POLYMERIC CYCLOALIPHATIC EPOXIDES

Abstract

Polymeric Cycloaliphatic Epoxides The present invention relates to an alkoxylated cycloaliphatic epoxide according to the following formula (I): (I) each R1 and R2 being independently chosen from H and Me; L being the radical of a polyol; each a being independently from 2 to 4; each b being independently from 0 to 20 provided that at least one b is not 0; c being at least 3. The invention also relates to compositions comprising a compound of formula (I) and a method for preparing a cured product. The cured products according to the invention are in particular 3D printed articles. Fig. 1

Description

Description Title of the invention: CYCLOALIPHATIC PO- EPOXIDES LYMERICS Scope of the invention

[0001] — The present invention relates to an alkoxylated cycloaliphatic epoxide and a process for its preparation, compositions containing such a cycloaliphatic epoxide alkoxylated, processes for hardening such compositions, hardened products thus obtained and uses of such products, particularly as articles 3D printed. Context of the invention

[0002] = In the field of 3D printing by photocuring, it is required that the Polymerizable products exhibit reduced toxicity, such as the risks mutagenics, as well as high performance in terms of characteristics such as the hardening speed, resistance to surface degradation by contact friction of hardened resins (friction) etc.

[0003] = The following difunctional cycloaliphatic epoxide, sold under the name UviCure® S105 produces transparent, hard, glossy coatings:

[0004] [Chem.1] O

[0005] Although this epoxy usually gives a good curing speed, fragile mechanical properties can be observed.

[0006] — In general, the viscosity profile of a resin may require management efficient. For example, 3D printing applications may require a "time of longer resting time allows the thin epoxy resins to initially flow and Spreading too much. Solvent resistance is also a characteristic to optimize. compared to existing resins, as well as curing efficiency, for example the curing speed maintained at a lower lamp power for UV-curable compositions, compared to existing epoxy resins. Summary of the invention A first aspect of the invention is an alkoxylated cycloaliphatic epoxide according to the following formula (I): [Chem.2] Eu) -e (D each R, and R; being independently chosen from H and Me; L being the radical of a polyol; each a being independently from 2 to 4; each b being independently 0 to 20 on the condition that at least one b is not 0; c being at least 3. Another aspect of the invention is a process for the preparation of an alkoxylated cycloaliphatic epoxide of formula (I) as defined above, the process comprising the following steps: reaction of a cyclohexene of formula (VI) with an alkoxylated polyol of formula (VII) to obtain an alkoxylated cyclohexene of formula (VIII); epoxidation of the alkoxylated cyclohexene of formula (VIII) to obtain an alkoxylated cycloaliphatic epoxide of formula (I); [Chem.3] o ( x __ (VD [Chem.4] = | noFens to —L 3 Ï at °_, (VID [Chem.5] oO UE S î sd fémarkrelr — en of (VID [Chem.6] oh It is L of (D L, R, R>, a, b and c being such as defined above; X being OH, O-AIk or CI; Alk being a C1-C6 alkyl. Other aspects of the invention relate to a composition comprising at least one alkoxylated cycloaliphatic epoxy according to formula (I) indicated above. Another aspect of the invention relates to a method for preparing a cured product, comprising curing such a composition, in particular by exposing the composition to radiation such as UV, near-UV, visible, infrared, and / or near-infrared radiation, or to an electron beam. Yet another aspect of the invention relates to a cured product obtained by curing a composition according to the invention. The cured product can be used as an ink, a coating, a sealant, an adhesive, a molded article, or a 3D-printed article, in particular a 3D-printed article. Detailed description Description of the Figures Figure 1 shows the results of tensile stress measurements on resin materials cured according to the present invention, and on resin materials cured not according to the invention. Figure 2 shows the results of conservation modulus measurements on resin materials cured according to the present invention, and on resin materials cured not according to the invention. Figure 3 presents the results of heat flux measurements on materials of hardened resin according to the present invention, and on hardened resin materials not according to the invention. Definitions In this application, the term "includes / comprise a" means "includes / comprise one or more". Unless otherwise stated, the % by weight of a compound or composition are expressed on the basis of the weight of the compound, respectively of the composition. The term "alkyl" means a monovalent saturated hydrocarbon radical of formula —CHz.1. An alkyl group can be linear or branched. A "C1-C20 alkyl" means an alkyl group with 1 to 20 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl. The term "alkylaryl" means an alkyl group substituted with an aryl group. A "C7-C20 alkylaryl" means an alkylaryl group with 7 to 20 carbon atoms. An example of an alkylaryl group is benzyl (-CH,-Phenyl). The term "halogen" means an atom chosen from Cl, Br and I. The term "alkylene" refers to a divalent saturated hydrocarbon radical with the formula -C,Ha,-. An alkylene can be linear or branched. A "C1-C20 alkylene" means an alkylene with 1 to 20 carbon atoms. Examples of alkylene groups include ethylene (-CH,-CH,-) and 1,2-propylene (-CH,-CH(CH;)-). The term "alkenyl" refers to a monovalent unsaturated hydrocarbon radical. An alkenyl can be linear or branched. A "C2-C20 alkenyl" means an alkenyl with 2 to 20 carbon atoms. Examples of alkenyl groups include vinyl (-CH=CH;) and allyl (-CH,-CH=CH,). The term "cycloalkyl" refers to a monovalent saturated alicyclic hydrocarbon radical containing a ring. A "C3-C8 cycloalkyl" means a cycloalkyl with 3 to 8 carbon atoms. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and isobornyl. The term "alkoxy" means a group with the formula -O-Alkyl. The term "aryl" refers to an aromatic hydrocarbon group. A "C6-C12 aryl" means an aryl with 6 to 12 carbon atoms. The term "heteroaryl" refers to an aromatic group comprising a heteroatom such as O, N, S, and corresponding mixtures thereof. A "CS-C9 heteroaryl" means a heteroaryl possessing 5 to 9 carbon atoms. The term "polyol" means a compound comprising at least two hydroxyl groups. The term "polyester" means a compound comprising at least two ester bonds. The term "polyether" means a compound comprising at least two ether bonds. The term "polycarbonate" means a compound comprising at least two carbonate bonds. The term "polyester polyol" means a polyester comprising at least two hydroxyl groups. The term "polyether polyol" means a polyether comprising at least two hydroxyl groups. The term "polycarbonate polyol" means a polycarbonate comprising at least two hydroxyl groups. The term "hydrocarbon radical" means a radical composed of carbon and hydrogen atoms. Unless otherwise specified, a hydrocarbon radical is not substituted or interrupted by any heteroatoms (O, N, or S). A hydrocarbon radical can be linear or branched, saturated or unsaturated, aliphatic, cycloaliphatic, or aromatic. The term "hydroxyl group" means a -OH group. The term "amine" means a group of -NR, R, R, and Rp, being independently H or a C1-C6 alkyl group. The term "primary amine" means a group of -NH. The term "secondary amine" means a group of -NHR, R, being a C1-C6 alkyl group. The term "tertiary amine" means a group of -NR, R, R, and R, being independently a C1-C6 alkyl group. The term "carboxylic acid" means a -COOH group. The term "isocyanate group" means a -N=C=O group, The term "ester bond" means a -C(=0)-O- or -OC(=0)- bond. The term "ether bond" means an -O- bond. The term "carbonate bond" means a -OC(=0)-0- bond. The term "urethane or carbamate" means a -NH-C(=O)-O- or -OC(=O)-NH- bond. The term "amide bond" means a -C(=0)-NH- or -NH-C(=0)- bond. The term "urea bond" means a -NH-C(=0)-NH- bond. The term "polyisocyanate" means a compound comprising at least two isocyanate groups. The term "aliphatic" means a non-aromatic acyclic compound. It may be linear or branched, saturated or unsaturated. It may be substituted by one or more groups, for example, alkyl, hydroxyl, halogen (Br, Cl, I), isocyanal, carbonyl, amine, carboxylic acid, -C(=O)-OR, -C(=O)-OC(=O)-R', each R' being independently a C1-C6 alkyl group. It may include one or more bonds chosen from ether, ester, amide, urethane, urea, and corresponding combinations thereof. The term "acyclic" means a compound that does not contain any rings. The term "cycloaliphatic" means a non-aromatic cyclic compound. It can It may be substituted by one or more groups as defined for the term "aliphatic". It may include one or more bonds as defined for the term "aliphatic". The term "aromatic" refers to a compound containing an aromatic ring, meaning it obeys Hückel's rule of aromaticity, specifically a compound containing a phenyl group. It may be substituted by one or more groups as defined for the term "aliphatic." It may also contain one or more bonds as defined for the term "aliphatic." The term "saturated" means a compound that does not contain any carbon-carbon double or triple bonds. The term "unsaturated" means a compound that includes a carbon-carbon double or triple bond, especially a carbon-carbon double bond. The term "possibly substituted" means a compound substituted by one or more groups selected from alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, al-kylaryl, haloalkyl, hydroxyl, halogen, isocyanate, nitrile, amine, amide, carboxylic acid, -C(=0)-R', -C(=0)-OR), -C(O)NH-R), -NH-C(=O)R), -OC(=0)-NH-R", -NH-C(=0)-OR", -C(F0)-OC(=0)-R' and -SO,-NH-R', each R' being independently a possibly substituted group selected from alkyl, aryl and al-kylaryl. The term "3D article" means a three-dimensional object obtained by 3D printing. C of the invention ] I Epoxy resins can be polymerized, for example by cationic polymerization, and, as mentioned above, cycloaliphatic epoxies such as those based on a cyclohexane ring are known. In the present invention, a polyol core is attached to several C6 cycloaliphatic groups bearing an epoxide by means of ethyleneoxy (-CH,-CH;-O-), 1,2-propyleneoxy (-CH,-CH(CH;)-O-), or similar spacers. In one aspect, the invention therefore relates to an alkoxylated cycloaliphatic epoxide according to the following formula (D: [Chem.7] O It's —L -e (D each R, and R; being independently chosen from H and Me; L being the radical of a polyol; each a being independently from 2 to 4; each b being independently 0 to 20 on the condition that at least one b is not 0; c being at least 3. Before hardening, the alkoxylated cycloaliphatic epoxy compounds of the present invention thus contain several epoxy groups separated from each other and available for hardening. In an illustrative example of an alkoxylated cycloaliphatic epoxide of the present invention, which is a preferred example, but to which the present invention is not limited, the alkoxylated cycloaliphatic epoxide may have the following structure: [Chem.8] 2 Se 20 8 # ah 87 as d- me É af A 0 0 0 _ this Æ 4 Fi èe Se sx. As 9 DOM 2"CHt 1, mo 9 2 pe 2 V5 Ÿ 0 Rd PE) BOET ENT gt 04 4 L & Pré LE 00 8 TS È £ 7 uen 07° #4 LS 20 0 to ,. o LA 2 CS 0 good os 8, e PT0 LA $ 0.” {D + a °F a LG 8; is A x Ë; quhE LP tVy*é Fe h pe 23 proud LS at home fs] The preferred hexafunctional molecule above is derived from (HO-CHz-)3C-CH2)20. This latter polyol is commercially available from Perstorp AB under the name Polyol R6405; its systematic name is poly(oxy-1,2-ethanediyl), α-hydro-γ-hydroxy-, ether with the 2,2"-[oxybis(methylene)]bis[2-(hydroxymethyl)-1,3-propanediol] (6:1). Its CAS number is 50977-32-7. In general, among the preferred alkoxylated cycloaliphatic epoxides of the invention, corresponding to the general formula (I) above, are those in which a is 2, the alkoxylated cycloaliphatic epoxide being according to the following formula (Ia): [Chem.9] o -L Loue CHR —e ve oO 1 of (there) L, b etc being such as defined in claim 1; each R, and R', being independently chosen from H and Me. Another preferred type of alkoxylated cycloaliphatic epoxide according to the invention, corresponding to the general formula (I) above, has a as being 4 and R, and Ra are both H. In preferred alkoxylated cycloaliphatic epoxides of the invention, according to the different preferences established above for a, and for R, and R', or R, and R', each b is independently from 1 to 20, in particular from 1 to 10, more particularly from 2 to 6. In preferred alkoxylated cycloaliphatic epoxides of the invention, the alkoxylated cycloaliphatic epoxide has a degree of alkoxylation of at least 6, in particular of at least 8, more particularly of at least 10, even more particularly of at least 12. In preferred alkoxylated cycloaliphatic epoxides of the invention, It is from 3 to 10, in particular from 3 to 8, more particularly from 4 to 6. In preferred alkoxylated cycloaliphatic epoxides of the invention, c is 3 and L is a trivalent linker according to the following formula (ID): [Chem.10] Ra 3—(CHo)e — (Ho, (Shawl Mann (ID R, being chosen from H, alkyl and alkoxy, in particular Ra being alkyl, more particularly R; being ethyl; d, d' and d' being independently 0 to 2, it being understood that at least 2 among d, d' and d' are not 0, in particular d, d' and d' being all 1 or d being 0 and d' and d' being 1. In other preferred alkoxylated cycloaliphatic epoxides of the invention, c is 4 and L is a tetravalent linker according to one of the following formulas (IIa), (IIb) or (IIIc): [Chem.11] mepae {CHay + i F-stCH D, 4 CHI 2 (Hz, dt (Ia) [Chem.12] N / A NA AN A ss (IIMb) [Chem.13] rep eadree OA 010 A TO (IMec) e, e, e“ ete” being independently 0 to 2, it being understood that at least 3 among e, e', e” and e”* are not 0, in particular e, e', e" and e" being all 1. In other preferred alkoxylated cycloaliphatic epoxides of the invention, c is 5 and L is a pentavalent linker according to the following formula (IV): [Chem.14] sopee men sogtes HELLO HELLO OVER THERE (IV). In other preferred alkoxylated cycloaliphatic epoxides of the invention, c is 6 and L is a hexavalent linker according to the following formula (Va), (Vb) or (Vc): [Chem.15] = To NO A kW (Go) [Chem.16] it NAS mdrée ane (Vb) [Chem.17] to (A RS AL A0 A 0, A TO (Ve). In processes according to the present invention, an esterification is carried out, forming an ester of an alkoxylated polyol and a cyclohexene bearing a carboxylic acid, followed by a subsequent reaction with an epoxidizing agent in an epoxidation step, converting the several C=C groups of cyclohexene into epoxide groups. Thus, in a process for the preparation of an alkoxylated cycloaliphatic epoxide of formula (I) according to the invention as defined above, the process comprises the following steps: a. Reaction of a cyclohexene of formula (VI) with an alkoxylated polyol of formula (VID) to obtain an alkoxylated cyclohexane of formula (VII); b. epoxidation of the alkoxylated cyclohexene of formula (VIII) to obtain a alkoxylated cycloaliphatic epoxide of formula (I) as defined above [Chem.18] (VD [Chem.19] Him | no eus —L ; ; £ (VID [Chem.20] o Cote #J 0 | — b Lut (VID L, R, Ra, a, b and c being as defined above in relation to the alkoxylated cycloaliphatic epoxide type compounds of the present invention; X being OH, O-Alk or CI]; Alk being a C1-C6 alkyl. As stated above, the alkoxylated polyol of formula (VID) can be linked to form the ester (VIII) either by direct etherification with acid 3-Cyclohexene-1-carboxylic acid, either via an intermediate such as cyclohex-3-ene-1-carbonyl acid chloride. The latter acid chloride can be obtained by reacting 3-cyclohexene-1-carboxylic acid with an agent such as thionyl chloride, phosphorus trichloride, phosphorus(V) oxychloride, and oxalyl chloride. The epoxidation step (b) can be carried out with a peracid such as 3-chloroperbenzoic acid, peracetic acid or with other epoxidizing agents such as hydrogen peroxide, tert-butyl hydroperoxide and sodium hypochlorite. Compositions of the invention The compositions of the present invention include, but are not limited to, compositions comprising: a. at least one alkoxylated cycloaliphatic epoxide of formula (I) as defined above; and b. at least one cationically polymerizable compound other than component a). Component (b) may be selected, in particular, from the group consisting of an oxetane, an oxolane, a cyclic acetal, a cyclic lactone, a thiirane, a thietane, a spiro-orthoester, a spiro-orthocarbonate, a vinyl ether, a vinyl ester, corresponding derivatives, and corresponding mixtures. Oxetanes are particularly preferred examples of component (b). Components (b), such as oxetanes, can serve as reactive diluents and provide a high curing rate and also high solvent resistance in compositions with (a) at least one alkoxylated cycloaliphatic epoxide of formula (I). In this first type of preferred compositions in the present invention, comprising a) at least one alkoxylated cycloaliphatic epoxide of formula (I) as defined above; and at least one cationically polymerizable compound, such as an oxetane, the composition preferably includes at least one cationic photoinitiator, in particular an onium salt or a metallocene salt, more particularly a halonium salt, a sulfonium salt (e.g. a triarylsulfonium salt such as a triarylsulfonium hexafluoroantimonate salt), a sulfoxonium salt, a diazonium salt, a ferrocene salt, and corresponding mixtures. Cationically polymerizable compound As mentioned above, in a first preferred option, the composition of The invention may further comprise, in addition to at least one alkoxylated cycloaliphatic epoxide of formula (I), a cationically polymerizable compound b), such as an oxetane, and / or c) polyols. The composition of the invention may comprise a mixture of cationically polymerizable compounds b) and c). When the composition includes a compound that can be cationically polymerized, the composition can be a free radical / cationic hybrid composition, i.e., a composition that is hardened by free radical polymerization and by cationic polymerization. The term "cationically polymerizable compound" means a compound comprising a polymerization functional group that polymerizes via a cationic mechanism, for example, a heterocyclic group or a carbon-carbon double bond substituted with an electron-donating group. In a cationic polymerization mechanism, a cationic initiator forms a Brünnsted or Lewis acid-like species that binds to the cationically polymerizable compound, which then becomes reactive and leads to chain growth by reaction with another cationically polymerizable compound. The cationically polymerizable compound may be selected from epoxy-functionalized compounds, oxetanes, oxolanes, cyclic acetals, cyclic lactones, thiiranes, thietanes, spiro-orthoesters, ethylenically unsaturated compounds other than (meth)acrylates, corresponding derivatives and corresponding mixtures. In a preferred embodiment, the cationically polymerizable compound can be selected from epoxy-functionalized compounds, oxetanes, and corresponding mixtures. In particular, oxetanes are preferred cationically polymerizable compounds in compositions of the present invention. Suitable epoxy-functionalized compounds capable of being cationically polymerized are glycidyl ethers, in particular monoglycidyl, diglycidyl, triglycidyl and polyglycidyl ether-type compounds, and alicyclic epoxy-type compounds including those comprising a carboxylic acid radical such as, for example, alkylcarboxylic acid residual groups, alkylcycloalkylcarboxylic acid residual groups and alkylene-dicarboxylic acid residual groups.For example, epoxy-functionalized compounds may include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, a novolak epoxy resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexyl-3',4'-epoxycyclohexanecarboxylate, the . 2-(7-oxabicyclo[4.1.0]heptan-3-yl)spiro[1,3-dioxane-5,3-7-oxabicyclo[4.1.0]heptane], bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, 4-vinylcyclohexene dioxide, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, the 3,4-epoxy-6-methylcyclohexyl-3',4"-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl)ethylene glycol ether, ethylenebis(3,4-epoxycyclohexanecarboxylate), epoxyhexahydrodioctyl phthalate, epoxyhexahydro-di-2-ethylhexyl phthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyether polyol polyglycidyl ethers obtained by the addition of one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerol, diglycidyl esters of long-chain aliphatic dibasic acids, ethers of mono-glycidyl of higher aliphatic alcohols, monoglycidyl ethers of phenol, cresol, butylphenol, or polyether alcohols obtained by the addition of alkylene oxide to these compounds, glycidyl esters of higher fatty acids, epoxidized soybean oil,Epoxybutylstearic acid, epoxyoctylstearic acid, epoxidized linseed oil, polybutadiene epoxide, and similar substances. Suitable oxetanes capable of being cationically polymerized include trimethylene oxide, 3,3-dimethyloxetane, the 3,3-Dichloromethyloxetane, 3-ethyl-3-phenoxymethyloxetane, and bis(3-ethyl-3-methyloxy)butane, 3-ethyl-3-oxetamenethanol. According to a preferred mode, in compositions according to the present invention comprising a component b) cationically polymerizable in the form of oxetane, it is in particular at least one oxetane according to the following formula (IX): [Chem.211] OX OR4 x, eo” (IX) R, being chosen from H, alkyl, aryl, alkylaryl, (meth)acryloyl, -CH.-oxetanyl-CH >-CH,, -L,-O-CH--oxetanyl-CH-CH; ; L, being a divalent linker, in particular -CH,-Ph-Ph-CH; or -CHz-Ph-CH,-[O-CH; - Ph-CH,]- Ph being phenylene; f being 0 to 10. More preferably, component b) comprises at least one oxetane according to formula (IX), R, being H, benzyl or -CH,-oxetanyl-CH,-CH, preferably R, being H or -CH,-oxetanyl-CH,-CH-. Suitable oxolanes capable of being cationically polymerized include tetrahydrofuran and 2,3-dimethyltetrahydrofuran. Suitable cyclic acetals capable of being cationically polymerized include trioxane, 1,3-dioxolane and 1,3,6-trioxacyclooctane. Suitable cyclic lactones capable of being cationically polymerized include β-propiolactone and e-caprolactone. Suitable thiiranes capable of being cationically polymerized include ethylene sulfide, 1,2-propylene sulfide, and thioepichlorohydrin. Suitable thietanes capable of being cationically polymerized include 3,3-dimethylthietane. Suitable spiro-orthoesters capable of being cationically polymerized are compounds obtained by the reaction of an epoxy-type compound and a lactone. Suitable ethylenically unsaturated compounds other than (meth)acrylates capable of being cationically polymerized include vinyl ethers such as ethylene glycol divinylether, triethylene glycol divinylether, and trimethylolpropane trivinylether. In the compositions of the invention comprising as component a) at least one alkoxylated cycloaliphatic epoxide of formula (I), and as component b) at least one cationically polymerizable compound different from component a), the weight ratio between component a) and component b) is preferably 20:80 to 80:20, in particular 30:70 to 70:30, more particularly 40:60 to 60:40. The polymerizable composition of the invention may comprise 10% to 80%, in particular 15% to 75%, more particularly 20% to 70%, by weight of cationically polymerizable compound on the basis of the total weight of the polymerizable composition. Free radical / cationic hybrid compositions In a further preferred composition option of the present invention, the composition may be one that is cured by both free radical polymerization and cationic polymerization. In preferred embodiments, (a) an alkoxylated cycloaliphatic epoxide according to formula (I) cited above, and optionally further an oxetane (b) on the one hand, and a monomer capable To participate in a C=C addition polymerization, on the other hand, for example a compound containing a (meth)acrylate group, normally, interpenetrating (intertwined) networks of distinct polyepoxide and poly(meth)acrylate are obtained with no covalent bonds between them. However, it can be advantageous to have a composition containing a monomer-like component with both epoxide / oxetane and (meth)acrylate groups. In this case, covalent bonds are formed between the two networks, which can provide a further improvement in physical properties. Examples of such commercially available compounds include UViCure S170 (3-Ethy-1-3-(Methacryloyloxy)Methyloxetane) and a glycidyl (meth)acrylate. Thus, in a second preferred composition of the invention, the composition comprises: a. at least one alkoxylated cycloaliphatic epoxide of formula (I) as indicated above or a composition comprising at least one cycloali- epoxide alkoxylated phatic compound of formula (I) and b) at least one polymerizable compound of cationic manner different from component a), in particular an oxetane, a oxolane, a cyclic acetal, a cyclic lactone, a thiirane, a thiethane, a spiro-orthoester, a spiro-orthocarbonate, a vinyl ether, an ester of vinyl, corresponding derivatives and corresponding mixtures; and b. at least one (meth)acrylate functionalized compound, in particular a compound functionalized by (meth)acrylate bearing at least 2 or at least 3 (meth)acrylate groups. In this second type of preferred composition of the invention, cationically curable oxetanes are possible components, although they can be used in preferred embodiments. Other possible components are cationically curable vinyl ethers, polyols, or polyfunctional alcohols, which can act as chain transfer agents. As used here, the term "methacrylate functionalized compound" means a monomer comprising a methacrylate group, specifically an acrylate group. The term "methacrylate functionalized compound" here encompasses compounds containing more than one methacrylate group, such as 2, 3, 4, 5, or 6 methacrylate groups, commonly referred to as oligomers. The term "methacrylate group" includes both acrylate groups (-O-CO-CH=CH2) and methacrylate groups (-O-CO-C(CH2)=CH2). Preferably, the compound functionalized by (meth)acrylate does not include any amino groups. As used here, the term "amino group" refers to a primary, secondary, or tertiary amine group, but does not include any other type of group. containing nitrogen such as an amide group, a carbamate (urethane), urea, or sulfonamide. The compound functionalized by (meth)acrylate may have a molecular weight of less than 600 g / mol, in particular from 100 to 550 g / mol, more particularly from 200 to 500 g / mol. The (meth)acrylate functionalized compound may have 1 to 6 (meth)acrylate groups, in particular 1 to 5 (meth)acrylate groups, more particularly 1 to 3 (meth)acrylate groups. (Meth)acrylate functionalized compounds may comprise a mixture of (meth)acrylate functionalized monomers possessing different functionalities. For example, a (meth)acrylate functionalized compound may comprise a mixture of a (meth)acrylate functionalized compound containing a single acrylate or methacrylate group per molecule (referred to herein as a "mono(meth)acrylate functionalized compound") and a (meth)acrylate functionalized compound containing two or more, preferably two or three, acrylate and / or methacrylate groups per molecule. In another example, (meth)acrylate functionalized compounds may comprise a mixture of at least one (meth)acrylate functionalized compound mono(meth)acrylate and at least one (meth)acrylate functionalized compound containing 3 or more, preferably 4 or more, (meth)acrylate groups per molecule. The (meth)acrylate functionalized compound may include a mono(meth)acrylate functionalized compound. The mono(meth)acrylate functionalized compound may advantageously act as a reactive diluent and reduce the viscosity of the composition of the invention. Examples of suitable mono(meth)acrylate functionalized compounds include, but are not limited to, mono(meth)acrylate esters of aliphatic alcohols (the aliphatic alcohol may be straight-chain, branched, or alicyclic and may be a monoalcohol, a dialcohol, or a polyalcohol, provided that only one hydroxyl group is esterified by (meth)acrylic acid); mono(meth)acrylate esters of aromatic alcohols (such as phenols, including alkylated phenols); mono(meth)acrylate esters of alkylaryl alcohols (such as benzyl alcohol); mono(meth)acrylate esters of oligomeric and polymeric glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol); mono(meth)acrylate esters of monoalkyl ethers of glycols and oligoglycols;mono(meth)acrylate esters of alkoxylated aliphatic alcohols (e.g., ethoxylated and / or propoxylated) (the aliphatic alcohol may be straight-chain, branched or alicyclic and may be a monoalcohol, a dialcohol or a polyalcohol, provided that only one hydroxyl group of the alkoxylated aliphatic alcohol is esterified with an acid; (meth)acrylic); mono(meth)acrylate esters of aromatic alcohols (such as alkoxylated phenols) alkoxylated (e.g., ethoxylated and / or propoxylated); mono(meth)acrylates of caprolactone; and similar. The following compounds are specific examples of mono(meth)acrylate functionalized compounds suitable for use in the hardenable compositions of the present invention: methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; n-dodecyl (meth)acrylate; tridecyl (meth)acrylate; tetradecyl (meth)acrylate; hexadecyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate and 3-hydroxypropyl (meth)acrylate; 2-methoxyethyl (meth)acrylate; 2-ethoxyethyl (meth)acrylate; 2-ethoxypropyl (meth)acrylate and 3-ethoxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; alkoxylated tetrahydrofurfuryl (meth)acrylate;2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate; lauryl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; alkoxylated phenol (meth)acrylates; alkoxylated non-nylphenol (meth)acrylates; cyclic trimethylolpropane (meth)acrylate; isoboryl (meth)acrylate; tricyclodecanemethanol (meth)acrylate; tert-butylcyclohexanol (meth)acrylate; trimethylcyclohexanol (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; ethoxylated lauryl (meth)acrylate; polyethylene glycol meth)acrylates; (meth)acrylates of 3-(2-hydroxyalkyl)oxazolidinone; and corresponding combinations. The (meth)acrylate functionalized compound may comprise a (meth)acrylate functionalized compound containing two or more (meth)acrylate groups per molecule. Examples of suitable (meth)acrylate functionalized compounds containing two or more (meth)acrylate-type groups per molecule include acrylate and methacrylate esters of polyhydric alcohols (organic compounds containing two or more hydroxyl groups per molecule, e.g., 2 to 6). Specific examples of suitable polyhydric alcohols include C2-20 alkylene glycols (glycols possessing a Cz..0 alkylene group may be preferred, in which the carbon chain may be branched; e.g., ethylene glycol, trimethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, tetramethylene glycol (1,4-butanediol), 1,5-pentanediol, 1,6-hexanediol, etc. 1,8-octanediol, 1,9-nonanediol, 1,12-dodecanediol, cyclohexane-1,4-dimethanol, bisphenols, and hydrogenated bisphenols, as well as corresponding alkoxylated derivatives (e.g.(ethoxylated and / or propoxylated), diethylene glycol, glycerin, alkoxylated glycerin, triethylene glycol, dipropylene glycol, triproxylene glycol, trimethylolpropane, alkoxylated trimethylolpropane, ditrimethylolpropane, alkoxylated ditrimethylolpropane, pentaerythritol, alkoxylated pentaerythritol, dipentaerythritol, alkoxylated dipentaerythritol, cyclohexanediol, alkoxylated cyclohexanediol, cyclohexanedimethanol, alkoxylated cyclohexanedimethanol, norbornenedimethanol, alkoxylated norbornenedimethanol, norbornanedimethanol, alkoxylated norbornanedimethanol, polyols containing an aromatic ring, adducts of cyclohexane-1,4-dimethanol and ethylene oxide, bisphenol and ethylene oxide adducts, hydrogenated bisphenol and ethylene oxide adducts, bisphenol and propylene oxide adducts, hydrogenated bisphenol and propylene oxide adducts, cy- adducts. clohexane-1,4-dimethanol and propylene oxide, sugar alcohols, and alkoxylated sugar alcohols. Such polyhydric alcohols may be fully or partially esterified (with (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, or the like), provided they contain at least two (meth)acrylate functional groups per molecule. As used here, the term "alkoxylated" refers to compounds containing one or more oxyalkylene fragments (e.g., oxyethylene and / or oxypropylene fragments). An oxyalkylene fragment corresponds to the general structure -RO-, where R is a divalent aliphatic fragment such as -CH,CH;- or -CH,CH(CH;)-. For example, an alkoxylated compound may contain from 1 to 30 oxyalkylene fragments per molecule. Examples of (meth)acrylate functionalized compounds containing two or more (meth)acrylate groups per molecule may include bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; 1,2-butanediol di(meth)acrylate; 2,3-butanediol di(meth)acrylate; 1,3-butanediol di(meth)acrylate; a 1,4-butanediol di(meth)acrylate; a 1,5-pentanediol di(meth)acrylate; a 1,6-hexanediol di(meth)acrylate; a 1,8-octanediol di(meth)acrylate;a 1,9-nonanediol di(meth)acrylate; a 1,10-nonanediol di(meth)acrylate; a 1,12-dodecanediol di(meth)acrylate; a di(meth)acrylate of; neopentyl glycol; a 2-methyl-2,4-pentanediol di(meth)acrylate; a polybutadiene di(meth)acrylate; a cy- di(meth)acrylate clohexane-1,4-dimethanol; a tricyclodecanedimethanol di(meth)acrylate; metallic di(meth)acrylates; modified metallic di(meth)acrylates; a glyceryl di(meth)acrylate; a glyceryl tri(meth)acrylate; a trimethylolethane tri(meth)acrylate; a trimethylolethane di(meth)acrylate; a trimethylolpropane tri(meth)acrylate; a trimethylolpropane di(meth)acrylate; a pentaerythritol di(meth)acrylate; a pentaerythritol tri(meth)acrylate; a pentaerythritol tetra(meth)acrylate; ditrimethylolpropane diacrylate; ditrimethylolpropane triacrylate; ditrimethylolpropane tetraacrylate; a sorbitol penta(meth)acrylate; dipentaerythritol tetraacrylate; dipentaerythritol pentaacrylate; a hexa(meth)acrylate of dipentaerythritol; a tri(meth)acrylate of tris(2-hydroxyethyl)isocyanurate; as well as the corresponding alkoxylated derivatives (e.g., ethoxylated and / or propoxylated); and corresponding combinations.. The hardenable composition of the invention may comprise 10% to 80%, in particular 15% to 75%, more particularly 20% to 70%, by weight of (meth)acrylate functionalized compound on the basis of the total weight of the hardenable composition. The (meth)acrylate functionalized compound in the form of an oligomer can be selected to increase the flexibility, strength, and / or modulus, among other attributes, of a hardened polymer prepared using the curable composition of the present invention. Here, the (meth)acrylate functionalized oligomer may have up to 18 (meth)acrylate groups, in particular 2 to 6 (meth)acrylate groups, more particularly 2 to 6 acrylate groups. The (meth)acrylate functionalized compound in the form of an oligomer may have a number-average molecular weight greater than or equal to 600 g / mol, in particular 800 to 15,000 g / mol, more particularly 1,000 to 5,000 g / mol. In particular, (meth)acrylate functionalized compounds may be selected from the group consisting of (meth)acrylate functionalized epoxy oligomers (sometimes also referred to as 'epoxy (meth)acrylate oligomers'), (meth)acrylate functionalized polyether oligomers (sometimes also referred to as 'polyether (meth)acrylate oligomers'), (meth)acrylate functionalized polydiene oligomers (sometimes also referred to as 'polydiene (meth)acrylate oligomers'), (meth)acrylate functionalized polycarbonate oligomers (sometimes also referred to as 'polycarbonate (meth)acrylate oligomers'), and (meth)acrylate functionalized polyester oligomers (sometimes also referred to as 'polyester (meth)acrylate oligomers') and corresponding mixtures. Examples of polyester (meth)acrylate oligomers include The reaction products of acrylic or methacrylic acid, or corresponding mixtures or synthetic equivalents, with polyester polyols terminated by a hydroxyl group. The reaction process can be conducted so that all, or essentially all, of the hydroxyl groups of the polyester polyol have been (meth)acrylated, particularly in cases where the polyester polyol is difunctional. Polyester polyols can be prepared by polycondensation reactions of polyhydroxyl-functionalized components (in particular, diols) and poly(carboxylic acid)-functionalized compounds (in particular, dicarboxylic acids and anhydrides). The polyhydroxyl-functionalized and poly(carboxylic acid)-functionalized components can each have linear, branched, cycloaliphatic, or aromatic structures and can be used individually or as mixtures. Examples of suitable epoxy (meth)acrylates include the reaction products of acrylic or methacrylic acid or corresponding mixtures with an epoxy resin (polyglycidyl ether or ester). The epoxy resin can, in particular, be selected from bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, a novolak epoxy resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4"-epoxycyclohexanecarboxylate, 2-(7-oxabicyclo[4.1.0]heptan-3-yl)spiro| 1,3-dioxane-5,3"-7-oxabicyclo[4.1.[0]heptane], bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl ethylene glycol ether, . ethylenebis(3,4-epoxycyclohexanecarboxylate), 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycidyl ether of a polyether polyol obtained by the addition of one or more alkylene oxides to an aliphatic polyhydric alcohol such as ethylene glycol, propylene glycol, and glycerol, diglycidyl esters of long-chain aliphatic dibasic acids, monoglycidyl ethers of higher aliphatic alcohols, monoglycidyl ethers of phenol, of cresol, butylphenol, or polyether alcohols obtained by the addition of alkylene oxide to these compounds, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxybutyl acid stearic acid, epoxyoctylstearic acid, epoxidized linseed oil, poly-butadiene epoxide, and similar. Suitable polyether (meth)acrylate oligomers include, but are not limited to, the condensation reaction products of acrylic or methacrylic acid, or corresponding synthetic mixtures or equivalents, with polyetherols that are polyether polyols (such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol). Suitable polyetherols may be linear or branched substances containing ether bonds and terminal hydroxyl groups. Polyetherols may be prepared by ring-opening polymerization of cyclic ethers such as tetrahydrofuran or alkylene oxides (e.g., ethylene oxide and / or propylene oxide) with a starting molecule. Suitable starting molecules include water, polyhydroxyl-functionalized materials, and polyester polyols. Suitable acrylic (meth)acrylate oligomers (sometimes also referred to in the art as "acrylic oligomers") include oligomers that can be described as substances possessing an oligomeric acrylic backbone functionalized with one or more (meth)acrylate groups (which may be at a termination of the oligomer or pendant to the acrylic backbone). The acrylic backbone may be a homopolymer, a random copolymer, or a block copolymer composed of repeating motifs of acrylic-like monomers. The acrylic-like monomers may be any monomeric (meth)acrylate, such as C1-C6 alkyl (meth)acrylates, as well as functionalized (meth)acrylates, such as (meth)acrylates bearing hydroxyl, carboxylic acid, and / or epoxy groups.Acrylic (meth)acrylate oligomers can be prepared using any procedures known in the art, such as the oligomerization of monomers, at least a portion of which is functionalized with hydroxyl, carboxylic acid and / or epoxy groups (e.g., hydroxyalkyl (meth)acrylates, (meth)acrylic acid, glycidyl (meth)acrylate) to obtain a functionalized oligomer intermediate, which is then reacted with one or more (meth)acrylate-containing reactants to introduce the desired (meth)acrylate functional groups. The hardenable composition of the invention may comprise 10% to 80%, in particular 15% to 75%, more particularly 20% to 70%, by weight of (meth)acrylate functionalized compound on the basis of the total weight of the hardenable composition. Non-limiting types of radical photoinitiators suitable for use in the hardenable compositions of the present invention include, for example, benzoins, benzoin ethers, acetophenones, α-hydroxyacetophenones, benzil, benzil ketals, anthraquinones, oxides phosphine, acylphosphine oxides, α-hydroxyketones, phenyl-glyoxylates, α-aminoketones, benzophenones, thioxanthones, xanthones, acridine derivatives, phenazene derivatives, quinoxaline derivatives, triazine compounds, benzoyl formates, aromatic oximes, metallocenes, acylsilyl or acylgermanyl type compounds, camphoquinones, corresponding polymeric derivatives, and corresponding mixtures. Examples of suitable radical photoinitiators include, but are not limited to, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-benzyanthraquinone, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, benzil, benzoins, benzoin ethers, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, alpha-methylbenzoin, alpha-phenylbenzoin, Michler ketone, acetophenones such as 2,2-dialkoxybenzophenones and 1-hydroxyphenyl ketones, benzophenone, 4,4'-bis-(diethylamino)benzophenone, acetophenone, 2,2-diethyloxyacetophenone, diethyloxyacetophenone, 2-isopropylthioxanthone, thioxanthone, diethylthioxanthone, 1,5-acetonaphthylene, benzyl ketone, α-hydroxy keto, 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, benzyl dimethyl ketol, 2,2-dimethoxy-1,2-diphenylethanone, 1-hydroxycylclohexylphenyl ketone, 2-methyl-1-[4-(methylthio) phenyl]-2-morpholinopropanone-1, 2-hydroxy-2-methyl-1-phenylpropanone, an oligomeric α-hydroxyketone, benzoylphosphine oxides, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenyl phosphinate, anisoin, anthraquinone, anthraquinone-2-sulfonic acid sodium salt monohydrate, (benzene)tricarbonylchrome, benzil, benzoin isobutyl ether, a 50 / 50 benzophenone / 1-hydroxycyclohexyl phenyl ketone mixture, 3,3',4,4-benzophenonetetracarboxylic dianhydride, 4-benzoylbiphenyl, the 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 4,4-bis(diethylamino)benzophenone, 4,4-bis(dimethylamino)benzophenone, camphoquinone, 2-chlorothioxanthen-9-one, dibenzosuberenone, 4,4-dihydroxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-(dimethylamino)benzophenone, 4,4"-dimethylbenzile, 2,5-Dimethylbenzophenone, 3,4-Dimethylbenzophenone, a 50 / 50 mixture of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide / 2-hydroxy-2-methylpropiophenone, 4'-Ethoxyacetophenone, 2,4,6-Trimethylbenzoyldiphenylphosphine oxide, phenyl-bis(2,4,6-trimethylbenzoyl)phosphine oxide, ferrocene, 3'-Hydroxyacetophenone, 4'-Hydroxyacetophenone, 3-Hydroxybenzophenone, 4-Hydroxybenzophenone, 1-Hydroxycyclohexyl phenyl ketone, 2-Hydroxy-2-methylpropiophenone, 2-methylbenzophenone, 3-methylbenzophenone, methylbenzoylformate, the 2-methyl-4-(methylthio)-2-morpholinopropiophenone, phenanthrenequinone, 4'-phenoxyacetophenone, (cumene)cyclopentadienone hexafluorophosphate, iron(II), 9,10-diethoxyanthracene and 9,10-dibutoxyanthracene, the 2-ethyl-9,10-dimethoxyanthracene, thioxanthen-9-one and corresponding combinations. In preferred compositions of the invention, a radical photoinitiator possessing Norrish type I activity may be used, such as a phosphine oxide. Acetophenone family photoinitiators are also a preferred choice in hybrid systems containing both cationically polymerizable compounds comprising an alkoxylated cycloaliphatic epoxide of formula (I) and radically polymerizable (meth)acrylate functionalized compounds. The quantity of the photoinitiator(s) may be from 0.01% to 5%, from 0.02% to 3%, from 0.05% to 2%, from 0.1% to 1.5%, or from 0.2% to 1%, by weight based on the total weight of the curable composition. The total quantity of the photoinitiator(s) may be from 0.01% to 10%, from 0.1% to 9%, from 0.2% to 8%, from 0.5% to 7%, or from 1% to 6%, by weight based on the total weight of the curable composition. Additives The hardenable composition of the present invention may include an additive. The hardenable composition may include a mixture of additives. In particular, the additive may be chosen from sensitizers, amine-type synergists, antioxidants / photostabilizers, light blockers / absorbers, polymerization inhibitors, antifoaming agents, flow-enhancing or leveling agents, coloring materials, pigments, dispersants (wetting agents, surfactants), sliding additives, fillers, chain transfer agents, thixotropic agents, mattifying agents, impact strength modifiers, waxes, corresponding mixtures, and any other additives conventionally used in coating techniques, sealants, adhesives, molding, 3D printing, or inks. The hardening composition may include a sensitizer. Sensitizers can be introduced into the curable composition of the present invention to extend the sensitivity of the photoinitiator to longer wavelengths. For example, the sensitizer can absorb light at longer or shorter wavelengths than the photoinitiator and be able to transfer energy from the photoinitiator and return to its ground state. Examples of suitable sensitizers include anthracenes and carbazoles. The concentration of sensitizer in the curable composition will vary depending on of the photoinitiator which is used. Typically, however, the curable composition is formulated to include from 0% to 5%, in particular 0.1% to 3%, more particularly 0.5% to 2%, by weight of sensitizer on the basis of the total weight of the curable composition. The hardenable composition may include a chain transfer agent. Chain transfer agents can be introduced into the hardening composition of the present invention to increase the curing rate. In particular, the chain transfer agent can be a polyol. Polythiols or polyamines can slow down cationic curing and are not a preferred choice in the present invention. The hardenable composition may include a stabilizer. Stabilizers may be introduced into the hardenable composition of the present invention to provide adequate storage stability and shelf life. Advantageously, one or more such stabilizers are present at each stage of the process used to prepare the hardenable composition, to protect against undesirable reactions during the processing of the ethylenically unsaturated components of the hardenable composition. In this context, the term "stabilizer" means a compound or substance that delays or prevents the reaction or hardening of actinically hardenable functional groups present in a composition in the absence of actinic radiation.However, it will be advantageous to choose an amount and type of stabilizer that allows the composition to still be able to harden when exposed to actinic radiation (i.e., the stabilizer does not prevent the composition from hardening by radiation). Typically, effective stabilizers in the context of the present invention will be classified as free radical stabilizers (i.e., stabilizers that work by inhibiting free radical reactions). All stabilizers known in the art associated with (meth)acrylate functionalized compounds can be used in the present invention. Quinones represent a particularly preferred type of stabilizer that can be used in the context of the present invention. In this context, the term "quinone" includes both quinones and hydroquinones, as well as ethers thereof, such as monoalkyl, monoaryl, monoaralkyl, and bis(hydroxyalkyl) hydroquinone ethers. Hydroquinone monomethyl ether is an example of a suitable stabilizer that can be used. Other stabilizers known in the art, such as BHT and derivatives, phosphite-type compounds, phenothiazine (PTZ), triphenylantimony, and tin(IT) salts, can also be used. The concentration of stabilizer in the hardenable composition will vary depending on the sta- The specific stabilizer or combination of stabilizers chosen for use also depends on the desired degree of stabilization and the susceptibility of the components in the curable compositions to degradation in the absence of stabilizer. Typically, however, the curable composition is formulated to comprise from 5 to 5,000 ppm of stabilizer. According to some embodiments of the invention, the reaction mixture during each stage of the process used to prepare the curable composition contains at least a certain amount of stabilizer, e.g., at least 10 ppm of stabilizer. The curable composition may include a light blocker (sometimes called a light absorber). The introduction of a light blocker is particularly advantageous when the curable composition is to be used as a resin in a 3D printing process involving photocuring. The light blocker can be any substance known in the art of 3D printing, including, for example, non-reactive pigments and dyes. The light blocker can be an agent that blocks visible light or a UV light blocker, for example.Examples of suitable light blockers include, but are not limited to, titanium dioxide, carbon black, and organic ultraviolet light absorbers such as hydroxybenzophenone, hydroxyphenylbenzotriazole, oxanilide, hydroxyphenyltriazine, Sudan I, bromothymol blue, 2,2*-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole) (marketed under the trade name 'Benetex OB Plus') and benzotriazole-based ultraviolet light absorbers. The amount of light-blocking agent can be modified as desired or appropriate for particular applications. Generally, if the curable composition contains a light blocker, it is present at a concentration of 0.001 to 10% by weight, based on the weight of the curable composition. Advantageously, the hardenable compositions of the present invention can be formulated to be solvent-free, that is, free from non-reactive volatile substances (substances having a boiling point at atmospheric pressure of 150 °C or less). For example, the hardenable compositions of the present invention may contain little or no non-reactive solvent, for example, less than 10%, less than 5%, less than 1%, or even 0% of non-reactive solvent, based on the total weight of the hardenable composition. As used herein, the term non-reactive solvent means a solvent that does not react when exposed to actinic radiation used to harden the hardenable compositions described herein. According to other advantageous embodiments of the invention, the hardenable composition is formulated to be usable as a one-component system or in a part. That is, the curable composition is cured directly and is not combined with another component or a second part (such as an amine monomer, as defined in U.S. Patent Application Publication Document No. 2017 / 0260418 A1) prior to being cured. Hardenable Composition In preferred embodiments of the invention, the hardenable composition is a liquid at 25°C. In various embodiments of the invention, the curable compositions described herein are formulated to have a viscosity of less than 10,000 mPa-s (cP), or less than 5,000 mPa-s (cP), or less than 4,000 mPa-s (cP), or less than 3,000 mPa-s (cP), or less than 2,500 mPa-s (cP), or less than 2,000 mPa-s (cP), or less than 1,500 mPa-s (cP), or less than 1,000 mPa-s (cP) or even less than 500 mPa-s (cP) as measured at 25 °C using a Brookfield viscometer, model DV-II, using a rod 27 (the speed of the rod typically varying between 20 and 200 rpm, depending on the viscosity). In advantageous embodiments of the invention, the viscosity of the hardenable composition is from 200 to 5000 mPa-s (cP), or from 200 to 2000 mPa-s (cP), or from 200 to 1500 mPa-s (cP), or from 200 to 1000 mPa-s (cP) at 25 °C.Relatively high viscosities can provide satisfactory performance in applications where the curable composition is heated above 25°C, for example in 3D printing or similar operations that use machines with heated resin tanks. The curable compositions described herein may be compositions that require curing by means of radical polymerization, cationic polymerization, or other types of polymerization. In particular embodiments, the curable compositions are photocured (i.e., cured by exposure to actinic radiation such as light, in particular visible or UV light). The hardenable composition of the invention may be a composition of ink, coating, sealing agent, adhesive, molding or 3D printing, in particular a 3D printing composition. End-use applications for curable compositions include, but are not limited to, inks, coatings, adhesives, additive manufacturing resins (such as 3D printing resins), molding resins, sealants, composites, antistatic coatings, electronic applications, recyclable materials, smart materials capable of detecting and responding to stimuli, packaging materials, personal care items, items for use in agriculture, water or food processing, or animal husbandry, and bio-materials medical. The hardenable compositions of the invention thus find use in the production of biocompatible articles. Such articles may, for example, exhibit high biocompatibility, low cytotoxicity, and / or a low content of extractable compounds. The composition according to the invention can in particular be used to obtain a hardened product, a 3D printed article according to the following processes. Process for preparing a hardened product, a 3D printed article The process for preparing a hardened product according to the invention comprises hardening the composition of the invention. In particular, the composition can be hardened by exposing it to radiation. More specifically, the composition can be hardened by exposing it to UV, near-UV, visible, infrared, and / or near-infrared radiation, or to an electron beam. Curing can be accelerated or facilitated by supplying energy to the curable composition, such as by heating it. Therefore, the cured product can be considered the reaction product of the curable composition, formed by the curing process. A curable composition can be partially cured by exposure to actinic radiation, with further curing achieved by heating the partially cured article. For example, an article formed from the curable composition (e.g., a 3D-printed article) can be heated to a temperature ranging from 40°C to 120°C for a period of time ranging from 5 minutes to 12 hours. Before curing, the curable composition can be applied to a substrate surface by any known conventional method, for example, by spraying, squeegee coating, roller coating, casting, drum coating, immersion, and similar methods and combinations thereof. Indirect application using a transfer process can also be used. A substrate can be any commercially relevant substrate, such as a high surface energy substrate or a low surface energy substrate, such as a metallic substrate or a plastic substrate, respectively. Substrates can include metal, paper, cardboard, glass, thermoplastics such as polyolefins, polycarbonate, acrylonitrile butadiene styrene (ABS), and corresponding mixtures, composites, wood, leather, and corresponding combinations thereof.When used as an adhesive, the curable composition can be placed between two substrates and then cured, the cured composition thus bonding the substrates together to produce a bonded article. Curable compositions according to the present invention can also be formed or cured by a bulk method (for example, the curable composition can be poured into a suitable mold and then cured). The hardened product obtained by the process of the invention can be an ink, a re-coat, a sealant, an adhesive, a molded article or a 3D printed article. In particular, the hardened product can be a 3D printed item. A 3D printed item can be defined as an item obtained with a 3D printer using a computer-aided design (CAD) model or a digital 3D model. The 3D printed article can, in particular, be obtained by a process for preparing a 3D printed article that includes printing a 3D article with the composition of the invention. In particular, the process may include printing a 3D article layer by layer or continuously. A plurality of layers of a curable composition according to the present invention can be applied to a surface of a substrate; the plurality of layers can be cured simultaneously (by exposure to a single dose of radiation, for example) or each layer can be cured successively before the application of an additional layer of the curable composition. The curable compositions described here can be used as resins in three-dimensional printing applications. Three-dimensional (3D) printing (also known as additive manufacturing) is a process in which a 3D digital model is created by the accumulation of build material. The printed 3D object is created using computer-aided design (CAD) data by sequentially building two-dimensional (2D) layers or slices that correspond to cross-sections of 3D objects. Stereolithography (SL) is a type of additive manufacturing in which a liquid resin is cured by selective exposure to radiation to form each 2D layer. The radiation can be in the form of electromagnetic waves or an electron beam. The most commonly used energy source is ultraviolet, visible, or infrared radiation. Stereolithography and other photocurable 3D printing processes typically use low-intensity light sources to irradiate each layer of a photocurable resin to form the desired part. Therefore, the polymerization kinetics of photocurable resins and the green strength of the printed part are important criteria that will determine whether a particular photocurable resin will polymerize (cure) sufficiently when irradiated and possess sufficient green strength to maintain its integrity throughout the 3D printing process and post-processing. The hardenable compositions of the invention are particularly useful as resin formulations for 3D printing, that is to say, compositions intended for use in the manufacture of three-dimensional articles using techniques 3D printing. Such three-dimensional articles may be self-supporting and may be essentially made of, or composed of, a composition according to the present invention that has been hardened. The three-dimensional article may also be a composite, comprising at least one component made essentially of, or composed of, a hardened composition as mentioned above, and at least one additional component made of one or more materials different from such a hardened composition (for example, a metallic component, a thermoplastic component, an inorganic filler, or a fibrous reinforcement).The curable compositions of the present invention are particularly useful in light-based digital printing (LBL), although other types of three-dimensional (3D) printing processes can also be carried out using the curable compositions of the invention (e.g., SLA, inkjet, multijet printing, piezoelectric printing, actinic-cured extrusion, and gel deposition printing). The curable compositions of the present invention can be used in a three-dimensional printing operation in conjunction with another material that functions as a scaffold or support for the article formed from the curable composition of the present invention. Therefore, the curable compositions of the present invention are useful in various types of three-dimensional manufacturing or printing techniques, including processes in which the construction of a three-dimensional object is carried out in stages or layer by layer. In such processes, layer formation can be achieved by solidification (hardening) of the curable composition under the effect of exposure to radiation, such as visible, UV, or other actinic radiation. For example, new layers can be formed on the upper surface of the growing object or on the lower surface of the growing object. The curable compositions of the present invention can also be advantageously used in additive manufacturing processes for the production of three-dimensional objects in which the process is carried out continuously.For example, the object can be produced from a liquid interface. Suitable processes of this type are sometimes referred to in the technical field as "continuous liquid interface (or interface phase) production (or printing) processes" ("CLIP"). Such processes are described, for example, in WO 2014 / 126830; WO 2014 / 126834; WO 2014 / 126837; and Tumbleston et al., "Continuous Liquid Interface Production of 3D Objects," Science Vol. 347, Issue 6228, pp. 1349-1352 (March 20, 2015), the description of which is hereby incorporated in full by reference for all purposes. When stereolithography is performed above a window constructed to be permeable to oxygen, the production of an article using a hard composition- The cuttable layer according to the present invention can be made in a CLIP procedure by creating an oxygen-containing "dead zone," which is a thin, uncured layer of the curable composition between the window and the surface of the article being cured as it is produced. In such a process, a curable composition is used in which curing (polymerization) is inhibited by the presence of molecular oxygen; such inhibition is typically observed, for example, in curable compositions that are capable of being cured by radical mechanisms. The desired dead zone thickness can be maintained by selecting various control parameters, such as the photon flux and the optical and curing properties of the curable composition.The CLIP process is conducted by projecting a continuous sequence of actinic radiation images (e.g., UV) (which can be generated by a digital light processing imaging unit, for example) through an oxygen-permeable window, transparent to actinic radiation (e.g., UV), below a bath of the curable composition maintained in liquid form. A liquid interface below the article being advanced (growing) is maintained by the dead zone created below the window. The article being cured is continuously extracted from the bath of curable composition above the dead zone, which can be replenished by introducing additional quantities of the curable composition into the bath to compensate for the amounts of curable composition being cured and incorporated into the growing article. In another embodiment, the curable composition is supplied by ejecting it from a print head rather than from a vat. This type of process is commonly referred to as inkjet or multijet 3D printing. One or more UV curing sources mounted directly behind the inkjet print head cure the curable composition immediately after it is applied to the constructed surface substrate or to previously applied layers. Two or more print heads can be used in the process, allowing different compositions to be applied to different areas of each layer. For example, compositions with different colors or different physical properties can be applied simultaneously to create 3D-printed parts with variable compositions.In common use, support materials, which are later removed during post-processing, are deposited along with the compositions used to create the desired 3D printed part. Print heads can operate at temperatures from approximately 25°C to approximately 100°C. The viscosities of the curable compositions can be less than 30 mPa·s at the print head's operating temperature. The process for preparing a 3D printed article may include the Next steps: a. application (e.g., coating) of a first layer of a composition hardenable according to the present invention on a surface; b. hardening of the first layer, at least partially, to obtain a first hardened layer; c. application (e.g., coating) of a second layer of the composition hardenable on the first hardened layer; d. hardening of the second layer, at least partially, to obtain a a second hardened layer bonded to the first hardened layer; and repeating steps c) and d) a desired number of times to construct the three-dimensional article. Although the hardening steps can be carried out by any suitable means, which in some cases will depend on the components present in the hardenable composition, in certain embodiments of the invention, hardening is accomplished by exposing the layer to be hardened to an effective amount of radiation, in particular actinic radiation (e.g., electron beam radiation, UV radiation, visible light, etc.). The three-dimensional article that is formed can be heated to perform thermal hardening. Consequently, in various embodiments, the present invention provides a method comprising the steps of: the application (e.g., coating) of a first layer of a composition hardenable according to the present invention and in liquid form on a surface; b. exposure of the first layer image by image to radiation actinic to form a first exposed imaged cross-section, the radiation being of sufficient intensity and duration to cause a hard- at least partial removal of the layer in exposed areas; and application (e.g., coating) of an additional layer of the composition hardenable position on the previously imaged cross-section exposed; d. exposure of the additional layer image by image to radiation actinic to form an additional imaged cross-section, the radiation being of sufficient intensity and duration to cause a hard- at least partial capping of the additional layer in the areas exposed and cause the additional layer to adhere to the section previously shown cross-sectional image; °. Repeat steps c) and d) a desired number of times to construct the three-dimensional article. After the 3D printed item has been processed, it can undergo one or more post-processing steps. These post-processing steps can be chosen from one or more of the following: removal of any printed support structures, washing with water and / or organic solvents to remove residual resins, and post-processing using heat treatment and / or actinic radiation, either simultaneously or sequentially. These post-processing steps can be used to transform the newly printed item into a finished, functional item ready for use in its intended application. The hardened product and the 3D printed articles obtained with the processes of the invention are described below. Hardened product, 3D printed item The hardened product of the invention is obtained by hardening the composition of the invention or according to the process of the invention. The cured product can be an ink, a coating, a sealant, a molded adhesive, or a 3D-printed item. In particular, the cured product can be a 3D-printed item. Uses The alkoxylated cycloaliphatic epoxy of the invention can be used to obtain an ink, a coating, a sealant, an adhesive, a molded article or a 3D printed article, in particular a 3D printed article. In this description, embodiments have been described in a way that permits a clear and concise description, but it is anticipated and will be appreciated that embodiments may be combined or separated in various ways without departing from the invention. For example, it will be appreciated that all preferred features described herein are applicable to all aspects of the invention described herein. In certain embodiments, the present invention may be considered as excluding any element or process step that does not materially affect the basic and novel features of the invention. Furthermore, in certain embodiments, the invention may be considered as excluding any element or process step not specified herein. Although the invention is illustrated and described herein by reference to specific embodiments, the invention is not intended to be limited to the details presented. Various modifications may instead be made to the details within the scope and range of equivalents of the claims and without departing from the invention. The present invention is illustrated with the following non-limiting examples. Examples Materials All materials used in the examples are available from standard commercial sources such as Sigma-Aldrich Company Ltd. and Tokyo Chemical Industry Ltd. unless otherwise stated. Polyol R3215, Polyol 4360, and Polyol R6405 are available from Perstorp AB. Example | : Synthesis of a trypoxide from Polyol R3215 (EI Synthesis of Cyclohex-3-ene-1-carbonyl chloride [Chem.22] ss aa To + 3-Cyclohexene-1-carboxylic acid (400.0 g, 3.1708 mol) is dissolved in chloroform (1870 mL) under nitrogen and N,N-dimethylformamide (10 mL) is added. Thionyl chloride (456.0 g; 3.8329 mol) is added to the stirred reaction mixture for 7 h. HCl and SO₂ gases are released, and the internal temperature is maintained at 15–22 °C during the addition. After the addition is complete, the reaction mixture is stirred for 18 h under nitrogen at 20 °C. Chloroform, DMF, and unreacted thionyl chloride are removed under vacuum. The pale yellow liquid product is then dried to constant weight under vacuum (30 mbar, 30 °C). Any precipitated white solid is removed by filtration. This yields cyclohex-3-ene-1-carbonyl chloride (451.5 g; 98.5% of the theoretical weight). !H NMR (400 MHz, CDCIs): 5.70 (m, 2H), 3.04-2.97 (m, 1H), 2.46-2.29 (m, 2H), 2.22-2.07 (m, 3H), 1.87-1.76 (m, 1H). Synthesis of a trialene derived from Polyol R3215 [Chem.23] fuse 1 on, 8 5 THAT A reaction vessel is loaded with Polyol R3215 (100.0 g; 125.8 mmol) and the material is dried under vacuum with stirring (20 mbar, 75 °C, 3 h). The reaction vessel is then cooled to 20 °C, rinsed with nitrogen, and loaded with dichloromethane (500 mL) and triethylamine (50.91 g, 503.1 mmol). The clear solution is then cooled with an ice-water mixture to 5 °C, and cyclohex-3-ene-1-carbonyl chloride (78.4 g, 542 mmol) is added over 40 min while maintaining the internal temperature at 5 °C (the reaction is exothermic). The cloudy reaction mixture is then allowed to warm to 20 °C for 2 h and stirred at this temperature for a further 18 h. The reaction mixture is then loaded into a solution of sodium bicarbonate (100 g) in water (1000 mL) and stirred rapidly for 6 h at 20 °C. The organic phase is separated and extracted with water (2 x 350 mL). The organic phase is collected, and all volatile compounds are removed under vacuum. The liquid product is then dried to constant weight under vacuum (30 mbar, 50 °C). This yields the desired trialene product (147.6 g). 'EH NMR (400 MHz, CDCL,): 5.68 (m, 6H), 4.25 (m, 6H), 3.71-3.53 (m, 54H), 3.32 (m, 6H), 2.63-2.54 (m, 3H), 2.39-1.95 (m, 15H), 1.75-1.63 (m, 3H), 1.45-1.36 (m, 2H), 0.87-0.81 (m, 3H). Synthesis of a trypoxide derived from Polyol R3215 (El [Chem.24] ae Killed Fa € 2 ar to RAI =, (ai 5, ESS . > - se ver w,] su A reaction vessel is loaded with Polyol R3215 trialene (147.6 g, 131.9 mmol) and dichloromethane (1100 mL) is added. The reaction mixture is cooled to an internal temperature of 3 °C. 3-Chloroperbenzoic acid (73.5% active, 99.1 g, 422.1 mmol) is added over 5 h with vigorous stirring, while maintaining the internal temperature at 3–4 °C. The cloudy mixture is stirred vigorously for 18 h and allowed to warm to 20 °C. The reaction mass is then filtered, and the white solid is washed with dichloromethane (2 x 50 mL). A sodium sulfite solution (50 g) in water (500 mL) is added to the resulting filtrate, and the two-phase mixture is stirred for 60 min. The mixture is then separated into phases, and the organic phase is washed with a sodium bicarbonate solution (83.6 g) in water (750 mL), and then with water (2 x 500 mL). The phases of the mixture are allowed to separate for 18 hours, and the organic phase is collected, dried with sodium sulfate (100 g), and filtered. The filtrate is concentrated under vacuum, and the liquid product is then dried to constant weight (30 mbar, 35 °C). This provides the desired trypoxide product El (141.5 g, 91.9% of theory). 'H NMR (400 MHz, CDCI): 4.22 (m, 6H), 3.80-3.54 (m, 54H), 3.31 (m, 6H), 3.25-3.14 (m, 6H), 2.58-2.50 (m, 3H), 2.32-1.88 (m, 12H), 1.82-1.74 (m, 3H), 1.68-1.56 (m, 2H), 1.48-1.35 (m, 3H), 0.86-0.81 (m, 3H). FT-IR (ATR, pure): 2866 (m), 1729 (s), 1303 (m), 1254 (m), 1232 (m), 1173 (m), 1099 (vs), 1061 (m), 991 (m), 973 (m), 938 (m), 873 (m), 796 (m). Example 2: Synthesis of a tetraepoxide from Polyol 4360 (E2 Synthesis of a tetraalkene derived from Polyol 4360 [Chem.25] 4 has, 8 8 — Li $ 4 has A reaction vessel is loaded with Polyol 4360 (99.0 g; 157.1 mmol) and the material is dried under vacuum with stirring (20 mbar, 75 °C, 3 h). The reaction vessel is then cooled to 20 °C, rinsed with nitrogen, and loaded with dichloromethane (500 mL) and triethylamine (82 g, 810 mmol). The clear solution is then cooled with an ice-water mixture to 5 °C, and cyclohex-3-ene-1-carbonyl chloride (100.0 g, 691.5 mmol) is added over 50 min while maintaining the internal temperature at 5–10 °C (the reaction is exothermic). The cloudy reaction mixture is then allowed to warm to 20 °C for 2 h and stirred at this temperature for a further 18 h. The reaction mixture is then loaded into a solution of sodium hydrogen carbonate (50 g) in water (1000 mL) and stirred rapidly for 1 h at 20 °C. The organic phase is separated and extracted with water (350 mL), then again with a solution of sodium hydrogen carbonate (25 g) in water (500 mL) and finally with cau (400 mL). The organic phase is collected and all volatile compounds are removed under vacuum. The liquid product is then dried to constant weight under vacuum (30 mbar, 50 °C). This yields the desired tetraalkene product (178.7 g). !H NMR (400 MHz, CDCI;): 5.68 (m, 8H), 5.08-5.00 (m, 4H), 3.59-3.23 (m, 28H), 2.58-2.49 (m, 4H), 2.25-1.96 (m, 20H), 1.72-1.62 (m, 4H), 1.23-1.10 (m, 24H). Synthesis of a tetraepoxide | Polvol 4360 (E2 [Chem.26] 5, ++ Pre Eat 4 RE TE TS rt A reaction vessel is loaded with Polyol 4350 tetraalkene (178.7 g, 168.2 mmol) and dichloromethane (1250 mL) is added. The reaction mixture is cooled to an internal temperature of 2 °C. 3-Chloroperbenzoic acid (72.0% active, 169.3 g, 706.3 mmol) is added over 5 h with vigorous stirring. maintaining the internal temperature at 3–4 °C. The turbid mixture is vigorously stirred for 18 h and allowed to warm to 20 °C. The reaction mass is then filtered, and the white solid is washed with dichloromethane (2 x 50 mL). A sodium sulfite solution (50 g) in water (500 mL) is added to the resulting filtrate, and the two-phase mixture is stirred for 60 min. The mixture is then separated into phases, and the organic phase is washed with a solution of sodium hydrogen carbonate (50 g) and sodium sulfite (21 g) in water (500 mL), and then with water (2 x 500 mL). The phases of the mixture are allowed to separate for 18 h, and the organic phase is collected, dried with sodium sulfate (220 g), and filtered. The filtrate is concentrated under vacuum, and the liquid product is then dried to constant weight (30 mbar, 35 °C). This yields the desired tetraepoxide product E2 (180.6 g, 95.3% of the theoretical value). !H NMR (400 MHz, CDCIs): 5.08-4.97 (m, 4H), 3.59-3.10 (m, 36H), 2.54-2.45 (m, 4H), 2.30-1.35 (m, 24H), 1.25-1.06 (m, 24H). FT-IR (ATR, pure): 2976 (w), 2933 (w), 2871 (w), 1726 (vs), 1376 (m), 1304 (m), 1255 (m), 1231 (m), 1174 (s), 1144 (m), 1100 (vs), 1006 (m), 989 (m), 974 (m), 935 (m), 905 (m), 859 (m), 796 (m), 785 (m). Synthesis of a hexaalkene derived from Polyol R6405 [Chem.27] prearhqe S »+ 0 2 » Pa 5 DRE 4 mi fu” pue mi à Fe ; pe 5 13 $5 pe dy gi A reaction vessel is loaded with Polyol R6405 (385.0 g; 465.5 mmol) and the material is dried under vacuum with stirring (20 mbar, 80 °C, 2.5 h). The reaction vessel is then cooled to 20 °C, rinsed with nitrogen, and loaded with dichloromethane (2500 mL) and triethylamine (353.3 g, 3.4915 mol). The clear solution is then cooled with an ice-water mixture to 12 °C, and cyclohex-3-ene-1-carbonyl chloride (445.0 g, 3.077 mol) is added over 2 h while maintaining the internal temperature at 12–15 °C (the reaction is exothermic). The cloudy reaction mixture is then allowed to warm to 20°C for 2 hours and stirred at this temperature for another 18 hours. The reaction mixture is then loaded into a solution of sodium bicarbonate (205 g) in water (2300 mL) and stirred rapidly for 4 h at 20 °C, The organic phase is separated and extracted with water (3 x 1500 mL). The organic phase is collected, and all volatile compounds are removed under vacuum. The liquid product is then dried to constant weight under vacuum (30 mbar, 50 °C). This yields the desired hexaalkene product (701.6 g). *H NMR (400 MHz, CDCI;): 5.68 (m, 12H), 4.29-4.06 (m, 12H), 3.71-3.35 (m, 56H), 2.63-2.52 (m, 6H), 2.27-2.22 (m, 12H), 2.14-1.96 (m, 18H), 1.74-1.62 (m, 6H). FT-IR (ATR, pure): 3025 (w), 2869 (m), 1729 (vs), 1303 (m), 1288 (m), 1247 (m), 1222 (s), 1166 (s), 1099 (vs), 1064 (s), 1039 (s), 952 (m), 919 (m), 878 (m), 650 (s). Synthesis of a hexaalkene from Polyol R6405 by direct esterification Polyol R6405 from Perstorp (515.2 g, 622.97 mmol), the acid 3-Cyclohexene-1-carboxylic acid (565.8 g, 4.485 mol) and toluene (2500 mL) are combined in a reaction vessel equipped with a condenser and a Dean-Stark trap. The reaction vessel is rinsed with nitrogen, methanesulfonic acid (4.2 g) is added with stirring, and the reaction mixture is heated under reflux (internal temperature 114–116 °C). Water is removed from the reaction by azeotropic distillation for 16.5 h (the collected toluene is replaced). The reaction mixture is cooled to 20 °C and extracted with a solution of sodium bicarbonate (100 g) in water (1500 mL). More toluene (1000 mL) and water (400 mL) are added, and the phases of the mixture are allowed to separate. The organic phase is separated and washed with a 1% aqueous solution of sodium bicarbonate (2 x 1000 mL), then with water (2 x 750 mL). The organic phase is collected and all volatile compounds are removed under vacuum. The liquid product is then dried to constant weight under vacuum (12 mbar, 55 °C). This yields the desired hexaalkene product (933.5 g). Synthesis of a Li Polyol R6405 (E3 [Chem.28] you SE BTS at 5 f° PT Li MATE 8 éret va MAÉ EEE ë RS a Ce A ms , it 0 A reaction vessel is loaded with Polyol R6405 hexaalkene (500.0 g, 338.75 mmol) and dichloromethane (2500 mL) is added. The reaction mixture is cooled to an internal temperature of 6 °C and 3-chloroperbenzoic acid (70.2% active, 532.96 g, 2.168 mmol) is added over 5 h with vigorous stirring. Maintaining an internal temperature of 46 °C, the turbid mixture is vigorously stirred for 18 h and allowed to warm to 20 °C. The reaction mass is then filtered, and the white solid is washed with dichloromethane (350 mL). A sodium sulfite solution (100 g) in water (1500 mL) is added to the resulting filtrate, and the two-phase mixture is stirred for 30 min. The mixture is then separated from its surrounding phase, and the organic phase is washed with water (2 x 500 mL). The organic phase is collected, and all volatile compounds are removed under vacuum. The liquid product is then dried to constant weight under vacuum (30 mbar, 40 °C). This yields the desired hexaepoxide product E3 (492.1 g, 92.5% of the theoretical value). 'H NMR (400 MHz, CDCI,): 4.21-4.00 (m, 12H), 3.66-3.30 (m, 56H), 3.21-3.09 (m, 12H), 2.54-2.43 (m, 3H), 2.27-1.31 (m, 39H). FT-IR (ATR, pure): 2868 (m), 1727 (vs), 1305 (m), 1255 (m), 1231 (m), 1215 (m), 1173 (s), 1100 (vs), 1058 (s), 1015 (m), 991 (m), 974 (m), 936 (m), 904 (m), 874 (m), 859 (m), 837 (m), 796 (m), 786 (m). Comparative Example 1 For comparison, the commercially available UviCure S105E epoxy resin and UviCure S130 oxetane (available from Sartomer) were used. The difunctional cycloaliphatic epoxy, sold as UviCure® S105, has the following structure: [Chem.29] O ANS Hardening Experiments The following example illustrates the UV curing speed of the epoxy resins of the present invention. For all the curing tests below, the SpeedCure 938 photoinitiator (Sartomer) was used. The formulations were cured to film thicknesses of 100 µm under a mercury lamp using a belt curing instrument (Jenton International Ltd., model no. JA2000VPXI-0000) with a belt speed of 15 m / min and a lamp intensity of 50% (UV dose per pass: UVV: 58 mJ / m², UVA: 10⁸ mJ / m², UVB: 10⁸ mJ / cm², UVC: 20 mJ / cm²). The substrate used was black and white paper. standard (Lèneta formula 3N-31). Viscosity measurements were carried out on a Brookfield viscometer (pin no. 31, 25 °C). Each epoxy resin tested (E1, E2, or E3) was mixed with UviCure S130 at various weight ratios from 0 to 100%. Data obtained for mixtures of UviCure S1O5E and UviCure S130 were used as a reference. The photoinitiator SpeedCure 938 (Sartomer) was used at a dosage of 1% by weight in the tested resin mixtures. The curing rate was evaluated by the number of passes under the lamp required to give a surface-cured “non-sticky” (TF) coating (as determined when the coating surface no longer appears sticky when lightly touched) or the depth of curing as determined by the “thumb twist” (TT) test (i.e., until no visible mark is made when a thumb is pressed down firmly on the coating with a twisting motion). Solvent resistance was tested on cured samples using a double rub test with MEK according to ASTM D4752. The results are given in Tables 1, 2, 3 and 4. [Table 1] Viscosity |curing |surface MEK depth (cP) curing |doubles (number of |(number of = |frictions | passes) passes) qe | 12 9 # Ÿ dr 6 se: No hardening # No hardening No hardening 0 8 1 j - 100 5 |- |- [Tables 2] Surface hardening depth of MEK (eP) | doubles ) (number of | (number of | friction passes) passes) Ja0 | - | 1700 | 3- 5 8 800 = 3 = a2 | 3 100 230 1 3 50 = + 3 45 0. pe 3 quo 60 | 6 quo 43 No hardening | No hardening | hardening 120 [30 [43 No hardening- No hardening- |- hardening hardening fo 100 25 | | - [Tables 3] Example 3: |UviCure |Curing viscosity [depth |MEK Hexaepoxide |S130(% |(cP) of hardening surface by weight) (number of |cling friction (% by weight) passes) (number of 0 >100 3600 |- | 1475 5 6 750 3 = 400 2 “a 258 8 x 187 1 2 sp 3 65 3 5 45 No hardening | |No hardening 120 [80 (45 No hardness |No hardness |- cissement cissement fo 100 s |- | [Tables 4] Example UviCure | Viscosity | Curing | Depth | MEK Comparison 1: [S130(% |(cP) of curing surface - double UviCure S105E Jen by weight) (number of | curing friction (% by weight) passes) (number of Viscosity|curing [depth |MELI (eP) of hardened surface (number of |shearing / friction passes) (number of passes) 250 3 6 2 160 2 3 1 110 1 2 3 80 1 2 5 65 1 2 8 50 1 2 6 45 1 2 Z 40 2 3 6 35 No hardening |No hardening |shearing and ais (meth)acrylates 1) Materials [Tables 5] Material | Composition Supplier SR833 ' © To = Sartomer ® 0 | Death tricyclo[S.2,1.026]decanedimethanol diacrylate Uvicure S105 (ECC) | Sartomer-Lambson Uvicure? Sartomer-Lambson (ECC) 3,4-Epoxycyclohexanecarboxylate of 3,4-Epoxycyclohexylmethyl PI-031-20 $, 2 | Sartomer-Lambson PPS: 8 The 18-B The pl m0A 9 Lo ! La. 0 a COLE à Le Nes ene TO 9 AIO AA OLA fo FPS 7 3 A 155 e ct = ? Lie “ie , A à ( La bd ei À" à born to” |Sartomer-Lambson Poly(oxy-1,2-ethanediyl), o-hydro-o-hydroxy-, | ether with 2,2'-[oxybis(methylene)]bis[2-(hydroxymethyl)- | 1,3-propanediol] (6:1) | PS "E Uvicure s130 (OXT) J_ 3-ethyl-1-3-hydroxymethyl-oxetane 3-Ethy-1-3-Hydroxymethyloxetane Speedcure Î Ze Sartomer-Lambson re BKL ( T Fe F è, © 2,2-dimethoxy-1,2-diphenylethan-1-one Speedcure f sd, => | Sartomer-Lambson 938 hey LAS Bis(4-tert-butylphenyDiodonium) hexafluorophosphate Speedcure $ | Sartomer-Lambson cho” / s 2-isopropyl-9H-thioxanthen-9-one 2) Sample preparation and procedure [Table 6] summary of formulations and their properties Comparative Example 2 [Example 4 |Example 5 65.00 65.00 65.00 5.76 5.76 5.76 23.04 | 11.52 23.04 11.52 2.00 2.00 2.00 4.00 4.00 4.00 0.20 0.20 0.20 100.00 100.00 — |100.00 102.5 20 = 180 ) 4181 34.82 44.85 ) |183 3.36 2.58 2721 1717 2306 328.3 247 341.2 0.177 0.272 0.268 81.18 85.36 85.3 -|e47 83.48 SpeedCure BKL 200 SpeedCure 938 4.00 SpeedCure ITX 0.20 Total 100.00 Viscosity (at 25°C), cPs 102.5 Tensile strength (MPa) 4181 Elongation at break (%) |1.83 Young's modulus (MPa) 2721 Maximum load (N) 328.3 Energy at break (J) 0.177 Acrylate conversion (%) 81.18 After 7 days of aging Epoxy conversion (%) 83.41 After 7 days of aging A25 preservation modulus 3134 2906 [3119 39.88 59.77 65.61 81.75 44.72 47.44 0.02 |°C, MPa Peak loss modulus, °C |80.59 Peak tan delta, °C 110.45 Maximum heat flux (W / g) 52.68 (365 nm) Peak time (min) (365 nm) 0.02 0.02 1.66 Preparation of formulations in the Table In a 125 mL amber glass bottle, SR833, UVicure S130, UVicure S105, or PI-031-2018-B were loaded first, followed by Speedcure ITX, 938, and BKL. A 100 g mixture of each sample was sealed in the bottle by securing the lid with white tape. Three glass bottles were then placed on a trolley in an oven at 65 °C for approximately 2 hours, until the solution became clear. Viscosity measurement Viscosity measurements were taken using a Brookfield DV-II+ Pro viscometer. A standard S18 size spindle was used for viscosity measurement. Viscosity readings were taken at 25 °C, with the % torque between 30-80%. 1 sample ion of t; ja Viper SL 355 a cut of the PET film (approximate size 7.5” x 6.5”) into a square which corresponds to the shape of the glass (8" x 8") and attaches the PET film to the glass using double-sided tape. b. spraying of non-stick substances (Rust-o-leum Never spray) Wet Coat 1) evenly on the PET film. c. Selecting the Viper SLA's "elevator movement" to fix the position elevator at 2.1740. d. Use the pipette to trace approximately 2 mL of liquid onto the glass. e. Use the 5 µm side of the coating applicator to apply the first layer of film. f. establish a moderate E and D (E = 65, D = 5 for all three formulations), start of printing Once the first layer of printing is complete, use the side 10 µm applicator to apply the second 5 µm film layer. h. Repeat printing and thin film applications until the 30 µm side pm was used. Thus, three thin green strips measuring 4" x 0.5" with 6 layers, each layer of 5 µm, and a 35 mm x 12 mm DMA strip were printed by im- pressure. J- Drainage of uncured liquid resin, cleaning with IPA and air drying. k. Careful peeling of each thin strip from the PET film. ï Post-curing of the thin strips for 15 min at 30 °C with 100% intensity. (EnvisionTEC PCA 2000 curing unit) m storage at 23 + 2 °C and 50 + 10% relative humidity for at least 7 days before the test Tensile test An Instron 5966 tensile testing apparatus with a load capacity of 10 kN and tensile test setups was used to measure tensile properties. Thin strips were prepared for tensile testing. Six specimens were prepared for each sample, and the tensile test speeds were set at 5 mm / min. The tests were conducted according to the protocol of ASTM D882. The results are shown in [Fig. 1]. DMA test Using a TA Instruments DMA Q800 apparatus, changes in mechanical properties were observed in each cured DMA strip across a temperature range. To study the materials within this range, a DMA program operating from -150 °C to 250 °C at 3 °C / min with a frequency of 1 Hz was used. The resulting curves of conservation modulus (G'), loss modulus (G''), and tan(delta) were analyzed to understand the changes in polymer behavior. The results are presented in [Fig. 2]. FTIR Test A Fourier transform infrared (FTIR) spectrometer with an attenuated total reflection (ATR) configuration was used. All polymerization rate measurements were performed using a Thermo Scientific Nicolet iS50 FT-IR spectrometer equipped with a standard DLaTGS detector. For the measurement, a drop of liquid sample was placed in the center of an ATR crystal to collect the IR spectrum, and then a flat surface of a printed and cured thin strip was pressed onto the ATR crystal to collect a new IR spectrum for both acrylate and epoxy conversion calculations. Measurements were taken at the area under the reference peak at approximately 1720 cm⁻¹. The acrylate peak at approximately 1407 cm⁻¹ and the epoxy peak at approximately 790 cm⁻¹ were also measured.The peak area was determined using the baseline technique, where a baseline is chosen to be tangent to the absorbance minimum on both sides of the peak. The area below the peak and above the baseline was then determined. The limits... integration values ​​for the liquid and the hardened sample are not identical but are similar, especially for the reference peak. The ratio of the acrylate or epoxy peak area to the reference peak was determined for both the liquid and cured samples. The degree of curing or conversion, expressed as a percentage of acrylate or epoxy that reacted, was calculated from the equation below: Conversion (%) = [(Rjig- Re) x 100] / Riig Where Ra is the area ratio of the liquid sample and Rb is the area ratio of the cured tensile strip. The resulting acrylate and epoxy conversions were tested using the FTIR method described above. LED-DSC Test A scanning differential scanning calorimetry (DSC) instrument with a suitable 365 nm LED lamp configuration was used. All photopolymerization rate measurements were performed using a TA Instruments Q2000 DSC unit. A lamp holder for the DSC unit can be adapted and printed from Arkema's N3xtDimension® N3D-TOUGH784 resin to ensure a precise fit for a Digital Light Labs Accucure ULM-2-365 365 nm lamp. The LED lamp was automatically triggered by connecting the DSC unit's "Event" output to an Accure photorheometer-based ultraviolet illumination and measurement system. LED light exposure can be programmed using the "Event" on / off control in the Photo DSC software, while the light intensity can be preset from the Accure photorheometer-based ultraviolet illumination and measurement system. For the measurement, a liquid sample Approximately 5 mg was placed in the center of a T130522 DSC Tzero tray, cured by exposing it to 550 mW / cm² of 365 nm LED light for 5 minutes at a flow rate of 50 mL / min and 45°C. The resulting heat flux curve (W / g) was collected to analyze the maximum heat flux peak value and the maximum peak time. The results are presented in Fig. 3. Volume shrinkage test A. Determination of density for formulated resins: a. after formulation and mixing of a resin, filling of a pre-sized volumetric flask Weighing 5 mL or 10 mL of such resin up to the mark. b. Weighing the entire volumetric flask and calculating the density by dividing the net weight by the resin formulated by volume. € repeating this step 3 times, the average value being considered as the density of the formulated resin (D, unit: kg / L). d. The shrinkage measurement method is based on a volumetric principle metric: a certain weight of formulated resin (W1) was carefully dispersed into a pre-weighed aluminium foil weighing pod to fill the pod to a height of approximately 3-5 mm. Ensure that bubbles are trapped inside the resin. The volume of the sheet weighing pod is limited to approximately 1 mL per sheet. This is to ensure that the piece of hardened resin is narrow enough to fit through the neck of a volumetric flask. The hardening was carried out under a mercury lamp condition for enough passes to harden the surface. The tray of sheets was placed in a 60°C oven for further deep curing until fully hardened. The trays of sheets were then removed from the oven and left to cool to room temperature. filling a 50 mL or 100 mL volumetric bottle with deionized water up to the mark. Peel the sheet and place the hardened resin into the volumetric flask. The resin should be completely submerged and sink. Shake to ensure no air bubbles remain inside the flask. Place the volumetric flask on an analytical balance and set it to zero. Use a pipette to aspirate the excess water and bring the water volume back to the mark. Record the weight loss for the entire volumetric flask (W2). at least three repetitions are required for each of the resin formulations. Next, a calculation was performed to determine the weight loss of the volumetric flask in terms of water volume. The calculated water volume should equal the final volume of hardened resin according to the test design. The density of the applied water is 0.998 kg / L at 20 °C. The volume shrinkage ratio is calculated using the following equation: % shrinkage = ((W1 / D) — (W2 / 0.998)) / (W1 / D) x 100%

Claims

Demands

1. Alkoxylated cycloaliphatic epoxy according to the following formula (I): [Chem.30] {© Chr L of (D each R, and R; being independently chosen from H and Me; L being the radical of a polyol; each a being independently from 2 to 4; each b being independently 0 to 20 provided that at least one b not be 0; c being at least 3.

2. Alkoxylated cycloaliphatic epoxide according to claim 1, a being 2 and the alkoxylated cycloaliphatic epoxide being according to the following formula (there): [Chem.31] oO -L 5 CHR—CH} o_ iR o | CC b of (has) L, b and c being as defined in claim 1; each R, and R', being independently chosen from H and Me.

3. Alkoxylated cycloaliphatic epoxide according to claim 1, a being 4 and R, and R, both being H.

4. Alkoxylated cycloaliphatic epoxide according to any one of the claims indications 1 to 3, each b being independently from 1 to 20, in particular from 1 to 10, more specifically from 2 to 6.

5. Alkoxylated cycloaliphatic epoxide according to any one of the claims indications 1 to 4, the alkoxylated cycloaliphatic epoxide possessing a degree alkoxylation of at least 6, in particular of at least 8, more particularly lyrically of at least 10, more particularly of at least 12.

6. Alkoxylated cycloaliphatic epoxide according to any one of the claims- indications 1 to 5, c being from 3 to 10, in particular from 3 to 8, more particularly- linking from 4 to 6.

7. Alkoxylated cycloaliphatic epoxide according to any one of the claims indications 1 to 6, c being 3 and L being a trivalent linker according to the formula next (II): [Chem.32] KR d—(CHe —-tete-3 (Ha valax (M Rs being chosen from H, alkyl and alkoxy, in particular R; being alkyl, more specifically Rz being ethyl; d, d' and d' being independently 0 to 2, it being understood that at least 2 among d, d' and d" are not 0, in particular d, d' and d" being all l or d being 0 and d' and d” being |.

8. Alkoxylated cycloaliphatic epoxide according to any one of the claims indications 1 to 6, c being 4 and L being a tetravalent linker according to one of the the following formulas (IIIa), (IIIb) and (IIIc): [Chem.33] worm (CH #-(cH), ——CHac—À (EHah, spedas (Ia) [Chem.34] N / A NASA (IIIb) [Chem.35] ver mgee HELLO A TO (IIc) e, €', e” and e” being independently 0 to 2, it being understood that at least 3 among e, e, e ete” are not 0, in particular e, e', e" and e” being all 1,

9. Alkoxylated cycloaliphatic epoxide according to any one of the claims indications 1 to 6, c being 5 and L being a pentavalent linker according to the formula next (IV): [Chem.36] green res rises RAR AO AA (IV).

10. | Alkoxylated cycloaliphatic epoxide according to any one of the claims indications 1 to 6, c being 6 and L being a hexavalent linker according to the formula next (Va), (Vb) or (Ve): [Chem.37] N / A NO A F5 (Go) [Chem.38] IMANE vase veter pd (Vb) [Chem.39] mat mr mp Aa É LA AO ALLO AU À (Ve).

11. Process for the preparation of an alkoxylated cycloaliphatic epoxide of formula (D) as defined in any one of claims 1 to 10, the process comprising the following steps: a) reaction of a cyclohexene of formula (VI) with a polyol alkoxylated of formula (VII) to obtain an alkoxylated cyclohexene of formula (VIII); b) epoxidation of alkoxylated cyclohexene of formula (VIII) to obtain an alkoxylated cycloaliphatic epoxide of formula (D); [Chem.40] (VD [Chem.41] Read ï — | ete, — L & (VID [Chem.42] Eu] ( { — Case j —k L of (VII) [Chem.43] Oo L of (D L, R, R, a, b and c being such as defined in any one of the re- demands 1 to 10; X being OH, O-AIk or CI; AIKk being a C1-C6 alkyl.

12. Composition comprising a mixture of cycloaliphatic epoxides alkoxylated compounds of formula (T): [Chem.44] Oo Centro = THE ACE (D L, R, R"," a and b being such as defined in any one of the claims- instructions 1 to 10; c being at least 2, in particular from 2 to 10; and at least one of the alkoxylated cycloaliphatic epoxides of formula (I) in the mixture having c which is at least 3, of minus 4 or at least 5 or at least 6.

13. Composition comprising: a) at least one alkoxylated cycloaliphatic epoxide of formula (I) according any one of claims 1 to 10 or a composition according to the claim 12; and b) at least one different cationically polymerizable compound of component a).

14. Composition according to claim 13, component b) comprising at minus a cationically polymerizable compound chosen from a epoxy functionalized compound other than component a), a oxetane, an oxolane, a cyclic acetal, a cyclic lactone, a thiirane, a thietane, a spiro-orthoester, a spiro-orthocarbonate, a vinyl ether, a vinyl ester, corresponding derivatives and corresponding mixtures.

15. Composition according to claim 13 or 14, component b) comprising at least one oxetane, in particular at least one oxeta according to the following formula (IX): [Chem.45] XD OR N / A" (IX) R4 being chosen from H, alkyl, aryl, alkylaryl, (meth)acryloyl, -CH, - oxetanyl-CH,-CH,, -L,-O-CH,-oxetanyl-CH,-CH; ; L, being a divalent linker, in particular -CH,-Ph-Ph-CH, or -CH, - Ph-CH,-[O0-CH,-Ph-CH>]= Ph being phenylene; celebrating 0 to 10.

16. | Composition according to claim 15, component b) comprising at minus one oxetane according to formula (IX), R4 being H, benzyl or -CH, - oxetanyl-CH,-CH. preferably R, being H or -CH,-oxetanyl-CH--CHz.

17. Composition according to any one of claims 13 to 16, the The weight ratio between component a) and component b) is 20: 80 to 80:20, in particular from 30:70 to 70:30, more particularly from 40:60 to 60:

40.

18. Composition according to any one of claims 13 to 17, the com- position comprising at least one cationic photoinitiator, in part- particularly an onium salt or a metallocene salt, more specifically a halonium salt, a sulfonium salt (e.g., a triaryl- salt sulfonium such as a triarylsulfonium hexafluoroantimonate salt), a sulfoxonium salt, a diazonium salt, a ferrocene salt, and corresponding mixtures.

19. Composition comprising: a) at least one alkoxylated cycloaliphatic epoxide of formula (I) according any one of claims 1 to 10 or a composition according to any one of claims 12 to 18; and c) at least one compound functionalized with (meth)acrylate, in particular a compound functionalized by (meth)acrylate bearing at least 2 or at minus 3 (meth)acrylate groups.

20. Composition according to any one of claims 13 to 19, the com- position including at least one free radical photoinitiator, in in particular a Norrish type I free radical photoinitiator, plus particularly a phosphine oxide or an acetophenone.

21. | Composition according to any one of claims 13 to 20, the com- position being a composition of ink, coating, agent of sealing, molding, or 3D printing, in particular an ink or a 3D printed composition.

22. A process for preparing a hardened product, comprising the hard- modification of the composition according to any one of the claims 13 to 21, in particular by exposing the composition to a radiation such as UV, near-UV, visible, infrared radiation and / or near-infrared or electron beam.

23. A method according to claim 22, the method being for the preparation of a 3D printed article and the process including the printing of a 3D article with composition according to any of the following specifications indications 11 to 19, in particular layer by layer or in a way continue.

24. Hardened product obtained by hardening the composition according to one of any of claims 13 to 21 or according to the method according to any one any of claims 22 and 23.

25. Hardened product according to claim 24, the hardened product being an ink, a coating, a sealant, an adhesive, a molded article or a 3D printed article, in particular a 3D printed article.

26. | Use of an alkoxylated cycloaliphatic epoxy according to one any of the claims | to 10, to obtain an ink, a re- clothing, a sealant, an adhesive, a molded article or a 3D printed article, in particular an ink or an article printed in 3D.