materials in the catalysis of any one of the following reactions:

(i) the esterification of olefins with alcohols;

(ϋ) the dehydration of alcohols to olefins or ethers;

(iii) the alkylation of phenols to alkyl phenols;

(iv) the dehydration/condensation reactions;

(v) the acetylation and acetoxylation reactions;

(vi) olefin hydration to form alcohols;

(vii) oxidation reactions;

(viii) ester hydrolysis;

(ix) the degradation of biomass;

(x) etherification reactions (i.e. during biodiesel production); or

(xi) silylation reactions.

[00110] In an embodiment, there is provided the use of a functionalised hypercrosslinked porous polymeric material comprising one or more organic acid functional groups and one or more organic base functional groups, in the catalytic conversion of glucose to 5- hydroxymethylfurfural.

[00111 ] In another aspect, there is provided the use of a functionalised hypercrosslinked porous polymeric material, as defined herein, in gas adsorption. [00112] As the materials of the present invention are porous, they are particularly well suited to storing and absorbing gas. It will be appreciated that the functionalised porous polymeric materials of the present invention may be used to store, absorb and/or separate any suitable gas. Furthermore, it will be understood that the gas storage/ absorption capabilities of the functionalised hypercrosslinked porous polymeric materials of the present invention, will vary according to the functional group appended to the functionalised hypercrosslinked porous polymeric material.

[00113] Suitably, the gas to be stored, absorbed and/or separated is selected from natural gas, biogas, methane, hydrogen or carbon dioxide. More suitably, the gas to be stored, absorbed and/or separated is selected from methane, hydrogen or carbon dioxide, and most suitably, the gas is carbon dioxide.

[00114] In another aspect, there is provided the use of a functionalised hypercrosslinked porous polymeric material, as defined herein, in the storage of ammonia.

[00115] In another aspect, there is provided the use of a functionalised hypercrosslinked porous polymeric material, as defined herein, in the purification of water.

[00116] In another aspect, there is provided the use of a functionalised hypercrosslinked porous polymeric material, as defined herein, in the separation of alkanes from alkane/alkene mixtures. Suitably, the functionalised hypercrosslinked porous polymeric material when used in the separation of alkanes from alkane/alkene mixtures is impregnated with a metal ions ans/or nanoparticles. Most suitably, the the functionalised hypercrosslinked porous polymeric material is impregnated with silver ions and/or nanoparticles.

[00117] In an embodiment, the alkane is selected from (2-10C)alkane and the alkene is selected from a (2-10C)alkene. More suitably, the alkane is selected from (2-6C)alkane and the alkene is selected from a (2-6C)alkene. Most suitably, the alkane is propane and the alkene is propene.

[00118] In a further aspect, there is provided the use of a functionalised hypercrosslinked porous polymeric material comprising fluorobenzene monomer units as a proton conductor. Suitably, the functionalised hypercrosslinked porous polymeric materials comprising fluorobenzene monomer units may be used as proton conductors in applications, such as, for example, fuel cells, electrochemical sensors and electrochemical devices. EXAMPLES

Description of drawings

[00107] Embodiments of the invention will be described, by way of example only, with reference to the accompanying drawings, in which:

Figure 1 shows the yields of respective products from the acid-catalysed hydrolysis of cellobiose by Amberlyst-15, SAM-HCP-4 and SAM-HCPs-T2. Reaction conditions: 160 Ό, for 1 min, in a microwave, 100 mg cellobiose, 50 mg catalyst and 1 ml water.

Figure 2 shows the selectivity of respective products from the acid-cataylsed hydrolysis of cellobiose by Amberlyst-15, SAM-HCP-4 and SAM-HCPs-T2. Reaction conditions: 160 Ό, for 1 min, in a microwave, 100 mg cellobiose, 50 mg catalyst and 1 ml water.

Figure 3 shows the yields of respective products from the acid-cataylsed hydrolysis of cellobiose by fresh SAM-HCPs-T2, reused SAM-HCPs-T2 (run 1 ) and reused SAM-HCPs-T2 (run 2). Reaction conditions: 160°C, for 1 min, in a microwave, 100 mg cellobiose, 50 mg catalyst and 1 ml water.

Figure 4 shows the selectivities of respective products from the acid-cataylsed hydrolysis of cellobiose by fresh SAM-HCPs-T2 (blue), reused SAM-HCPs-T2 (run 1 ) and reused SAM- HCPs-T2 (run 2). Reaction conditions: Ι ΘΟ'Ό, for 1 min, in a microwave, 100 mg cellobiose, 50 mg catalyst and 1 ml water.

Figure 5 shows the yields of respective products from the acid-cataylsed hydrolysis of cellobiose by Amberlyst-15. Analysis performed using HPLC analysis on an Aminex HPX-87H column. Reaction conditions: 160°C, microwave, 100 mg cellulose, 50 mg catalyst, 1 ml water.

Figure 6 shows the selectivities of respective products from the acid-cataylsed hydrolysis of cellobiose by Amberlyst-15. Analysis performed using HPLC analysis on an Aminex HPX-87H column. Reaction conditions: 160°C, microwave, 100 mg cellulose, 50 mg catalyst, 1 ml water.

Figure 7 shows the yields of respective products from the acid-cataylsed hydrolysis of cellobiose by SAM-HCPs-4. Analysis performed using HPLC analysis on an Aminex HPX-87H column. Reaction conditions: 160°C, microwave, 100 mg cellulose, 50 mg catalyst, 1 ml water.

Figure 8 shows the selectivities of respective products from the acid-cataylsed hydrolysis of cellobiose by SAM-HCPs-4. Analysis performed using HPLC analysis on an Aminex HPX-87H column. Reaction conditions: 160°C, microwave, 100 mg cellulose, 50 mg catalyst, 1 ml water.

Figure 9 shows the yields of respective products from the acid-cataylsed hydrolysis of cellobiose by SAM-HCPs-T-2. Analysis performed using HPLC analysis on an Aminex HPX- 87H column. Reaction conditions: 160°C, microwave, 100 mg cellulose, 50 mg catalyst, 1 ml water.

Figure 10 shows the selectivities of respective products from the acid-cataylsed hydrolysis of cellobiose by SAM-HCPs-T-2. Analysis performed using HPLC analysis on an Aminex HPX- 87H column. Reaction conditions: 160°C, microwave, 100 mg cellulose, 50 mg catalyst, 1 ml water.

Figure 1 1 shows the yields of respective products from the acid-cataylsed hydrolysis of cellobiose by SAM-HCPs-3. Reaction conditions: 160°C, microwave, 100 mg cellulose, 50 mg catalyst, 1 ml water.

Figure 12 shows the yields of respective products from the acid-cataylsed hydrolysis of cellobiose by SAM-HCPs-T1 . Reaction conditions: 160°C, microwave, 100 mg cellulose, 50 mg catalyst, 1 ml water.

Figure 13 shows the selectivities of respective products from the acid-cataylsed hydrolysis of cellobiose by SAM-HCPs-3. Reaction conditions: 160°C, microwave, 100 mg cellulose, 50 mg catalyst, 1 ml water.

Figure 14 shows the selectivities of respective products from the acid-cataylsed hydrolysis of cellobiose by SAM-HCPs-T1 . Reaction conditions: 160°C, microwave, 100 mg cellulose, 50 mg catalyst, 1 ml water.

Figure 15 shows the FTIR spectrum of SAM-HCPs-T-1 .

Figure 16 shows the FTIR spectrum of SAM-HCPs-T-1 -CO.

Figure 17 shows the FTIR spectrum of SAM-HCPs-T-2-CO.

Figure 18 shows the Cross-polarization (CP) 13C MAS natural abundance NMR spectrum of SAM-HCPs-T-1 -CO.

Figure 19 shows the Cross-polarization (CP) 13C MAS natural abundance NMR spectrum of SAM-HCPs-T-2-CO.

Figure 20 shows the C0₂ adsorption profile of SAM-HCPs-T-1 .

Figure 21 shows the CH₄ adsorption profile of SAM-HCPs-1 .

Figure 22 shows the H₂ adsorption profile of SAM-HCPs-1 .

Figure 23 shows the breakthrough curve of 50:50 propane/propene flowing through a bed of SAM-HCPs-Ag-4. The total flow rate was 4 ml min ¹ , 298 K, 500 mbar. Time 0 is when the propane/propene mixture starts flowing through the column. Figure 24 shows the outlet composition of effluent gas derived from breakthrough curve of 50:50 propane/propene flowing through a bed of SAM-HCPs-Ag-4. The total flow rate was 4 ml mirr¹ , 298 K, 500 mbar. Time 0 is when propane first breaks through the column.

Figure 25 shows the outlet composition of effluent gas derived from breakthrough curve of 90:10 propane/propene flowing through a bed of SAM-HCPs-Ag-4. The total flow rate was 1 .5 ml min ¹ , 298 K, 500 mbar. Time 0, as shown, is when propane first breaks through the column.

Abbreviations

BET Braunauer, Emmett and Teller

BPL Bituminous coal - commercial type of granular activated carbon

DCE Dichloroethane

DMF Dimethylformamide

FDA Formaldehyde dimethyl acetal

HCP Hypercrosslinked polymer

HMF Hydroxymethylfurfural

HPLC High performance liquid chromatography

FTIR Fourier Transform Infrared Spectroscopy

MAS Magic angle spinning

NMR Nuclear magnetic resonance

SAM Sulforic acid modified

THF Tetrahydrofuran

Methods and Synthetic Procedures

[00108] The hypercrosslinked polymers, HCPs-3, HCPs-4, HCPs-T-1 and HCPs-T-2, were prepared using an adapted method for the synthesis for porous polymer networks, previously described by Robert T. Woodward et al.¹³ and Buyi Li et al. whereby, the Friedel-Crafts alkylation of benzene with formaldehyde dimethyl acetal, produces a microporous, "knitted" hypercrosslinked polymer network.¹⁵

Preparation of hypercrosslinked porous polymeric materials of the present invention (step (i) of the process)

Synthesis of HCPs-3 andHCPs-4 (hypercrosslinked polymers, using benzene as a monomer)

[00109] FeCI₃ (anhydrous 6.5g, 40 mmol - forHCPs-3; anhydrous 3.25g, 20 mmol - for HCPs- 4), was added to a solution of benzene (1 .56g, 0.02 mol) and FDA (3.04g, 40 mmol - for HCPs-3; 1 .52g, 20 mmol - for HCPs-4) in 20ml 1 ,2-DCE. The resulting mixtures were stirred at room temperature to ensure a good mix of reactants, and then were heated to 80 °C and stirred for a further 24 h to form the original framework and react completely. The resulting precipitate was washed 3 times with methanol, to remove excess FeCI₃, and was then further washed with methanol in a Soxhlet for 24 h, followed by vacuum drying at 60 °C for 24 h.

Synthesis of HCPs-T-1 and HCPs-T-2 {hypercrosslinked polymers, using 1,3,5- triphenylbenzene as a monomer)

[00110] FeCI₃ (anhydrous 6.5g, 40 mmol - for HCPs-T-1; anhydrous 3.25 g, 20 mmol - for HCPs-T-2) was added to a solution of 1 ,3,5-triphenylbenzene (3.06 g, 0.01 mol) and FDA (3.04g, 40 mmol - for HCPs-T-1; 1 .52g, 20 mmol - for HCPs-T-2) in 20ml 1 ,2-DCE. The resulting mixtures were stirred at room temperature to ensure a good mix of reactants, and then were heated to 80 ° and stirred for a further 24 h to form the original framework and react completely. The resulting precipitate was washed 3 times with methanol, to remove excess FeCI₃, and was then further washed with methanol in a Soxhlet for 24 h, followed by vacuum drying at 60 °C for 24 h.

[00111 ] The synthetic approach to preparing the sulfonic acid treated hypercrosslinked polymers, SAM-HCPs-3, SAM-HCPs-4, SAM-HCPs-T-1 and SAM-HCPs-T-2, was modified from an approach noted by Estibaliz Merino et al.³⁴ where in order to functionalise with the acid groups, a simple treatment with chlorosulfonic acid in the presence of dichloromethane was used, to yield the product.

Synthesis of HCPs-OH- 1

[00112] FeCI₃ (9.75 g, 60 mmol) was added to a solution of phenol (0.94 g, 20 mmol) and FDA (4.56 g, 60 mmol) in 20 mL DCE. The resulting mixtures were stirred at room temperature for good mix, and then heated at 80 °C for 24 h to react completely. The reaction was processed under nitrogen atmosphere. The resulting precipitate was washed three times with methanol, then washed with methanol in a Soxhlet for 24h, and finally dried under reduced pressure at 60 °C for 24 h.

Synthesis of HCPs-OH-2

[00113] FeCI₃ (6.5 g, 40 mmol) was added to a solution of 2,2'-Biphenol (1 .86 g, 10 mmol) and FDA (3.04 g, 40 mmol) in 20 mL DCE. The resulting mixtures were stirred at room temperature for good mix, and then heated at 80 °C for 24 h to react completely. The reaction was processed under nitrogen atmosphere. The resulting precipitate was washed three times with methanol, then washed with methanol in a Soxhiet for 24h, and finally dried under reduced pressure at 60 °C for 24 h.

Synthesis of HCPs-NA

[00114] FeCI₃ (6.5 g, 40 mmol) was added to a solution of naphthalene (2.56 g, 20 mmol) and FDA (3.04 g, 40 mmol) in 20 mL DCE. The resulting mixtures were stirred at room temperature for good mix, and then heated at 80 °C for 24 h to react completely. The reaction was processed under nitrogen atmosphere. The resulting precipitate was washed three times with methanol, then washed with methanol in a Soxhiet for 24h, and finally dried under reduced pressure at 60 °C for 24 h.

Synthesis of HCPs-TH

[00115]FeCI₃ (6.5 g, 40 mmol) was added to a solution of thiophene (1 .68 g, 20 mmol) and FDA (3.04 g, 40 mmol) in 20 mL DCE. The resulting mixtures were stirred at room temperature for good mix, and then heated at 80 °C for 24 h to react completely. The reaction was processed under nitrogen atmosphere. The resulting precipitate was washed three times with methanol, then washed with methanol in a Soxhiet for 24h, and finally dried under reduced pressure at 60 °C for 24 h.

Synthesis of HCPs-P-OH

[00116] FeCI₃ (6.5 g, 40 mmol) was added to a suspension of 1 ,1 '-Binaphthyl-2,2'-diyl hydrogen phosphate (3.48 g, 10 mmol) and FDA (3.04 g, 40 mmol) in 20 mL DCE. The resulting mixtures were stirred at room temperature, to ensure a good mix, and then heated at 80 °C for 24 h. The resulting precipitate was washed three times with methanol, then washed with methanol in a Soxhiet for 24h, and finally dried under reduced pressure at 60 °C for 24 h.

Synthesis of HCPs-F- 1 and HCPs-F-2 (hypercrosslinked polymers, using Fluorobenzene as a monomer)

[00117] FeCI₃ (anhydrous 6.5g, 40 mmol - for HCPs-F-1 ; anhydrous 3.25g, 20 mmol -for HCPs-F-2), was added to a solution of Fluorobenzene (1 .92g, 0.02 mol) and FDA (3.04g, 40 mmol - for HCPs-F-1 ; 1 .52g, 20 mmol - for HCPs-F-2) in 20ml 1 ,2-DCE. The resulting mixtures were stirred at room temperature to ensure a good mix of reactants, and then were heated to 80 °C and stirred for a further 24 h to form the original framework and react completely. The resulting precipitate was washed 3 times with methanol, to remove excess FeCb, and was then further washed with methanol in a Soxhlet for 24 h, followed by vacuum drying at 60 °C for 24 h.

Preparation of the functionalised hypercrosslinked porous polymeric materials of the present invention (step (ii) of the process)

Synthesis of SAM-HCPs-3. SAM-HCPs-4. SAM-HCPs-T- 1. SAM-HCPs-T-2. SAM-HCPs-OH- 1. SAM-HCPs-OH-2. SAM-HCPs-NA. SAM-HCPs-TH

[00118] HCPs-3, HCPs-4, HCPs-T-1 , HCPs-T-2, HCPs-OH-1 , HCPs-OH-2, HCPs-NA, or HCPs-TH (1 .2g) were suspended in dichloromethane (50ml), and were stirred for 5 minutes, before slowly adding chlorosulfonic acid (1 .5ml) drop-wise. The reaction mixtures were then warmed to room temperature and stirred for 18 h. The resulting solids were then filtered, and were washed with dichloromethane (3 times), methanol (3 times) and water (3 times), followed by vacuum drying at 60°C for 24 h. The reaction of SAM-HCPs-OH-1 and SAM-HCPs-OH-2 were under nitrogen atmosphere.

Synthesis of SAM-HCPs-T-1-CO and SAM-HCPs-T-2-CO

[00119] Firstly SAM-HCPs-T-1 and SAM-HCPs-T-2 were ion-exchanged with by NaCI aqueous (2 mol/L) to yield SAM-HCPs-T-1 -Na and SAM-HCPs-T-2-Na. To the solution of SAM-HCPs-T-1 -Na or SAM-HCPs-T-2-Na(930 mg) and Oxone® (18.44 g, 30 mmol) in MeN0₂ (60 mL) was added KBr (596 mg, 5 mmol) at room temperature, and stirred at 50 °C for 24 h. The resulting precipitate was washed with water (3 times), then ion-exchanged to hydrogen form by HCI aqueous (2 mol/L) and finally washed with water (3 times), followed by vacuum drying at 60 °C for 24 h.

Synthesis of HCPs-4-NH? (Base functionalised HCPs)

[00120] Firstly, HCPs-4 (220 mg) was added to trifluoroacetic acid (16 mL) cooled at 0 ^eC. After 10 minutes, nitric acid (100 μί) was slowly added and the mixture was stirred for 4 hours at 50^eC. The mixture was added to ice/water. The solid was filtered, washed with water, THF and diethylether, followed by vacuum drying at 50 °C for 24 h.

[00121 ] Next, Tin(ll) chloride dihydrate (580 mg) was added to a suspension of HCPs-4-N0₂ (50 mg) in THF (8 mL) and the mixture was refluxed during 2 days. The solid was filtrated and washing with NaOH (10%), water, THF and diethylether, followed by vacuum drying at 50 °C for 24 h. Synthesis of SAM-HCPs-4-NH₂ (Mixed acid/base functionalised HCPs)

[00122] Firstly, SAM-HCPs-4 (220 mg) was added to trifluoroacetic acid (16 mL) cooled at

0 °C. After 10 minutes, nitric acid (100 μΙ_) was slowly added and the mixture was stirred overnight at 50 °C. The mixture was added to ice/water. The solid was filtered, washed with water, THF and diethylether, followed by vacuum drying at 50 °C for 24 h.

[00123] Next, Tin(ll) chloride dihydrate (2.34 g) was added to a suspension of SAM-HCPs-

NO2 (244 mg) in THF (27 mL) and the mixture was refluxed overnight. The solid was filtrated and washing with NaOH (10%), water, buffer AcOH/AcONa (pH=4), water, THF and diethylether, followed by vacuum drying at 50 °C for 24 h.

Synthesis of SAM-HCPs-F-1 and SAM-HCPs-F-2

[00124] HCPs-F-1 or HCPs-F-2 (1 .2g) were suspended in dichloromethane(50ml), and were stirred for 5 minutes, before slowly adding chlorosulfonic acid (1 .5ml) drop-wise. The reaction mixtures were then warmed to room temperature and stirred for 18 h. The resulting solids (SAM-HCPs-F-1 or SAM-HCPs-F-2, respectively) were then filtered, and were washed with dichloromethane (3 times), methanol (3 times) and water (3 times), followed by vacuum drying at 60 °C for 24 h.

Synthesis of HCPs-T-2-Ru NPs (Metal nanoparticle impregnated HCPs)

[00125] 20 mg RuCI₃. xH₂0 was dissolved into 2 ml ethanol, then 200 mg HCPs-T-2 was added. The slurry was stirred until most of ethanol was evaporated, and then the slurry was dried at the room temperature. The HCPs-T-2 with RuC was reduced to HCPs-T-2-Ru NPs in H₂ flow at 150 °C for 5 hours.

Synthesis of SAM-HCPs-T-2-Ru NPs (Mixtured acid functionalised/metal nanoparticle impregnated HCPs)

[00126] 20 mg RuCI₃. xH₂0 was dissolved into 2 ml ethanol, then 200 mg SAM-HCPs-T-2 was added. The slurry was stirred until most of ethanol was evaporated, and then the slurry was dried at the room temperature. The SAM-HCPs-T-2 with RuC was reduced to SAM- HCPs-T-2-Ru NPs in H₂ flow at 150 Ό for 5 hours.

Hydrolysis of Cellobiose, or Cellulose, in a Microwave Reactor

[00127] The hydrolysis reactions were performed in a 35 mL pressurised vessel (tube) in a CEM Discover SP (CD) microwave. In the microwave tubes, the hydrolysis was carried out using 100 mg substrate, 50 mg catalyst, and 1 .0 ml of distilled water. The microwave was set to dynamic mode, allowing for the conditions under which the reaction was performed, to be controlled, such as allowing for a system with a controlled variable power input, in order to achieve a desired temperature. The controlled variable power input, during the initial water heating phase, was recording a maximum power input of 300 W.

HPLC Conditions

[00128] HPLC was performed using an Aminex HPX-87H column, a mobile phase of 25 mM H2SO4 and a flow rate of 0.65 ml/min, over a period of 60 minutes.

Sulfonic Acid Modified Hypercrosslinked Porous Polymers (SAM-HCPs)

[00129] To prepare the sulfonic acid modified hypercrosslinked porous polymers (SAM-HCPs) of the present invention, firstly hypercrosslinked polymers were synthesised and these were then sulphonated to yield the corresponding SAM-HCPs.

Hypercrosslinked Porous Polymers (HCPs)

[00130] The preparation and synthesis of the hypercrosslinked polymers, HCPs-3, HCPs-4, HCPs-T-1 and HCPs-T-2, were all carried out using a simple one-step Friedel-Crafts alkylation reaction, as shown in Scheme 1 below.

Scheme 1 - . Synthesis of the "knitted" hypercrosslinked polymer networks, using Friedel- Crafts alkylation of the monomers benzene and 1 ,3,5-triphenylbenzene, under the given reaction conditions.

Sulfonic Acid Modified Hypercrosslinked Porous Polymers (SAM-HCPs)

[00131 ] The functional acid group exemplified was S0₃H, a strong Bronsted acid that would bond to the pore surface of the hypercrosslinked polymers synthesised, in order to fabricate the required solid acid catalyst. This reaction scheme was adapted from Estibaliz Merino et a/.¹⁶ and was modified in order to give the best selectivity and yield.

Scheme 2 - Synthesis of SAM-HCPS-3, SAM-HCPS-4; and SAM-HCPS-T- 1, SAM-HCPS-T- 2, from their respective HCPs and chlorosulfonic acid, under the given conditions.

SAM-HCPs-3 or SA -HCPs-4

[00132] Once synthesised, FTIR was conducted on the SAM-HCPs (Figure 15), the characteristic bands in the FTIR for the SO3H groups were shown to be present. Peaks in the region 1018 cm ¹ are representative of S-0 asymmetrical stretching and peaks at 820 cm ¹ are representative of S-0 symmetrical stretching. A broad peak at 3300 cm ¹ also showed the presence of the stretching of the -OH group.

SAM-HCPs-T- 1-CO and SAM-HCPs-T-2-CO

[00133] The synthesis of SAM-HCPs-T-1 -CO and SAM-HCPs-T-2-CO was achieved by the post-synthetic modification of SAM-HCPs-T-1 and SAM-HCPs-T-2, as detailed above and shown below in Scheme 3. The FTIR characteristic bands of keto group in SAM-HCPs-T-1 - CO (Figure 16) and SAM-HCPs-T-2-CO (Figure 17) were present in the peak of 1700 cm ¹. Cross-polarization (CP) 13C MAS natural abundance NMR spectrum showed resonance peaks at 138 and 130 ppm due to substituted aromatic carbon and non-substituted aromatic carbon respectively, the resonance peaks at 36 ppm due to carbon in methylene linker formed, and the resonance peaks at 191 ppm due to carbon in keto group formed (Figure 18, Figure

19).

Scheme 3 - Synthesis of SAM-HCPs-3. SAM-HCPs-4; and SAM-HCPs-T-1, SAM-HCPs-T-2, from their respective HCPs and Chlorosulfonic Acid, under the given conditions.

Surface area, porosity and properties.

[00134] The physical properties of the SAM-HCPs were compared to commercially available analogues, namely Amberlyst-15, Amberlyst-36 and Nation. Amberlyst-15 and Amberlyst-36 are strongly acidic (-S0₃H), macroreticulated styrene-divinylbenzene resins, with a continuous open pore, macroporous structure. They are commercially available, inexpensive, and stable in most solvents.¹⁷ By contrast, Nation is a very expensive catalyst with low sulfonic acid content, although the acid degree is very strong.

[00135] The comparative data is summarised in Table 1 below. Table 1 - Surface area, porosity and properties

^* Cannot be defined because of including F element; ^** hydrophobicity, and floating on water; ^*** literature data

Hydrolysis of cellobiose

[00136] On performing cellobiose hydrolysis, at Ι ΘΟ'Ό, with the same amount of catalyst (SAM-HCP of the present invention) each time (50mg), the resulting solution was analysed using HPLC. The experiments showed that in the absence of a catalyst, cellobiose was not hydrolysed. However, in the presence of a catalyst (a SAM-HCP of the present invention) successful and clean hydrolysis did take place. Note, clean hydrolysis refers to hydrolysis wherein no formic or levulinic acid is produced.

[00137] Both SAM-HCPs-4 and SAM-HCPs-T-2, gave higher conversion percentages and higher carbon mass balance when compared to the commercially available standard, Amberlyst-15. The glucose yields recorded were 88.37%, 85.27% and 66.85%, for SAM- HCPs-T-2, SAM-HCPs-4 and Amberlyst-15 respectively (Figures 1 and 2). Of the 3 porous polymer acids, SAM-HCPs-T-2 clearly gives the highest yield of glucose, as well as the highest conversion and carbon mass balance percentage. This can be attributed to SAM-HCPs-T-2 having the largest BET surface area, Langmuir surface area, and pore volume size, meaning it has the most area for the cellobiose to react upon, resulting in a larger conversion rate.

[00138] The yield and corresponding selectivity results for the hydrolysis of cellobiose by SAM-HCPs is summarised Figures 1 and 2 and Tables 2 and 3. Table 2 - Hydrolysis of cellobiose yields. Reaction conditions: 160 V, for 1 min, in a microwave, WOrng cellobiose, 50mg catalyst, 1ml water.

Table 3 - Hydrolysis of cellobiose selectivity data. Reaction conditions: 160 V, for 1 min, in a microwave, WOrng cellobiose, 50mg catalyst, 1ml water.

[00139] The recycling of the catalyst in the hydrolysis of cellobiose, in this case, the best performing polymer acid, SAM-HCPs-T-2, showed that the catalyst could be recycled with only a modest compromise in glucose yield (see Table 4). The recycled catalyst (SAM-HCPs-T-2), also showed a good retention in glucose selectivity as illustrated in Table 5.

Table 4 - Hydrolysis of cellobiose, using recycled SAM-HCPs-T-2 yields. Reaction conditions: 160 V, for 1 min, in a microwave, WOrng cellobiose, 50mg catalyst, 1ml water.

Products / Glucose Fructose HMF Formic Levulinic Furfural Conversion Carbon

Acid Acid Mass

Balance / Catalysts

SAM-HCPs- 88.37 1 .62 1 .21 0.00 0.00 0.05 91 .91 91 .24 T-2 (fresh)

SAM-HCPs- 83.56 2.23 1 .36 0.00 0.00 0.05 91 .96 88.25 T-2 (run 1)

SAM-HCPs- 79.04 1 .56 0.52 0.00 0.00 0.00 84.43 81 .12 T-2 (run 2) Table 5 - Hydrolysis of cellobiose, using recycled SAM-HCPs-T-2, selectivity data. Reaction conditions: 160 V, for 1 min, in a microwave, WOrng cellobiose, 50mg catalyst, 1ml water.

Cellulose Hydrolysis Data for Amberlyst-15, SAM-HCPs-4 & SAM-HCPs-T-2

[00140] Once the acid-catalysed hydrolysis of cellulose had been performed, the contents of the microwave tubes were analysed by HPLC, using an Aminex HPX-87H column. This gave a comparison of catalytic performance, comparing Amberlyst-15 with SAM-HCPs-4 and SAM- HCPs-T-2 (Figures 5 to 10).

[00141 ] Amberlyst-15 was shown to have a yield of carbon mass balance at a peak of approximately 17.5% after 120 minutes, a yield somewhat smaller than the 25% exhibited after approximately 60 minutes for SAM-HCPs-4, and approximately 32.5% after 120 minutes for SAM-HCPs-T-2 (See Figures 5, 7, and 9 respectively).

[00142] This trend continues with the selectivity of the catalysts. Amberlyst-15 displays instant glucose selectivity of 60%, which is smaller than the instant 70% glucose selectivity of SAM- HCPs-T-2 (See Figures 6 and 10 respectively).

[00143] Next, catalysts synthesised using a larger molar amount of FDA and FeCI₃ (SAM- HCPs-3 and SAM-HCPs-T-1 ) were compared to those catalysts synthesised with lower molar amounts of FDA and FeCI₃ (SAM-HCPs-4 and SAM-HCPs-T-2). The results are summarised in Figures 7, 9, 1 1 and 12.

[00144] It was shown that when compared to SAM-HCPs-4 and SAM-HCPs-T-2, SAM-HCPs- 3 and SAM-HCPs-T-1 demonstrated much better total carbon mass balance yields, as well as glucose yields (Figures 7, 9, 1 1 and 12 respectively).

[00145] The selectivity displayed by catalysts SAM-HCPs-4 and SAM-HCPs-T-2, when compared to SAM-HCPs-3 and SAM-HCPs-T-1 is illustrated in Figures 8, 10, 13 and 14 respectively. Ammonia cut-off experiments

[00146]15mg samples were loosely packed between glass wool plugs in 4mm i.d. glass tubes and then 500 ppm ammonia was passed with flow rate of 15 ml/min through the tubes. The gas was then analysed with a PhoCheck Tiger photoionisation detector.

[00147] The results are summarised in Table 6 and show an increased ammonia cut-off (absorption) for the catalysts of the present invention when compared to unsulphonated HCPs and the commercial standard commercial activated carbon (BPL).

Table 6 - The surface area, porosity, sulfonic acid group amount and ammonia breakthrough time for various materials.

SBET¹" S_L ^C. PV^d -SO3H time

Sample.

(m²/g) (m²/g) (cm³/g) (mmol/g) min

HCPs-2 1350 1704 2.04 / 12

HCPs-3 1376 1742 1.80 / 8

HCPs-4 823 1195 0.63 / 4

HCPs-5 571 830 0.40 / 2

HCPs-OH-1 375 554 0.31 / 28

HCPs-OH-2 698 930 0.41 / 33.5

SAM-HCPs-2 889 1116 0.83 1.29 50

SAM-HCPs-3 948 1288 1.30 1.71 69

SAM-HCPs-4 511 691 0.35 3.12 42

SAM-HCPs-5 18 38 0.014 3.12 28

SAM-HCPs-OH-1 35 48 0.073 1.15 90

SAM-HCPs-OH-2 528 701 0.30 0.87 67.5

SAM-HCPs-T-2 530 719 0.41 3.70 114

BPL (commercial

1100 / / / 6

standard) One-pot Cascade Reaction of Glucose to 5-Hvdroxymethylfurfural catalysed by SAM- HCPs-4-NH₂

[00148] The catalytic reaction shown in Scheme 4 was performed using 100 mg SAM-HCPs- 4-NH₂, 50 mg of glucose and 1 .5 mL of DMF at 80 °C for 5 h. The products were analysed by high-performance liquid chromatography (HPLC) using a Bio-rad Aminex HPX-87H column. Glucose conversion calculated as 81 .7 %, and HMF yield was determined to be 41 .53 %.

Scheme 4 - Schematic representation of the catalytic cascade reaction of glucose to 5- hydroxymethylfurfural (HMF).

[00149] For comparison, the catalytic reaction was also performed using a two component catalytic procedure. In this instance, the reaction was performed using 50 mg SAM-HCPs-4, 50 mg HCPs-4-NH₂, 50 mg of glucose and 1 .5 mL of DMF at 80 °C for 5 h. The products were analysed by high-performance liquid chromatography (HPLC) using a Bio-rad Aminex HPX- 87H column. Conversion of glucose was 76.9 %, HMF yields was 3.3 %.

[00150] The bifunctional catalyst with both acidic (sulfonic acid) and basic (amine) group displayed both higher glucose conversion and substantially improved HMF yields, comparing with physically mixed acidic catalyst and basic catalyst.

Impedance spectroscopy

[00151 ] 100 mg of SAM-HCPs-F-1 or SAM-HCPs-F-2 were accurately-approximately weighed using an analytical balance and subsequently ground to a fine powder using a pestle and mortar. The powder was then transferred to a standard die and pressed into pellets of approximately 10 mm diameter and 1 mm thickness. The pellets were dried overnight under vacuum at 90 °C. In order to perform conductivity measurements in the plane of thickness, the thickness was accurately measured using a Fisher Scientific digital caliper before pressing between two discs of platinum foil (Advent Research Materials) which was cut using a 10 mm foil punch. These served to act as current collectors. A T-shaped Teflon Swagelok cell was assembled sandwiching the pellets between two stainless steel rods (blocking electrodes). The assembled Swagelok cell was connected to an EC Labs Biologic VMP3 potentiostat using banana plug cables. 2 probe (quasi four probe) electrochemical impedance spectroscopy (EIS) was measured using a sinus perturbation of 100 mV over the frequency range 100 mHz- 1 MHz. In order to investigate the effect of humidification and temperature, a Memmertt Celsius humidity chamber was used. Impedance measurements were taken between 30-95% relative humidity and 30-1 10°C. For the humidity investigation, an equilibration time of four hours was required between taking measurements in order for water sorption to stabilise.

[00152] The mean proton conductivity for the two samples of SAM-HCPs-F-1 after 24 hour at 95%RH at 30 °C was 3.61 x 10-3 S/cm, and it remained fairly stable.

[00153]The mean proton conductivity for the two samples of SAM-HCPs-F-2 after 24 hour at 95%RH at 30 °C was 2.1 x 10-3 S/cm, and it remained fairly stable.

Table 7 - The proton conductivity for SAM-HCPs-F-1 at 30 °C at varying relative humidities.

Table 8 - The proton conductivity for SAM-HCPs-F-2 at 30 °C at varying relative humidities.

Application of removing CO2 from CH₄ and the storage of CH₄ or H₂

[00154] The adsorption of C0₂, CH₄ and H₂ were analysed by Volumetric nitrogen gas sorption measurements were performed on roughly 100 mg of each sample, weighed accurately, using a Micromeritics ASAP 2050 or 2020 (Micromeritics Instrument Corporation, Norcross, USA) at a temperature of 77.3 K. Prior to measurements, samples were heated to 120 °C under dynamic vacuum (<15 μbar) overnight.

[00155] Figures 20 shows the C0₂ adsorption profile of SAM-HCPs-T-1 . [00156] Figures 21 and 22 shows the CH₄ and H₂ adsorption profiles of SAM-HCPs-1 respectively.

Alkane/Alkene separation

Preparation of SAM-HCP- 4-Ag

[00157] SAM-HCP-4 was impregnated with silver by soaking in a 1 M solution of silver nitrate for 24 h, and then SAM-HCP-4 was filtrated and washed by water, following by dried at 40 °C in vacuum oven for 24 h.

Breakthrough measurements

[00158] The breakthrough curves were measured using an automated breakthrough analyser (manufactured by Hiden Isochema, Warrington, U.K.). The SAM-HCPs-4-Ag material (2.01 g) was packed into an adsorption bed for the breakthrough experiment. The pre-mixed gases were introduced through the bottom inlet of the adsorption bed which was held between two layers of quartz wool and two sample holders, with frit gaskets installed at both the top and bottom ends. The flow rate of each gas was controlled by individual mass flow controllers. The mass flow controllers and the pressure in the column were controlled by the software supplied by Hiden. The effluent was monitored using an in-line Hiden mass-spectrometer.

[00159] The m/z values used to detect the effluent gas were 29 for Propane and 41 for Propene. There was some overlap at the mass-fragment 41 - propane also gives a signal at this mass unit. It was determined that the signal from propane at m/z 41 was 1 1 % of the signal it gave at m/z 29. This was therefore deducted to give purely the propene signal at m/z 29. This method of normalizing for mass fragment overlap for propane and propene has been used before.¹⁸

[00160] The material was activated in situ by heating to 100 °C and flowing helium through the column. The gases of interest were also desorbed from the column by flowing helium through at the same rate as the gases of interest in the breakthrough curve.

[00161 ] The propane and propene capacity of SAM-HCPs-4-Ag at 298 K was calculated using equation 1 and the method described previously.¹⁹ The selectivity for propene over propane under breakthrough conditions is calculated using equation 2.

(2) Results

[00162] Breakthrough curves were measured for a fixed bed of SAM-HCPs-4-Ag at 298 K using a 50:50 or 90:10 propane/propene gas mixture. Breakthrough curves give a far more realistic picture of the separation potential of a material than IAST calculations. The separation under breakthrough conditions requires good kinetics, something not accounted for by IAST selectivities calculated from single component isotherms.

[00163] The results from the breakthrough of a 50:50 propane/propene mixture are shown in Figure 23. The propane breaks through the column first and has the characteristic 'roll up' until the propene breaks through approximately 15 minutes later. Figure 24 shows the outlet composition from when propane first breaks through; the propane has a >99 % purity for approximately 15 minutes as determined by the mass spectrometer.

[00164] Capacities for the material were calculated as 0.26 and 1 .04 mmol g^~1 for propane and propene respectively. This gave a calculated selectivity of 3.4, lower than expected from IAST calculations. However, it is still clear to see that the material does separate the propane and propene very efficiently under the kinetic conditions of the breakthrough experiment.

[00165] The results from the breakthrough curve of a 90:10 propane/propene mixture are shown in Figure 25. The outlet composition shows that the effluent has a >99 % purity of propane for approximately 175 minutes as determined by the mass spectrometer.

[00166] Capacities for the material under these conditions were calculated as 0.54 and 0.70 mmol g^~1 for propane and propene respectively. This gave a calculated selectivity of 1 1 .7, again lower than expected from IAST calculations. With a separation of approximately 175 minutes between the two gases breaking through, it is clear that the material is effective at separating propane and propene.

[00167] While specific embodiments of the invention have been described herein for the purpose of reference and illustration, various modifications will be apparent to a person skilled in the art without departing from the scope of the invention as defined by the appended claims.

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Claims

CLAIMS:

1 . A process for the preparation of a functionalised hypercrosslinked porous polymeric material, the process comprising the steps of:

ii) reacting the hypercrosslinked porous polymeric material of step i) to introduce one or more functional groups;

with the proviso that the aromatic monomer of step i) does not comprise a vinyl group.

2. A process for the preparation of a functionalised hypercrosslinked porous polymeric material according to claim 1 , wherein in step (i) of the process the aromatic monomer units that form the hypercrosslinked porous polymeric material comprise one or more aromatic rings, and the crosslinking molecule reacts with, and crosslinks, the aromatic rings of adjacent aromatic monomer units.

3. A process according to any one of claims 1 or 2, wherein in step (i) of the process the reaction between the aromatic monomer units and the crosslinking molecule is a Friedel-Crafts alkylation or Friedel-Crafts acylation.

4. A process for the preparation of a functionalised hypercrosslinked porous polymeric material according to any one of claims 1 to 3, wherein the hypercrosslinked porous polymeric material of step (i) or the functionalised hypercrosslinked porous polymeric material of step (ii) of the process is impregnated with a metal nanoparticle.

5. A process for the preparation of a functionalised hypercrosslinked porous polymeric material according to claim 4, wherein the metal nanoparticle is selected from Ru, Rh, Pd, Co, Au, Ag, Ni or Fe₃0₄.

6. A process for the preparation of a functionalised hypercrosslinked porous polymeric material according to any one of claims 1 to 5, wherein the reaction of step i) is carried out in the presence of an activating agent.

7. A process for the preparation of a functionalised hyper-cross-linked porous polymeric material according to claim 6, wherein the activating agent is a Bronsted or Lewis acid.

8. A process for the preparation of a functionalised hyper-cross-linked porous polymeric material according to any one of claims 6 or 7, wherein the activating agent is selected from FeCI₃, SnCU, AICI₃ or CF₃C0₂H.

9. A process for the preparation of a functionalised hyper-cross-linked porous polymeric material according to any one of claims 6 to 8, wherein the activating agent is selected from FeCI₃, AICI₃ or CF₃C0₂H.

10. A functionalised hypercrosslinked porous polymeric material obtainable by the

process of any one of claims 1 to 9.

1 1 . The functionalised hypercrosslinked porous polymeric material according to claim 10, wherein the aromatic monomer units of step (i) of the process, as defined in any one of claims 1 to 9, are selected from an aryl or heteroaryl, and wherein each aryl or heteroaryl is optionally substituted with one or more substituents selected from (1 - 6C)alkyl, (1 -6C)alkoxy, halo, hydroxyl, aryl, heteroaryl, phosphate, sulfate or NR_aRt>, wherein R_a and Rb are independently selected from H or (1 -4C)alkyl.

1 2. The functionalised hypercrosslinked porous polymeric material according to any one of claims 10 or 1 1 , wherein the aromatic monomer units of step (i) of the process, as defined in any one of claims 1 to 9, are selected from benzene, biphenyl, 1 ,3,5- triphenylbenzene, naphthalene, anthracene, pyrene, thiophene, pyrrole, furan, carbazole, 1 , 1 '-binaphthyl-2,2'-diyl hydrogen phosphate or 2,2'-biphenyldiol cyclic phosphate, and wherein each of the aforementioned is optionally substituted with one or more substituents selected from (1 -6C)alkyl, (1 -6C)alkoxy, halo, hydroxyl or NR_aRb, and wherein R_a and Rb are independently selected from H or (1 -4C)alkyl.

13. The functionalised hypercrosslinked porous polymeric material according to any one of claims 10 to 12, wherein the aromatic monomer units of step (i) of the process, as defined in any one of claims 1 to 9, are selected from benzene, biphenyl, 1 ,3,5- triphenylbenzene, naphthalene, anthracene, pyrene, thiophene, pyrrole, furan, carbazole, 1 ,1 '-binaphthyl-2,2'-diyl hydrogen phosphate or 2,2'-biphenyldiol cyclic phosphate, and wherein each of the aforementioned is optionally substituted with one or more substituents selected from (1 -4C)alkyl, (1 -4C)alkoxy, halo or hydroxyl.

14. The functionalised hypercrosslinked porous polymeric material according to any one of claims 10 to 13, wherein the aromatic monomer units of step (i) of the process, as defined in any one of claims 1 to 9, are of the Formula (I) or Formula (II), shown below:

Formula (I) Formula (II)

Formula (III)

wherein:

q is an integer between 0 and 3;

Ri is selected from (1 -6C)alkyl, (1 -6C)alkoxy, halo, hydroxyl, aryl, heteroaryl or NR_aRb, wherein R_a and Rb are independently selected from H or (1 - 4C)alkyl; R₂ is selected from hydrogen or (1 -4C)alkyl;

A is absent or phenyl; and

X is selected from O, NH or S.

15. The functionalised hypercrosslinked porous polymeric material according to any one of claims 10 to 14, wherein the aromatic monomer units of step (i) of the process, as defined in any one of claims 1 to 9, are selected from:

wherein Ri is selected from (1 -4C)alkyl, (1 -2C)alkoxy, halo or hydroxyl.

16. The functionalised hypercrosslinked porous polymeric material according to any one of claims 10 to 15, wherein the aromatic monomer units of step (i) of the process, as defined in any one of claims 1 to 9, are selected from benzene, biphenyl, 1 ,3,5- triphenylbenzene, naphthalene, thiophene or 1 ,1 '-binaphthyl-2,2'-diyl hydrogen phosphate.

17. The functionalised hypercrosslinked porous polymeric material according to any one of claims 10 to 16, wherein the crosslinking molecule of step (i) of the process, as defined in any one of claims 1 to 9, is selected from formaldehyde,

paraformaldehyde, chloromethyl methyl ether, formaldehyde dimethyl acetal, dichloromethane, p-xylylene dichloride, bis(chloromethyl)anthracene or 1 ,3,5-tris[4- chloromethyl)phenyl]benzene.

18. The functionalised hypercrosslinked porous polymeric material according to any one of claims 10 to 17, wherein the crosslinking molecule of step (i) of the process, as defined in any one of claims 1 to 9, is selected from formaldehyde, chloromethyl methyl ether or formaldehyde dimethyl acetal.

19. The functionalised hypercrosslinked porous polymeric material according to any one of claims 10 to 18, wherein the crosslinking molecule of step (i) of the process, as defined in any one of claims 1 to 9, is formaldehyde dimethyl acetal.

20. The functionalised hypercrosslinked porous polymeric material according to any one of claims 10 to 19, wherein the functional group introduced in step (ii) of the process, as defined in any one of claims 1 to 9, is selected from an organic acid, an organic base, a carbonyl or a nitro.

21 . The functionalised hypercrosslinked porous polymeric material according to any one of claims 10 to 20, wherein the functional group introduced in step (ii) of the process, as defined in any one of claims 1 to 9, is selected from S0₃H, C0₂H, PO(OH)₂, C(O), NH₂ or N0₂.

22. The functionalised hypercrosslinked porous polymeric material according to any one of claims 10 to 21 , wherein the functional group introduced in step (ii) of the process, as defined in any one of claims 1 to 9, is an organic acid.

23. The functionalised hypercrosslinked porous polymeric material according to claim 22, wherein the functional group introduced in step (ii) of the process, as defined in any one of claims 1 to 9, is selected from S0₃H, C0₂H or PO(OH)₂.

24. The functionalised hypercrosslinked porous polymeric material according to any one of claims 10 to 21 , wherein the functional group introduced in step (ii) of the process, as defined in any one of claims 1 to 9, is an organic base.

25. The functionalised hypercrosslinked porous polymeric material according to claim 24, wherein the functional group introduced in step (ii) of the process, as defined in any one of claims 1 to 9, is amino.

26. The functionalised hypercrosslinked porous polymeric material according to any one of claims 10 to 21 , wherein the functional groups introduced in step (ii) of the process, as defined in any one of claims 1 to 9, comprise one or more organic acid functional groups and one or more organic base functional groups.

27. The use of the functionalised hypercrosslinked porous polymeric material, as defined in any one of claims 10 to 26, in catalysis.

28. The use of the functionalised hypercrosslinked porous polymeric material, as defined in any one of claims 8 to 26, in gas adsorption.

29. The use of the functionalised hypercrosslinked porous polymeric material, as defined in any one of claims 22 or 23, as a solid acid catalyst.

30. The use of the functionalised hypercrosslinked porous polymeric material, as defined in any one of claims 22 or 23, in the hydrolysis of oligo- and polysaccharides.

31 . The use of the functionalised hypercrosslinked porous polymeric material, as defined in any one of claims 24 or 25, as a solid base catalyst.

32. The use of the functionalised hypercrosslinked porous polymeric material according to claim 31 , wherein the solid base catalyst is used in the catalysis of base promoted organic reactions (e.g. alkylation reactions)

33. The use of the functionalised hypercrosslinked porous polymeric material, as defined in claim 26, as an ion-exchange resin.

34. The use of the functionalised hypercrosslinked porous polymeric material, as defined in claim 26, in the catalytic conversion of glucose to 5-hydroxymethylfurfural.

35. The use of the functionalised hypercrosslinked porous polymeric material, as defined in claims 24 or 25, in the absorption of ammonia.

36. The use of a functionalised hypercrosslinked porous polymeric material, as defined in any one of claims 8 to 26, in the purification of water.