A photocurable acrylate resin monomer and the use thereof

Abstract

The present disclosure relates to an improved fluorocarbon resin monomer for use in field of dental restorations, biomedical and healthcare applications, and to a photocurable composition containing a photocurable acrylate resin monomer comprising multiple structurally different fluorocarbon blocks, a method for producing the monomer and the resin, and applications therefor.

Description

Dkt # 104-01-A-PCT A PHOTOCURABLE ACRYLATE RESIN MONOMER AND THE USE THEREOF CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the priority of Australian Patent Application No. 2024206912, filed August 19, 2024, the content of which is hereby incorporated by reference into this application. FIELD OF THE INVENTION

[0002] The present disclosure relates to an improved fluorocarbon resin monomer for use in field of dental restorations, biomedical and healthcare applications, and in particular to a photocurable composition containing a photocurable acrylate resin monomer composed of multiple structurally different fluorocarbon blocks, a method for producing the monomer, and application therefor. BACKGROUND OF THE INVENTION

[0003] Fluorinated resin composite / compositions have emerged as an important class in engineering materials. They are characterized by rigidity, hydrophobicity and oleophobicity, low good resistance to heat and light, and long term chemical stability. These properties make them highly desirable for applications of dental restoration, biomedical and healthcare applications. Within the composition, the fluorinated resin monomer plays an important role in determining the properties of the final resin composite / composition,which requires tailored-made chemical structure to meet specific needs. For examples, a3D printed clear aligner requires the end-product to be elastic and tough to move the teeth and jaws resiliently in incremental steps towards a desired arrangement, but not too brittle to fail to yield and exhibit low elongation. This requires a relatively flexible fluorinated segment, such as trifluoromethyl or fluorinated aliphatic chain with medium to long chain length, to facilitate crosslinking, which in turn enhances the strength / modulus of the final photocurable resin composite / composition. In another application such as resin composite fillings and sealants, the resin composition needs to be low in both polymerization shrinkage and shrinkage stress, together with low water sorption, to maintain physically adherent to tooth surface and surroundings against the oral environment. This makes the fluorinated aryl moieties and high molecular weight fluorinated oligomer more suitable candidates to provide a rigid scaffold for long term use. Additionally, the fluorinated aryl moieties provide abundant intermolecular interactions from their coplanar structures. As a result, monomers with tailored fluorinated chemical architectures come to the market to address and improve functional properties in various applications.

[0004] Unfortunately, most well-studied resin monomers usually contain only onetype of fluorocarbon segment / block, which provides limited degree of physical propertiesto specific applications. Monomers composed of multiple structurally different fluorocarbon blocks, which possess varied physical properties, can offer adjustable advantages. For instance, there is a market trend towards limiting the number of conventional long linearperfluoroalkyl group(i.e. CnF2n+1, n = 6–10) with more rigid ring structures.Thesemonomers are designed in an attempt to enhance the mechanical properties but decrease the compressibility of fluorocarbon polymers. Less toxic and less bio-accumulatively fluorocarbon blocks can also be introduced into the monomers. One of the examples is the use of flexible fluorinated polyether as a building block in functional fluoropolymers in the application with fluorinated coatings. As a result, it is desired to prepare a single fluorinated resin monomer with diverse control in property tuning within the resin matrix, together with less environmental concern.

[0005] The present application discloses the synthesis and preparation of a photocurable resin composition containing a photocurable acrylate resin monomer comprising multiple structurally different fluorocarbon blocks (i.e. structurally different in chain length or functional group existed). SUMMARY OF THE INVENTION

[0006] One aspect of the present disclosure is to provide the synthesis of the photocurable acrylate resin monomer, containing multiple structurally different fluorocarbon moieties, to allow improved chemical, physical or mechanical properties of its final photocurable composition to specific applications.

[0007] Still another aspect of the present disclosure is to provide a photocurable composition, containing a photocurable acrylate resin monomer, containing multiple structurally different fluorocarbon, for cavity sealing, filling and 3D printing for the applications of dental restoration, biomedical and healthcare applications, which show enhanced chemical, physical or mechanical properties in its photocurable composition, such as improved double bond conversion percentage (DC%), volume shrinkage, elastic modulus, tensile strength and flexural strength.

[0008] According to a further aspect, a photocurable acrylate resin monomer is provided.

[0009] In some embodiments, the photocurable acrylate resin monomer can have a structure shown in Figure 1.

[0010] In some embodiments, the photocurable acrylate resin monomer has Formula 1:wherein F is -Fa- or -CH2-Fa-CH2-, wherein Fais a fluorinated moieties,a fluorinated alkyl group, afluorinated aryl group, or a fluorinated cycloalkyl group;F' is -CH2-Fb-CH2-, wherein Fbis a fluorinated alkyl group, a fluorinated aryl group or one or more fluorinated alkoxyalkyl groups; or -CHFc-, wherein Fcis a fluorinated moiety which is a fluorinated alkyl group; C' (in the direction of F'- C' - F) is cycloalkyl-(CH2)n- group, wherein the cycloalkylisoptionally substituted with one or more alkyls and n is 1 to 10; R1 is H or -CH3; and R2 is alkyl group.

[0011] In some embodiments, F and F' are different from each other.

[0012] In some embodiments, Faand Fbare different from each other.

[0013] In some embodiments, Fais a fluorinated moiety in which each of the carbon atoms of the moiety is substituted by a fluoro. Fbis a fluorinated moiety in which each of the carbon atoms of the moiety is substituted by a fluoro. Fcis a fluorinated moiety in which each of the carbon atoms of the moiety is substituted by a fluoro. The carbon can be substituted by one or two fluoros.

[0014] In some embodiments, Fais a perfluorinated moiety. Fbis a perfluorinated moiety. Fcis a fluorinated moiety.

[0015] In some embodiments, F is -CH2-Fa-CH2- and F' is -CH2-Fb-CH2-; F is -Fa- and F' is -CH2-Fb-CH2-; or F is -CH2-Fa-CH2- and F' is -CHFc-.

[0016] In some embodiments, F is -CH2-Fa-CH2-, wherein Fais a fluorinated aryl group; and F' is - CH2-Fb-CH2- or -CHFc-, wherein Fbis afluorinated alkyl group, afluorinated aryl group or one or more fluorinated alkoxyalkyl groups.In this aspect, F' is -CH2-Fb-CH2-, wherein Fb is afluorinated alkyl group or one or more fluorinated alkoxyalkyl groups, preferably fluorinated alkyl group.

[0017] In some embodiments, Fais a fluorinated alkyl group and Fbis a fluorinatedalkyl group. Fa is a fluorinated aryl group and Fb is a fluorinated aryl group. Fa is afluorinated alkyl group and Fb is a fluorinated aryl group. Fa is a fluorinated aryl groupand Fb is a fluorinated alkyl group. Fa is a fluorinated alkyl group and Fb is one or morefluorinated alkoxyalkyl groups. Fais a fluorinated cycloalkyl group and Fbis a fluorinated alkyl group. Fais a fluorinated aryl group and Fcis a fluorinated alkyl group.

[0018] In some .

[0019] In someresin monomer is 1A ,1B , 2A , 2B , 2C , 3A , 3B , or 3C .

[0020] According to another aspect, a photocurable composition is provided comprising the photocurable acrylate resin monomer of the present invention.

[0021] In some embodiments, the photocurable composition comprising the photocurable acrylate resin monomer according to present invention, includes an acrylate resin diluent monomer, a photo- initiator, an inorganic filler material, and optionally a stabilizer.

[0022] In some embodiments, the photocurable composition comprising 5% – 45% by weight of the photocurable acrylate resin monomer, 5% – 55% by weight of the crylate resin diluent monomer, 0.1% – 5% by weight of the photo-initiator, 30% – 80% by weight of the inorganic filler material, and 0% – 5% by weight of a stabilizer, based on the weight of the composition. In some embodiments, the ratio of the photocurable acrylate resin monomer to acrylate resin diluent monomer ranges from 1:10 to 10:1 by weight.

[0023] According to another aspect, the photocurable acrylate resin monomer or the photocurable composition is used in dental restorations, biomedical or healthcare applications. The dental restorations can include 3D printing transparent orthodontic devices, pit-and- fissure sealants and resin composite fillings. The biomedical applications include bone integration and tissue coating. The healthcare applications include anti-fouling / anti- bacterial and superhydrophobic coating.

[0024] According to another aspect, a method for preparing the photocurable acrylate resin monomer according to present invention is provided.

[0025] In some embodiments, the method for preparing the photocurable acrylate resin monomer is shown in Figure 2.

[0026] In some embodiments, the method for preparing the photocurable acrylate resin monomer comprises the steps of a) reacting a diisocyanate compound of OCN-C'-NCO with a dihydroxyl compound of HO- F-OH in the presence of a catalyst in a solvent under a temperature to provide the compound of Formula 2; OCN-C'-NH-C(O)-O-F-O-C(O)-NH-C'-NCO, Formula 2 b) reacting the compound of Formula 2 with another dihydroxyl compound of HO-F’-OH to provide the compound of Formula 3; and HO-F’-OC(O)-NH-C'-NH-C(O)O-F-OC(O)-NH-C'-NH-C(O)O-F’-OH, Formula 3c)reacting the compound of Formula 3 with a capping mono-isocyanate of CH2=CR1- C(O)O-R2-NCO to provide the compound of Formula 1, wherein the F, F', C', R1, and R2 are as defined herein.

[0027] In some embodiments, the catalyst is an organometallic based catalyst(including dibutyltin dilaurate (DBTDL), a dibutyltin diacetate (DBTDA), a Zirconiumacetylacetonate (Zr(acac)4), a Bismuth neodecanoate, a Zinc neodecanoate, a n Iron(II)triflate or Titanium diisopropoxide bis(acetylacetonate)); or an organic base based catalyst (including 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or N-heterocyclic Carbene (NHC)), preferably DBTDL or DBTDA.

[0028] In some embodiments, the solvent is acetone, chloroform, dichloromethane, diethyl ether, N,N-dimethylformamide, ethyl acetate, methyl tert-butyl ether, tetrahydrofuran, and toluene, preferably dichloromethane. In some embodiments, the preferred temperature of reaction is between 25oC – 90oC.

[0029] The method according to the invention allows more control of the physical or mechanical property tuning of its final photocurable compositions for specific applications.

[0030] The photocurable composition comprising the photocurable acrylate resin monomer inserted with multiple structurally different fluorocarbons has enhanced chemical, physical or mechanical properties in its photocurable composition, such as double bond conversion percentage (DC%), volume shrinkage, elastic modulus, tensile strength and flexural strength, for cavity sealing, filling and 3D printing for the applications of dental restoration, biomedical and healthcare applications.

[0031] Moreover, the present application reduces the health concern from using conventional long linear perfluoroalkyl groups.BRIEF DESCRIPTION OF THE FIGURES

[0032] Fig. 1. General structural formula of the photocurable acrylate resin monomer, which contains multiple structurally different fluorocarbon blocks. The general structural formula of the monomer consists of 2 end-capping moieties (L), 3 fluorinated moieties (F’ & F’’, structurally different from each other) and 2 non-fluorinated moieties (C), shown inFormula1. They are linked up to each other with carbamate linkage (-NHCO2-, in symbolof --- inFigure 1). The end capping L is chosen from acrylate or methacrylate with chemicalformulaof CH2=C(R1)CO2(R2)-, wherein R1 represents either H or CH3, and R2 is asubstituted orunsubstituted alkyl group with 2 to 8 carbon atoms. The fluorinated moieties F’ & F’’ are different from other and are independently chosen from fluorinated alkyl groups; fluorinated alkoxyalkyl groups; fluorinated cycloalkyl groups; fluorinated aryl groups; fluorinated alkylaryl groups. The non-fluorinated moiety C is chosen from alkyl groups; cycloalkyl groups; cycloalkyl-alkyl groups; aryl groups; acycloalkylsilylalkyl groups; cycloalkylsilylalkyl groups; and arylsilylalkyl groups.

[0033] Fig. 2. General synthetic scheme of the photocurable acrylate resin monomer, which contains multiple structurally different fluorocarbon blocks. This photocurable acrylate resin monomer is synthesized with 3 step reactions, without any extraction and work-up in-between, represented by the synthetic scheme in Figure 2. Under catalytic condition, a diisocyanate compound (OCN-C-NCO) is reacted with dihydroxyl compound (HO-F’’-OH) to form an intermediate (OCN-C-F’’-C-NCO). Upon half of the -NCO unit is consumed, the intermediate is transferred into another dihydroxyl compound solution (HO-F’-OH), which is structurally different from the initial dihydroxyl compound, to completely consume all -NCO unit. After that, a capping mono-isocyanate (L-NCO) is added to yield the product in Formula 1, followed by extraction and washing with water. The overall mole ratio among reactants HO-F’’-OH : OCN-C-NCO : HO-F’-OH : L-NCO is 1: 1.95 – 2.05 : 1.95 – 2.05 : 1.95 – 2.05. Suitably, the mole ratio of HO-F’’-OH : OCN-C-NCO : HO-F’-OH : L-NCO may be 1: 1.97 – 2.03 : 1.97 – 2.03 :1.97 – 2.03, more suitably the molar ratio of HO-F’’-OH : OCN-C-NCO : HO-F’-OH : L-NCO may be 1: 2 : 2 : 2. Insertion of multiple fluorocarbon blocks in a single monomer allows one to gain more control on property tuning of its final composition. DETAILED DESCRIPTION OF THE INVENTION

[0034] Hereinafter, embodiments of the present disclosure will be described in detail so as to be easily carried out by those of ordinary skill in the art to which the present disclosure pertains. However, the present disclosure may be implemented in various different forms and is not limited to examples described herein.

[0035] According to an aspect, provided is a photocurable acrylate resin monomer having Formula 1:wh F is -Fa- or -CH2-Fa-CH2-, wherein Fais a fluorinated moiety selected from the group consisting of fluorinated alkyl group, fluorinated aryl group, or fluorinated cycloalkyl group; F' is -CH2-Fb-CH2-, wherein Fbis a fluorinated moiety selected from the group consisting of fluorinated alkyl group, fluorinated aryl group or one or more fluorinated alkoxyalkyl groups; or -CHFc-, wherein Fcis a fluorinated moiety which is a fluorinated alkyl group; C' (in the direction of F'- C' - F) is cycloalkyl-(CH2)n- group, wherein the cycloalkylisoptionally substituted with one or more alkyl and n is 1 to 10; R1 is H or -CH3; and R2is alkyl group.

[0036] In some embodiments, F and F' are different from each other. In some embodiments, Faand Fbare different from each other.

[0037] In some embodiments, Fbcan be one to ten alkoxyalkyl groups, such as two, three, four or five alkoxyalkyl groups, preferably two alkoxyalkyl groups.

[0038] In some embodiments, each of the carbon atoms of the fluorinated alkyl group, the fluorinated aryl group, the fluorinated cycloalkyl group, or the fluorinated alkoxyalkyl group in Fa, Fbor Fccan be substituted by a fluoro, such as one, two or three fluoro atoms.

[0039] In some embodiments, F is -CH2-Fa-CH2-, wherein Fais a perfluorinatedmoiety, including a perfluorinated alkyl group, or a perfluorinated aryl group.

[0040] In some embodiments, F is -Fa-, wherein Fais a fluorinated cycloalkyl group, forexample,fluorinated C3-C8cycloalkyl .

[0041] In some embodiments, F'wherein Fbis a perfluorinatedmoiety, including a perfluorinated alkyl group, a perfluorinated aryl group or one or moreperfluorinated alkoxyalkyl groups.

[0042] In some embodiments, F' is -CHFc-, wherein Fcis a fluorinated alkyl group.

[0043] In some embodiments, F is -CH2-Fa-CH2- and F' is -CH2-Fb-CH2-; F is -Fa- and F' is -CH2-Fb-CH2-; or F is -CH2-Fa-CH2- and F' is -CHFc-.

[0044] In some embodiments, F is -CH2-Fa-CH2-, wherein Fais a fluorinated arylgroup; and F' is - CH2-Fb-CH2- or -CHFc-, wherein Fb isfluorinated alkyl group, a fluorinatedaryl group or one or more fluorinated alkoxyalkyl groups,and Fc is a fluorinated moiety whichis a fluorinated alkyl group. In this aspect, F' is -CH2-Fb- CH2-, wherein Fbis a fluorinatedalkylgroup or one or more fluorinated alkoxyalkyl groups, preferably a fluorinated alkyl group.

[0045] In some embodiments, Fais a fluorinated alkyl group and Fbis a fluorinatedalkyl group. Fa is a fluorinated aryl group and Fb is a fluorinated aryl group. Fa is afluorinated alkyl group and Fbis a fluorinated aryl group. Fais a fluorinated aryl group andFb is a fluorinated alkyl group. Fa is a fluorinated alkyl group and Fb is one or morefluorinated alkoxyalkyl groups. Fais a fluorinated cycloalkyl group and Fbis a fluorinated alkyl group. Fais a fluorinated aryl group and Fcis a fluorinated alkyl group.

[0046] In some embodiments, F is -CH2-Fa-CH2-, wherein Fais a perfluorinated C1- C6alkyl group or a perfluorinated phenyl group. In addition, Facan be -CF2-, -(CF2)2-, -(CF2)3-, -(CF2)4-, -(CF2)5- or -(CF2)6-, .

[0047] In some embodiments, F' is - C1- C6alkyl group or a perfluorinated phenyl, -(CF2)2-, In2-, a-CF2CF2CF2CF3, or - CF2CF2CF2CF2CF3.

[0048] In some embodiments, C' in the direction of F'- C' - F is cycloalkyl-(CH2)n-group, whereinthe cycloalkyl is optionally substituted with one or more alkyl groups and n is 1 to 10. In this embodiment, the cycloalkyl can be substituted with one, two,three, four, five or six alkylgroups, preferably three. The alkyl is preferably -CH3. The ncan be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.In the formula "F'- C' -F" or "F'~ C' ~F", the symbol "-"interchangeable with "~" means that the variable C' is indirectly attached to F' and F, respectively, e.g., thorugh the group of "-NH-C(O)-O-". The formula "F'- C' -F" or "F'~C' ~F" only aims to clearly define thedirection of cycloalkyl-(CH2)n- group attached to thetwo adjacent groups of "-NH-C(O)-O-".More specifically, "F'- C' -F" or "F'~ C' ~F" means"-F'-O-C(O)-NH-C'-NH-C(O)-O-F-". In addition, C' .

[0049] According to another aspect, ais provided which comprises the photocurable acrylate resin monomer of the present invention, an acrylate resin diluent monomer, a photo-initiator, an inorganic filler material, and optionally a stabilizer.

[0050] In some embodiments, the composition can comprise at least 1%, at least 2%, at least 3%, at least 4%, or at least 5% by weight of the photocurable acrylate resin monomer of present invention, based on the weight of the composition. Specifically, the composition can comprise 5%–60% or 5%–45% by weight of the photocurable acrylate resin monomer, for example, 10%, 15%, 20%, 30%, 35%, 40%, 45%, 50% or 55% by weight of the photocurable acrylate resin monomer.

[0051] In some embodiments, the composition can comprise at least 1%, at least 2%, at least 3%, at least 4%, or at least 5% by weight of the acrylate resin diluent monomer, based on the weight of the composition. Specifically, the composition can comprise 5%–70%or 5%–55% by weight of the acrylate resin diluent monomer, for example, 10%, 15%, 20%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, or 65% by weight of the acrylate resin diluent monomer.

[0052] In some embodiments, the composition can comprise 0% or at least 0.01%, at least 0.05% or at least 0.1% by weight of the photo-initiator, based on the weight of the composition. Specifically, the composition can comprise 0.1%–10% or 0.1%–5% by weight of the acrylate resin diluent monomer, for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8% or 9% by weight of the photo-initiator.

[0053] In some embodiments, the composition can comprise 0% or at least 5%, at least 10%, at least 15%, at least 20%, at least 25% or at least 30% by weight of the inorganic filler material, based on the weight of the composition. Specifically, the composition can comprise 30%–90% or 30%–80% by weight of the inorganic filler material, for example, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 85% by weight of inorganic filler material.

[0054] In some embodiments, the composition can comprise 0% or at least 0.1%, at least 0.2%, at least 0.3%, at least 0.4% or at least 0.5% by weight of stabilizer, based on the weight of the composition. Specifically, the composition can comprise 0%–10% or 0%–5% by weight of the stabilizer, for example, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% by weight of the stabilizer.

[0055] In some embodiments, the ratio of the photocurable acrylate resin monomer to acrylate resin diluent monomer is ranging from 1:20 to 20:1 by weight or 1:10 to 10:1 by weight, for example, 1:15, 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, or 15:1.

[0056] In some embodiments, the acrylate resin diluent monomer is acyclic acrylate- or methacrylate-based diluent monomer (including allyl methacrylate (AMA), 1,3- butanediol diacrylate (1,3-BDDA), 1,4-butanediol diacrylate (1,4- BDDA), butyl methacrylate (nBMA), tert-butyl methacrylate (tBMA), 1,10-decanediol dimethacrylate (DDDMA or D3MA), di(ethylene glycol) dimethacrylate, 2- (diethylamino)ethyl methacrylate (DEAME), 2-(dimethylamino)ethyl methacrylate (DMAEMA), dithiodi-2,1- ethanediyl bismethacrylate, diurethane dimethacrylate, ethyl methacrylate (EMA), ethyleneglycol methyl ether methacrylate, 2-ethylhexyl acrylate (2EHA), 2-ethoxyethyl methacrylate (2EOEMA), glycerol dimethacrylate (GDMA), hexafluoro-iso- propyl methacrylate (HFiPMA), 1,6-hexanediol dimethacrylate (HDODA), n-hexyl methacrylate (nHMA), 2- hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate (HPMA), 2- isocyanatoethyl methacrylate (IEM), methyl methacrylate (MMA), 2,2,3,3,4,4,5,5- octafluoropentyl methacrylate, poly(caprolactone) methacrylate (PCLMA), tetraethylene glycol dimethacrylate (Te EGDMA), triethylene glycol dimethacrylate (TEGDMA), 2,2,2- trifluoroethyl methacrylate (TFEMA) or urethane dimethacrylate (UDMA)); cyclic acrylate- or methacrylate-based diluent monomer (including benzyl methacrylate (BZMA), cyclohexyl methacrylate (CHMA), furfuryl methacrylate (FMA), glycidyl methacrylate (GMA), isobornyl Acrylate (IBOA), isobornyl methacrylate (IBOMA), 2-morpholinoethyl methacrylate (MEMA), pentafluorophenyl acrylate (PFPA), pentafluorophenyl methacrylate (PFPMA), phenyl methacrylate, pyromellitic dianhydride glycerol dimethacrylate (PMGDM) or tetrahydrofurfuryl methacrylate (THFMA)); silyl acrylate- or methacrylate-based (including 2- (trimethylsilyloxy)ethyl methacrylate, 3-(trimethoxysilyl)propyl acrylate (TMSPA), 3- (trimethoxysilyl)propyl methacrylate (TMSPMA) or 3-[tris(trimethylsiloxy)silyl]propyl methacrylate); charged acrylate- or methacrylate-based diluent monomer (including potassium 3-sulfopropyl methacrylate, 2-(N-3-sulfopropyl-N,N-dimethylammonium)ethyl methacrylate (DMAPS) or 2-trimethylammonioethyl methacrylate chloride.

[0057] Preferably, the acrylate resin diluent monomer is triethylene glycol dimethacrylate (TEGDMA), or 2-(dimethylamino)ethyl methacrylate (DMAEMA), more preferably TEGDMA.

[0058] In some embodiments, the photo-initiator is camphorquinone / amine / diphenyliodonium hexafluorphosphate (DPI)-based photo-initiator (amine including ethyl 4-(dimethylamino)benzoate, 2-(dimethylamino)ethyl methacrylate (DMAEMA), 2-ethyl-dimethylbenzoate, N,N-dimethyl-p-toluidine or N-phenylglycine); phenone-based photo-initiator (including benzophenone, 2-hydroxy-2-methyl-1-phenyl- propan-1-one, 2,2-dimethoxy-2-phenylacetophenone (DMPA) or 2-Hydroxy-1-[4-(2- hydroxyethoxy)phenyl]-2-methylpropan-1-one); phosphine oxide-based photo-initiator (including trimethylbenzoyl-diphenyl-phosphine oxide (TPO), bis(2,4,6-trimethylbenzoyl)- phenyl-phosphine oxide (BAPO), 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (TPO-L) or 2,4,6-trimethylbenzoyl-bis(4-methylphenyl)-phosphinyl oxide (TMO)); and germanium-based photo-initiator (including Ivocerin).

[0059] Preferably, the photo-initiator is camphorquinone, 2-(dimethylamino)ethyl methacrylate and diphenyliodonium hexafluorphosphate. The ratio of CQ, DMAEMA and DPI can be 2:8:5.

[0060] In some embodiments, the inorganic filler material is inorganic filler with particle size between 0.01 μm to 10 μm, including metal oxide particle, glass particle or bioactive glass filler), and inorganic fibre with length between 0.8 mm to 400 mm and diameter between 0.1 mm to 1 mm (including glass fibre). In addition, the inorganic filler material can be calcium aluminum borosilicate, e.g. calcium aluminum borosilicate with particle size of 1-1.5 µm.

[0061] In some embodiments, the stabilizer is a stabilizer with building block containing phenolic (including 2,6-di-tert-butyl-p-cresol (BHT), 4-methoxyphenol (MEHQ) and 4-tert- butylcatechol (TBC)); hydroquinone (including hydroquinone (HQ), ortho- benzoquinones (oBQ), para-benzoquinones (pBQ), tert-butyl hydroquinone (TBHQ) and 2,5-di-tert-butyl- hydroquinone (2,5-DTBHQ)); benzotriazole (including 2-(2-Hydroxy-3,5- dicumyl)benzotriazole); N,N-substituted hydroxylamine (including N,N- dibenzylhydroxylamine (DBHA)); hindered amine or aminoxyl (including 2,2,6,6- tetramethylpiperidin-1-yl)oxyl (TEMPO)) or organophosphorus (including tris(2,4-ditert- butylphenyl)phosphite).

[0062] In some embodiments, the method for preparing the photocurable acrylate resin monomer comprises the steps of a) reacting a diisocyanate compound of OCN-C'-NCO with a dihydroxyl compound of HO- F-OH in the presence of a catalyst in a solvent under a temperature to provide the compound of Formula 2; OCN-C'-NH-C(O)-O-F-O-C(O)-NH-C'-NCO, Formula 2 b)reacting the compound of Formula 2 with another dihydroxyl compound of HO-CH2- F’-CH2-OH to provide the compound of Formula 3; and HO-F’-OC(O)-NH-C'-NH-C(O)O-F-OC(O)-NH-C'-NH-C(O)O-F’-OH, Formula 3 c)reacting the compound of Formula 3 with a capping mono-isocyanate of CH2=CR1- C(O)O-R2-NCO to provide the compound of Formula 1, wherein the F, F', C', R1, and R2are as defined herein.

[0063] In some embodiments, the catalyst is an organometallic based catalyst (including dibutyltin dilaurate (DBTDL), dibutyltin diacetate (DBTDA),Zirconiumacetylacetonate (Zr(acac)4), Bismuth neodecanoate, Zinc neodecanoate, Iron(II)triflate orTitanium diisopropoxide bis(acetylacetonate)); and an organic base based catalyst (including 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or N-heterocyclic Carbene (NHC)). Preferably, the catalyst is DBTDL or DBTDA. The total amount of catalyst used is accounted for 0.01 to 1% of the total weight of reactants. Suitably, the catalyst may account for 0.05 to 0.5% of the total weight of reactants, more suitably the catalyst may account for 0.05 to 0.1 % of total weight of reactants.

[0064] In some embodiments, the solvent is acetone, chloroform, dichloromethane, diethyl ether, N,N-dimethylformamide, ethyl acetate, methyl tert-butyl ether, tetrahydrofuran, and toluene. Preferably, the solvent is dichloromethane. The total solvent used in reaction is ranging from 5:1 to 1:5 by weight of solvent to weight of all reactants, suitably from 4:1 to 1:4, and more suitably from 2:1 to 1:2.

[0065] In some embodiments, the temperature is between 25oC – 90oC, e.g.25oC, 30oC,35oC, 40oC, 45oC, 50oC, 55oC, 60oC, 65oC, 70oC, 75oC, 80oC or 85oC.

[0066] In some embodiments, the method comprises the steps of a) to c) without any extraction and work-up in-between.

[0067] In some embodiments, the method further comprises a step of d) extraction and washing with water. The extraction is carried out with a water-immiscible organic solvent. The immiscible organic solvent is chloroform, dichloromethane, diethyl ether, ethyl acetate. The method can further comprise a step of e) adding a drying agent and removing solvent in vacuo.

[0068] In some embodiments, the overall mole ratio among reactants HO-F-OH :OCN-C'-NCO :HO-F’-OH : CH2=CR1-C(O)O-R2-NCO is 1: 1.95 – 2.05 : 1.95 – 2.05 : 1.95 –2.05. Suitably, themole ratio of HO-F-OH : OCN-C'-NCO : HO-F’-OH : L-NCO may be 1: 1.97–2.03 :1.97–2.03 : 1.97–2.03, more suitably the molar ratio of HO-F-OH :OCN-C'-NCO : HO-F’-OH : CH2=CR1-C(O)O-R2-NCO may be 1 : 2 : 2 : 2.

[0069] In some embodiments, the 3 step reaction lasts for 10 to 96 hours, e.g. 12, 24, 32, 48, 60, 72, 84 hours.

[0070] The term "alkyl" can include alkyl or alkylene, wherein alkyl is a fullysaturated linear orbranched monovalent non-aromatic (aliphatic) hydrocarbon group (generalformula -CnH2n+1),and alkylene is fully saturated linear or branched bivalent aliphatic radical(general formula -CnH2n-), where n represents the number of carbon atoms. Typically, unlessotherwise defined,a linear or branched alkyl group has 1 to 20 carbon atoms, such as 1 to 18 carbon atoms, such as 1 to 10 carbon atoms, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl,isopropyl, n-butyl,sec-butyl, tert-butyl, pentyl, hexyl, pentyl and octyl. C1-C6 linear orbranched alkyl groups arealso called "lower alkyl groups". Alkyl groups may be substituted with one or more substituents such as fluorine. The alkyl group may be a perfluoroalkyl group or perfluorinated alkyl group, i.e. all hydrogens are replaced by fluorine. The number of carbon atoms in the alkylene group is as defined for the alkyl group. Examples of alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene. Alkylene groups may be substituted with one or more substituents such as fluorine. The alkyllene group may be a perfluoroalkylene group or perfluorinated alkylene group, i.e. all hydrogens are replaced by fluorine. Substitutedalkylene may, for example, be(CF2)n-, where n represents the number ofcarbon atoms as defined above.

[0071] The term "alkoxyalkyl" refers to alkyl-O-alkyl which can have formula CnH2n+1-O- CmH2m- or -CnH2n-O-CmH2m-, where n and m represent the number of carbon atoms of the alkylgroups.The term "alkenyl" may include alkenyl or alkenylene, where alkenyl refers to a non- cyclic monovalent aliphatic group containing at least one double bond, and alkenylene refers to a non- cyclic bivalent aliphatic group containing at least one double bond. Alkenyl group can have 2 to 20 carbon atoms, such as 2 to 10 carbon atoms, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. The number of carbon atoms of "alkenylene" is as defined for "alkenyl".

[0072] The term "cycloalkyl" may include cycloalkyl or cycloalkylene groups, which are fully saturated monovalent or bivalent cyclic hydrocarbon radicals and include monocyclic and bicyclic rings. Unless otherwise defined, generally, a cycloalkyl or cycloalkylene group has 3 to 14 carbon atoms, typically 3 to about 10 carbon atoms, such as 3to 8 carbon atoms, such as 4, 5, 6, 7, 9, 11, 12 and 13 carbon atoms.

[0073] The term "aryl" may include aryl or arylene, generally refers to a monocyclic, bicyclic or polycyclic aromatic carbon atom ring structure radical which can be monovalent or bivalent. The aryl or arylene group can include 6 to 20 carbon numbers, such as 6 to 10 carbon numbers, such as 6, 8, 10, 12, 14, 16, 18 or 20 carbon atoms. Examples of aryl or arylene group include, but not limited to, phenyl, naphthyl, anthracenyl, fluorenyl, azulenyl, phenanthrenyl and the like.

[0074] The group or radical described herein may be substituted or unsubstituted, and the substituents on the group or radical may be selected from halogen, alkyl, alkenyl, cycloalkyl, amino, or carboxyl (-COOH).

[0075] Halogen can be fluorine, chlorine, bromine or iodine.

[0076] Chemical bond usually refers to a covalent bond, such as C-C bond, C-O bond, C-N bond, etc. EXAMPLES

[0077] Examples of Synthesis Table 1. Chemical structure for examples of photocurable acrylate resin monomer, which contains multiple structurally different fluorocarbon blocks: Examples Chemical structure 1A 1B 2A 2B 2C 3A 3B 3C

[0078] Synthesis of Example 1A

[0079] 8 g of 2,2,3,3-Tetrafluoro-1,4-butanediol was suspended in 50 mL DCM (Dichloromethane), followed by 22 g isophorone diisocyanate and 0.06 g dibutyltin dilaurate. The reaction was refluxed at 40oC until the -NCO was half consumed, which was monitored by titration in n-butylamine against hydrochloric acid.13 g of 2-hydroxyethyl methacrylate was then added to the reaction mixture and refluxed at 50oC until completed consumption of newly added -NCO units. The organic layer was washed with D.I. water 3 times and dried over anhydrous magnesium sulfate. After removal of solvent, 39 g glassy gel was obtained with yield of 90%. HRMS (ESI-MS, m / z): [M+Na]+: 889.4195; calcd for [M+Na]+: 889.4198.

[0080] Synthesis of Example 1B

[0081] 13 g of 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diol was suspended in 50 mL DCM, followed by 22 g isophorone diisocyanate and 0.06 g dibutyltin dilaurate. The reaction was refluxed at 40oC until the -NCO was consumed by half, which was monitored by titration in n- butylamine against hydrochloric acid. The reaction mixture was added dropwise to a flask containing 16 g 2,2,3,3- tetrafluorobutanediol suspended in 30 mL DCM and the temperature raised to 50oC. After completed consumption of -NCO units (by FTIR), 16 g 2- isocyanatoethyl methacrylate was added and reacted at 55oC until completed consumption of newly added -NCO units. The organic layer was washed with D.I. water 3 times and dried over anhydrous magnesium sulfate. After removal of solvent, 59 g glassy solid was obtained with yield of 88%. HRMS (ESI-MS, m / z): [M+Na]+: 1363.4637; calcd for [M+Na]+: 1363.4647.

[0082] Synthesis of Example 2A

[0083] 11 g of 2,3,5,6-Tetrafluoro-1,4-benzenedimethanol was suspended in 50 mL DCM, followed by 22 g isophorone diisocyanate and 0.06 g dibutyltin dilaurate. The reaction was refluxed at 40oC until the -NCO was consumed by half, which was monitored by titration in n-butylamine against hydrochloric acid. The reaction mixture was added dropwise to a flask containing 21 g 2,3,5,6-Tetrafluoro-1,4-benzenedimethanol suspended in 30 mL DCM and raise the temperature to 50oC. After completed consumption of -NCO units (by FTIR), 16 g 2- isocyanatoethyl methacrylate was added and reacted at 55oC until completed consumption of newly added -NCO units. The organic layer was washed with D.I. water 3 times and dried over anhydrous magnesium sulfate. After removal of solvent, 66 g glassy solid was obtained with yield of 95%. HRMS (ESI-MS, m / z): [M+Na]+: 1407.4706; calcd for [M+Na]+: 1407.4711.

[0084] Synthesis of Example 2B

[0085] 13 g of 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diol was suspended in 50 mL DCM, followed by 22 g isophorone diisocyanate and 0.06 g dibutyltin dilaurate. The reaction wasrefluxed at 40oC until the -NCO was half consumed, which was monitored by titration in n- butylamine against hydrochloric acid. The reaction mixture was added dropwise to a flask containing 21 g 2,3,5,6- Tetrafluoro-1,4-benzenedimethanol suspended in 30 mL DCM and raise the temperature to 50oC. After completed consumption of -NCO units (by FTIR), 16 g 2-isocyanatoethyl methacrylate was added and reacted at 55oC until completed consumption of newly added - NCO units. The organic layer was washed with D.I. water 3 times and dried over anhydrous magnesium sulfate. After removal of solvent, 69 g glassy solid was obtained with yield of 96%. HRMS (ESI-MS, m / z): [M+Na]+: 1459.4620; calcd for [M+Na]+: 1459,4647.

[0086] Synthesis of Example 2C

[0087] 11 g of 2,3,5,6-Tetrafluoro-1,4-benzenedimethanol was suspended in 50 mL DCM, followed by 22 g isophorone diisocyanate and 0.06 g dibutyltin dilaurate. The reaction was refluxed at 40oC until the -NCO was consumed by half, which was monitored by titration in n-butylamine against hydrochloric acid. The reaction mixture was added dropwise to a flask containing 26 g 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diol suspended in 30 mL DCM and raise the temperature to 50oC. After completed consumption of -NCO units (by FTIR), 16 g 2-isocyanatoethyl methacrylate was added and reacted at 55oC until completed consumption of newly added - NCO units. The organic layer was washed with D.I. water 3 times and dried over anhydrous magnesium sulfate. After removal of solvent, 64 g glassy solid was obtained with yield of 86%. HRMS (ESI-MS, m / z): [M+Na]+: 1511.4553; calcd for [M+Na]+: 1511.4583.

[0088] Synthesis of Example 3A

[0089] 11 g of 2,3,5,6-Tetrafluoro-1,4-benzenedimethanol was suspended in 50 mL DCM, followed by 22 g isophorone diisocyanate and 0.06 g dibutyltin dilaurate. The reaction was refluxed at 45oC until the -NCO was consumed by half, which was monitored by titration in n-butylamine against hydrochloric acid. The reaction mixture was added dropwise to a flask containing 17 g 2,2,3,3,3-pentafluoropropane-1,1-diol (CAS: 422-63-9) suspended in 30 mL DCM and raise the temperature to 50oC. After completed consumption of -NCO units (by FTIR), 16 g 2- isocyanatoethyl methacrylate was added and reacted at 55oC until completed consumption of newly added -NCO units. The organic layer was washed with D.I. water 3 times and dried over anhydrous magnesium sulfate. After removal of solvent, 26 g glassy solid was obtained with yield of 40%. HRMS (ESI-MS, m / z): [M+H]+: 1319.4199; calcd for [M+Na]+: 1319.4209.

[0090] Synthesis of Example 3B

[0091] 11 g of 2,3,5,6-Tetrafluoro-1,4-benzenedimethanol was suspended in 50 mL DCM, followed by 22 g isophorone diisocyanate and 0.06 g dibutyltin dilaurate. The reaction was refluxed at 40oC until the -NCO was consumed by half, which was monitored bytitration in n-butylamine against hydrochloric acid. The reaction mixture was added dropwise to a flask containing 29 g 2,2,4,4,5,5,7,7-Octafluoro-3,6-dioxaoctane-1,8-diol (CAS: 129301- 42-4) suspended in 30 mL DCM and raise the temperature to 55oC. After completed consumption of -NCO units (by FTIR), 16 g 2-isocyanatoethyl methacrylate was added and reacted at 55oC until completed consumption of newly added -NCO units. The organic layer was washed with D.I. water 3 times and dried over anhydrous magnesium sulfate. After removal of solvent, 59 g glassy solid was obtained with yield of 75%. HRMS (ESI-MS, m / z): [M+H]+: 1575.4321; calcd for [M+Na]+: 1575.4380.

[0092] Synthesis of Example 3C

[0093] 9 g of 2,3,5,6-tetrafluorocyclohexane-1,4-diol (synthesized according to Keddie et al., DOI: 10.1038 / nchem.2232) was suspended in 50 mL DCM, followed by 22 g isophorone diisocyanate and 0.06 g dibutyltin dilaurate. The reaction was refluxed at 40oC until the -NCO consumption by half, which was monitored titration in n-butylamine against hydrochloric acid. The reaction mixture was added dropwise to a flask containing 16 g 2,2,3,3- tetrafluorobutanediol suspended in 30 mL DCM and raise the temperature to 50oC. After completed consumption of -NCO units (by FTIR), 16 g 2-isocyanatoethyl methacrylate was added and reacted at 55oC until completed consumption of newly added -NCO units. The organic layer was washed with D.I. water 3 times and dried over anhydrous magnesium sulfate. After removal of solvent, 40 g glassy solid was obtained with yield of 63%. HRMS (ESI-MS, m / z): [M+H]+: 1289.4860; calcd for [M+Na]+: 1289.4867.

[0094] Preparation of photocurable composition formulation

[0095] General procedure of photocurable composition formulation preparation For the fabrication of photocurable composition, 17.5 g of photocurable acrylate resin monomer was mixed with 7.5 g triethylene glycol dimethacrylate (TEGDMA, as diluent monomer) at 50oC to partially homogenize the composition, the composition was then mixed homogenously at 2000 rpm for 6 minutes. 0.1 g camphorquinone (CQ), 0.4 g 2- (dimethylamino)ethyl methacrylate (DMAEMA), 0.25 g diphenyliodonium hexafluorphosphate (DPI) and 25 g calcium aluminum borosilicate (with size of 1-1.5 µm, as filler) were subsequently added and mixed at 2000 rpm for 2 minutes each to a homogenous resin composition. The resin composition was UV-cured at 400 nm for 20 seconds. Table 2. Weight ratio of components in each photocurable composition formulation Formulation Photocurable Wt% of Wt% of Wt% of Wt% of Wt% of arcylate resin TEGDMA CQ DMAEMA DPI Filler * monomer (wt%) F-1A 1A (34.5) 14.8 0.2 0.8 0.5 49.2F-1B 1B (34.5) 14.8 0.2 0.8 0.5 49.2 F-2A 2A (34.5) 14.8 0.2 0.8 0.5 49.2 F-2B 2B (34.5) 14.8 0.2 0.8 0.5 49.2 F-2C 2C (34.5) 14.8 0.2 0.8 0.5 49.2 F-3A 3A (34.5) 14.8 0.2 0.8 0.5 49.2 F-3B 3B (34.5) 14.8 0.2 0.8 0.5 49.2 F-3C 3C (34.5) 14.8 0.2 0.8 0.5 49.2 *Filler is calcium aluminium borosilicate with particle size between 1-1.5 um.

[0096] Result of physical / mechanical measurement of photocurable composition formulation Table 3. Physical and Mechanical properties of each photocurable composition formulation Examples C-1oF-1A F-1B F-2A F-2B F-2C F-3A F-3B F-3C Photocurable arcylate resin - 1A 1B 2A 2B 2C 3A 3B 3C monomer No. of fluorocarbon block in - 1 3 3 3 3 3 3 3 unit monomer Double bond conversion 45-55 50-60 60-70 35-45 35-45 55-65 50-60 60-70 60-70 (%)^ Normalized Polymerization ◊ 1 0.75 0.65 0.80 0.80 0.65 0.70 0.70 0.70 Shrinkage Normalized Average Depth 1 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 of cure* Normalized Average 1 1 1.2 0.45 0.5 1.5 1.2 1.4 1.2 Flexural Strength* Normalized Average Water 1 0.8 0.8 1.2 1.2 0.8 0.8 0.8 0.8 sorption* Normalized Average Water 1 2.25 2.25 2.75 2.75 2.25 2.30 2.40 2.40 solubility*oC-1is the commercial product, named 3M flowable Z350 Restorative. ^ Double bond conversion is measured by ATR-FTIR method following the procedure in Meng Zhang et al., J. Oral Sci. 2016, 58, 15-22, using absorbance ratio of C=C:C=O peaks before and after UV-curing. Measurement follows the procedure under ISO 17304:2013 (Dentistry — Polymerization shrinkage: Method for determination of polymerization shrinkage of polymer-based restorative materials). *Measurement follows the procedure under EN ISO 4049:2019 (Dentistry - Polymer-based restorative materials).

[0097] Discussion

[0098] Example 1: Comparison of resin monomer containing mono-fluorocarbonblock against multiple-fluorocarbon block

[0099] Moving from mono-fluorocarbon block (in F-1A) to multiple-fluorocarbon block- containing photocurable resin monomer (in F-1B), double bond conversion and flexural strength in F-1B was improved, whereas its polymerization shrinkage was reduced. This will hopefully reduce the disruption of network integrity within the dental matter during application.

[0100] Example 2: Compare multiple-fluorocarbon block resin monomer containing 1, 2 and 3 fluorinated benzene

[0101] In the second example, we further demonstrated the control in property tuning with our multiple-fluorocarbon block resin monomer by replacing the rigid fluorinated ring with fluorinated chain. With enhanced network formation, F-2C revealed an enhanced flexural strength, together with a reduced polymerization shrinkage, compared to F- 2A and F2B. This result emphasizes the benefits of having multi-fluorocarbon blocks in a single monomer unit for gaining wider control on physical / mechanical property tuning of the final product.

[0102] Example 3: Compare multiple-fluorocarbon block resin monomers containing widen spectrum fluorocarbon blocks, and that with commercial formulation C-1 .

[0103] In the third example, it showed the possibility in further optimizing / maintaining the properties by introduction of different fluorocarbons. For instance, replacing the side fluorocarbon in F-2C with ether-linked fluorocarbon (in F-3B) enhances double bond conversion, with little sacrifice in flexural strength, water sorption and solubility. As a result, the use of photocurable composition formulation with tunable multi-fluorocarbon block- containing resin monomers is potentially to allow one to achieve an optimized and even superior physical and mechanical performance when compared to commercial product, such as C-1.

[0104] In summary, the present disclosure provides the synthetic method of a photocurable acrylate resin monomer, which contains multiple structurally different fluorocarbon blocks. This disclosure also presents the preparation and application of the photocurable composition, which contains the photocurable acrylate resin monomer with multiple structurally different fluorocarbon blocks. The disclosure will allow more control on physical or mechanical property tuning of the final photocurable composition to specific applications, such as dental restoration, biomedical and healthcare applications.

Claims

Claims 1. A photocurable acrylate resin monomer having Formula 1:wherein F is -Fa- or -CH2-Fa-CH2-, wherein Fais a fluorinated moiety selected from the group consisting of fluorinated alkyl group, fluorinated aryl group, or fluorinated cycloalkyl group; F' is -CH2-Fb-CH2-, wherein Fbis a fluorinated moiety selected from the group consisting of fluorinated alkyl group, fluorinated aryl group or one or more fluorinated alkoxyalkyl groups; or -CHFc-, wherein Fcis a fluorinated moiety which is a fluorinated alkyl group; C' (in the direction of F'- C' -F) is cycloalkyl-(CH2)n- group, wherein the cycloalkyl is optionally substituted with one or more alkyl and n is 1 to 10; R1is H or -CH3; and R2is alkyl group.

2. The photocurable acrylate resin monomer according to claim 1, wherein Fais a fluorinated moiety in which each of the carbon atoms of the moiety is substituted by a fluoro; Fbis a fluorinated moiety in which each of the carbon atoms of the moiety is substituted by a fluoro; or Fcis a fluorinated moiety in which each of the carbon atoms of the moiety is substituted by a fluoro.

3. The photocurable acrylate resin monomer according to claim 2, wherein Fais a perfluorinated moiety; Fbis a perfluorinated moiety; or Fcis a perfluorinated moiety.

4. The photocurable acrylate resin monomer of any one according to claims 1-3, wherein a) Fais fluorinated alkyl group and Fbis fluorinated alkyl group; b) Fais fluorinated aryl group and Fbis fluorinated aryl group; c) Fais fluorinated alkyl group and Fbis fluorinated aryl group; d) Fais fluorinated aryl group and Fbis fluorinated alkyl group; e) Fais fluorinated alkyl group and Fbis one or more fluorinated alkoxyalkyl groups; or f) Fais a fluorinated cycloalkyl group and Fbis fluorinated alkyl group; or g) Fais fluorinated aryl group and Fcis a fluorinated alkyl group.

5. The photocurable acrylate resin monomer of any one according to claims 1-3, wherein.

6. e resin monomer having the following structure: 1A , 1B , 2A , 2B , 2C , 3A , 3B , or 3C .

7. A photocurable composition for use in dental restoration, biomedical or healthcare applications, the composition comprising, i. the photocurable acrylate resin monomer according to any one according to claims 1 to 6, ii. an acrylate resin diluent monomer, iii. a photo-initiator, iv. an inorganic filler material, and v. optionally a stabilizer.

8. The composition according to claim 7 comprising i.5% – 45% by weight of the photocurable acrylate resin monomer, ii. 5% – 55% by weight of the acrylate resin diluent monomer, iii. 0.1% – 5% by weight of the photo-initiator, iv.30% – 80% by weight of the inorganic filler material, and v.0% – 5% by weight of a stabilizer based on the weight of the composition.

9. The composition according to claim 7, wherein the ratio of the photocurable acrylate resin monomer to acrylate resin diluent monomer ranges from 1:10 to 10:1 by weight.

10. The composition according to claim 7, wherein the acrylate resin diluent monomer is acyclic acrylate- or methacrylate-based diluent monomer (including allyl methacrylate (AMA), 1,3-butanediol diacrylate (1,3-BDDA), 1,4-butanediol diacrylate (1,4-BDDA), butyl methacrylate (nBMA), tert-butyl methacrylate (tBMA), 1,10-decanediol dimethacrylate (DDDMA or D3MA), di(ethylene glycol) dimethacrylate, 2- diethylamino)ethyl methacrylate (DEAME), 2-(dimethylamino)ethyl methacrylate (DMAEMA), dithiodi-2,1-ethanediyl bismethacrylate, diurethane dimethacrylate, Ethyl methacrylate (EMA), ethylene glycol methyl ether methacrylate, 2-ethylhexyl acrylate (2EHA), 2-ethoxyethyl methacrylate (2EOEMA), glycerol dimethacrylate (GDMA), hexafluoro-iso-propyl methacrylate (HFiPMA), 1,6-hexanediol dimethacrylate (HDODA), n-hexyl methacrylate (nHMA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate (HPMA), 2-isocyanatoethyl methacrylate (IEM), methyl methacrylate (MMA), 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate, poly(caprolactone) methacrylate (PCLMA), tetraethylene glycol dimethacrylate (Te EGDMA), triethylene glycol dimethacrylate (TEGDMA), 2,2,2-trifluoroethyl methacrylate (TFEMA) or urethane dimethacrylate (UDMA)); cyclic acrylate- or methacrylate-based diluent monomer (including benzyl methacrylate (BZMA), cyclohexyl methacrylate (CHMA), furfuryl methacrylate (FMA), glycidyl methacrylate (GMA), isobornyl Acrylate (IBOA), isobornyl methacrylate (IBOMA), 2- morpholinoethyl methacrylate (MEMA), pentafluorophenyl acrylate (PFPA), pentafluorophenyl methacrylate (PFPMA), phenyl methacrylate, pyromellitic dianhydride glycerol dimethacrylate (PMGDM) or tetrahydrofurfuryl methacrylate (THFMA)); silyl acrylate- or methacrylate-based (including 2-(trimethylsilyloxy)ethyl methacrylate, 3- (trimethoxysilyl)propyl acrylate (TMSPA), 3-(trimethoxysilyl)propyl methacrylate (TMSPMA) or 3-[tris(trimethylsiloxy)silyl]propyl methacrylate); or charged acrylate- or methacrylate-based diluent monomer (including potassium 3- sulfopropyl methacrylate, 2-(N-3-sulfopropyl-N,N-dimethylammonium)ethyl methacrylate (DMAPS) or 2-trimethylammonioethyl methacrylate chloride).

11. The composition according to claim 7, wherein the photo-initiator is camphorquinone / amine / diphenyliodonium hexafluorphosphate (DPI)-based photo- initiator (amine including ethyl 4-(dimethylamino)benzoate, 2-(dimethylamino)ethyl methacrylate (DMAEMA), 2-ethyl-dimethylbenzoate, N,N-dimethyl-p-toluidine or N- phenylglycine);phenone-based photo-initiator (including benzophenone, 2-hydroxy-2-methyl-1- phenyl- propan-1-one, 2,2-dimethoxy-2-phenylacetophenone (DMPA) or 2-Hydroxy-1-[4- (2- hydroxyethoxy)phenyl]-2-methylpropan-1-one); phosphine oxide-based photo-initiator (including trimethylbenzoyl-diphenyl- phosphine oxide (TPO), bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide (BAPO), 2,4,6- trimethylbenzoyl-ethoxyphenyl-phosphine oxide (TPO-L) or 2,4,6- trimethylbenzoyl- bis(4-methylphenyl)-phosphinyl oxide (TMO)); or germanium-based photo-initiator (including Ivocerin).

12. The composition according to claim 7, wherein the inorganic filler material is a n inorganicfiller with particle size between 0.01 μm to 10 μm (including metal oxide particles, glass particles or bioactive glass filler), and inorganic fibres with length between 0.8 mm to 400 mm and diameter between 0.1 mm to 1 mm (including glass fibres).

13. The composition according to claim 7, wherein the stabilizer is a stabilizer with building block containing phenolic (including 2,6-di-tert-butyl-p-cresol (BHT), 4-methoxyphenol (MEHQ) and 4-tert-butylcatechol (TBC)); hydroquinone (including hydroquinone (HQ), ortho-benzoquinones (oBQ), para-benzoquinones (pBQ), tert-butyl hydroquinone (TBHQ) and 2,5-di-tert-butyl-hydroquinone (2,5-DTBHQ)); benzotriazole (including 2-(2- Hydroxy-3,5-dicumyl)benzotriazole); N,N-substituted hydroxylamine (including N,N- dibenzylhydroxylamine (DBHA)); hindered amine or aminoxyl (including 2,2,6,6- tetramethylpiperidin-1-yl)oxyl (TEMPO)) or organophosphorus (including tris(2,4-ditert- butylphenyl)phosphite).

14. A method for preparing the photocurable acrylate resin monomer according to any one claim of claims 1 to 6, comprisinga) reacting a diisocyanate compound of OCN-C'-NCO with a dihydroxyl compound of HO- F-OH in the presence of a catalyst in a solvent under a temperature to provide the compound of Formula 2; OCN-C'-NH-C(O)-O-F-O-C(O)-NH-C'-NCO, Formula 2 b) reacting the compound of Formula 2 with another dihydroxyl compound of HO- F’-OH to provide the compound of Formula 3; and HO-F’-OC(O)-NH-C'-NH-C(O)O-F-OC(O)-NH-C'-NH-C(O)O-F’-OH, Formula 3 c)reacting the compound of Formula 3 with a capping mono-isocyanate of CH2=CR1- C(O)O-R2-NCO to provide the compound of Formula 1, wherein the F, F', C', R1, and R2are as defined in claim 1.

15. The method according to claim 14, wherein the catalyst is organometallic based catalyst (including dibutyltin dilaurate (DBTDL), dibutyltindiacetate (DBTDA),Zirconium acetylacetonate (Zr(acac)4), Bismuth neodecanoate,Zinc neodecanoate,Iron(II) triflate or Titanium diisopropoxide bis(acetylacetonate)); and organic base based catalyst (including 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,4- diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or N- heterocyclic Carbene (NHC)).

16. The method according to claim 14, wherein the solvent is acetone, chloroform, dichloromethane, diethyl ether, N,N-dimethylformamide, ethyl acetate, methyl tert-butyl ether, tetrahydrofuran, and toluene.

17. The method according to claim 14, wherein the reaction temperature is between 25oC – 90oC.

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