Polymeric Cycloaliphatic Epoxides

Abstract

The present invention relates to a compound represented by the following formula (I): TIFF2025501280000038.tif41170 (in the formula, each R1 and R2 is independently selected from H and Me; L is the residue of a polyol; each a is independently 2 to 4; Each b is independently 0 to 20, provided that at least one b is not 0; c is at least 3) The present invention also relates to a method for the preparation of compositions comprising the compounds of formula (I) and cured articles, in particular 3D printed articles.

Description

[Technical field]

[0001] The present invention relates to alkoxylated cycloaliphatic epoxides and methods for their preparation, compositions containing such alkoxylated cycloaliphatic epoxides, methods for curing such compositions, the cured products so obtained, and their use in products, such as, in particular, 3D printed articles. [Background technology]

[0002] In the field of light-curing 3D printing, there is a need for polymerizable products that exhibit high performance in terms of reduced toxicity, such as risk of mutagenesis, and features such as curing speed and resistance to surface degradation due to frictional contact (friction) of the cured resin.

[0003] The following difunctional cycloaliphatic epoxide, sold as UviCure® S105, gives a clear, hard, glossy coating. TIFF2025501280000002.tif62170

[0004] This epoxide generally provides good cure speed, but brittle mechanical properties may be observed.

[0005] Generally speaking, the viscosity profile of the resin may require effective management. For example, a longer "dwell time" may be required for 3D printing applications, resulting in initially thin epoxy resins flowing and spreading too much. Solvent resistance is also a feature to be optimized for existing resins, as is cure efficiency, e.g., cure speed maintained at lower lamp power for UV-curable compositions for existing epoxy resins. Summary of the Invention

[0006] The first aspect of the present invention is a compound represented by the following formula (I): TIFF2025501280000003.tif42170 (in the formula, each R1 and R2 is independently selected from H and Me; L is the residue of a polyol; each a is independently 2 to 4; Each b is independently 0 to 20, provided that at least one b is not 0; c is at least 3) is an alkoxylated alicyclic epoxide according to

[0007] Another aspect of the present invention is a process for the preparation of an alkoxylated cycloaliphatic epoxide of formula (I) as defined above, comprising the following steps: a) reacting a cyclohexene of formula (VI) with an alkoxylated polyol of formula (VII) to obtain an alkoxylated cyclohexene of formula (VIII); b) epoxidation of the alkoxylated cyclohexene of formula (VIII) to obtain an alkoxylated cycloaliphatic epoxide of formula (I); TIFF2025501280000004.tif121170 (in the formula, L, R1, R2, a, b and c are as defined above; X is OH, O-Alk or Cl; Alk is C1-C6 alkyl. The method includes:

[0008] A further aspect of the present invention relates to compositions comprising at least one alkoxylated cycloaliphatic epoxide according to formula (I) above.

[0009] Yet another aspect of the present invention relates to a method for the preparation of a cured product, in particular comprising curing such a composition by exposing it to radiation such as UV, near UV, visible, infrared and / or near infrared radiation or to an electron beam.

[0010] Yet another aspect of the invention relates to a cured product obtained by curing the composition according to the invention, which may be used as an ink, coating, sealant, adhesive, molded article or 3D printed article, in particular a 3D printed article. [Brief description of the drawings]

[0011] [Figure 1] 4 shows the results of tensile stress measurements on cured resin materials according to the present invention and cured resin materials not according to the present invention. [Diagram 2] 1 shows the results of measuring the storage modulus of a cured resin material according to the present invention and a cured resin material not according to the present invention. [Diagram 3] 4 shows the results of heat flow measurements on cured resin materials according to the invention and not according to the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] definition In this application, the term "comprise(s) a / an" means "comprise(s) one or more."

[0013] Unless otherwise stated, weight percentages in a compound or composition are expressed based on the weight of the compound or the weight of the composition, respectively.

[0014] The term "alkyl" refers to a group of the formula -C n H 2n+1 "C1-C20 alkyl" means an alkyl group having from 1 to 20 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl.

[0015] The term "alkylaryl" refers to an alkyl substituted with an aryl group. "C7-C20 alkylaryl" refers to an alkylaryl having 7 to 20 carbon atoms. An example of an alkylaryl group is benzyl (-CH2-phenyl).

[0016] The term "halogen" refers to an atom selected from Cl, Br and I.

[0017] The term "alkylene" refers to a group of the formula -C n H 2n - means a divalent saturated hydrocarbon radical. Alkylene may be straight or branched. "C1-C20 alkylene" means an alkylene having 1 to 20 carbon atoms. Examples of alkylene groups include ethylene (-CH2-CH2-) and 1,2-propylene (-CH2-CH(CH3)-).

[0018] The term "alkenyl" refers to a monovalent unsaturated hydrocarbon radical. Alkenyl may be straight-chained or branched. "C2-C20 alkenyl" refers to an alkenyl having 2 to 20 carbon atoms. Examples of alkenyl groups include vinyl (-CH=CH2) and allyl (-CH2-CH=CH2).

[0019] The term "cycloalkyl" refers to a monovalent saturated alicyclic hydrocarbon radical containing a ring. "C3-C8 cycloalkyl" refers to a cycloalkyl having from 3 to 8 carbon atoms. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and isobornyl.

[0020] The term "alkoxy" means a group of the formula -O-alkyl.

[0021] The term "aryl" refers to an aromatic hydrocarbon group. "C6-C12 aryl" refers to an aryl having 6 to 12 carbon atoms.

[0022] The term "heteroaryl" refers to an aromatic group containing heteroatoms such as O, N, S and mixtures thereof. "C5-C9 heteroaryl" refers to a heteroaryl having from 5 to 9 carbon atoms.

[0023] The term "polyol" means a compound containing at least two hydroxy groups.

[0024] The term "polyester" means a compound containing at least two ester bonds.

[0025] The term "polyether" means a compound containing at least two ether bonds.

[0026] The term "polycarbonate" means a compound containing at least two carbonate bonds.

[0027] The term "polyester polyol" means a polyester containing at least two hydroxy groups.

[0028] The term "polyether polyol" means a polyether containing at least two hydroxy groups.

[0029] The term "polycarbonate polyol" means a polycarbonate containing at least two hydroxy groups.

[0030] The term "hydrocarbon radical" means a radical consisting of carbon and hydrogen atoms. Unless otherwise stated, the hydrocarbon radical is not substituted or interrupted by any heteroatoms (O, N, or S). The hydrocarbon radical may be linear or branched, saturated or unsaturated, aliphatic, alicyclic, or aromatic.

[0031] The term "hydroxy" refers to an -OH group.

[0032] The term "amine" refers to -NR a R b R a and R b are independently H or C1-C6 alkyl. The term "primary amine" refers to the -NH2 group. The term "secondary amine" refers to the -NH2 group. a is C1-C6 alkyl -NHR a The term "tertiary amine" refers to the group -NR a R b R a and R bare independently C1 to C6 alkyl.

[0033] The term "carboxylic acid" refers to a -COOH group.

[0034] The term "isocyanate group" means a -N=C=O group.

[0035] The term "ester bond" means a -C(=O)-O- or -OC(=O)- bond.

[0036] The term "ether linkage" refers to an --O-- linkage.

[0037] The term "carbonate bond" means an --O--C(.dbd.O)--O-- bond.

[0038] The term "urethane or carbamate" refers to an --NH--C(.dbd.O)--O-- or --OC(.dbd.O)--NH-- bond.

[0039] The term "amide bond" means a -C(=O)-NH- or -NH-C(=O)- bond.

[0040] The term "urea bond" means a -NH-C(=O)-NH- bond.

[0041] The term "polyisocyanate" means a compound that contains at least two isocyanate groups.

[0042] The term "aliphatic" refers to a non-aromatic acyclic compound. It may be linear or branched, saturated or unsaturated. It may be substituted with one or more groups selected from, for example, alkyl, hydroxy, halogen (Br, Cl, I), isocyanate, carbonyl, amine, carboxylic acid, -C(=O)-OR', -C(=O)-OC(=O)-R', where each R' is independently a C1-C6 alkyl. It may contain one or more bonds selected from ether, ester, amide, urethane, urea, and combinations thereof.

[0043] The term "acyclic" means a compound that does not contain any rings.

[0044] The term "alicyclic" refers to a non-aromatic cyclic compound, which may be substituted with one or more groups as defined for the term "aliphatic". It may contain one or more bonds as defined for the term "aliphatic".

[0045] The term "aromatic" refers to a compound containing an aromatic ring, which obeys Hückel's aromaticity rules, in particular a compound containing a phenyl group. It may be substituted by one or more groups as defined for the term "aliphatic". It may contain one or more bonds as defined for the term "aliphatic".

[0046] The term "saturated" refers to a compound that does not contain either double or triple carbon-carbon bonds.

[0047] The term "unsaturated" refers to compounds that contain double or triple carbon-carbon bonds, especially double carbon-carbon bonds.

[0048] The term "optionally substituted" refers to a compound substituted with one or more groups selected from alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, alkylaryl, haloalkyl, hydroxy, halogen, isocyanate, nitrile, amine, amide, carboxylic acid, -C(=O)-R'-C(=O)-OR', -C(=O)NH-R', -NH-C(=O)R', -OC(=O)-NH-R', -NH-C(=O)-O-R', -C(=O)-OC(=O)-R' and -SO2-NH-R', where each R' is independently an optionally substituted group selected from alkyl, aryl and alkylaryl.

[0049] The term "3D article" means a three-dimensional object obtained by 3D printing.

[0050] Compounds of the Invention and Methods for Their Synthesis Epoxy resins can be polymerized, for example, by cationic polymerization, and as mentioned above, cycloaliphatic epoxides, such as those based on cyclohexane rings, are known. In the present invention, the polyol core is linked to a C6 cycloaliphatic group bearing multiple epoxides via an ethyleneoxy (-CH2-CH2-O-), 1,2-propyleneoxy (-CH2-CH(CH3)-O-) or similar spacer.

[0051] Thus, in one aspect, the present invention provides a compound of formula (I): TIFF2025501280000005.tif42170 (in the formula, each R1 and R2 is independently selected from H and Me; L is the residue of a polyol; each a is independently 2 to 4; Each b is independently 0 to 20, provided that at least one b is not 0; c is at least 3) This relates to alkoxylated alicyclic epoxides according to the invention.

[0052] In particular, the value of c may be 3, 4, 5, 6, 7, 8, 9 or 10. In one embodiment, c may be equal to 3. In another embodiment, c may be greater than 3, for example, c may be between 4 and 10.

[0053] Thus, prior to curing, the alkoxylated cycloaliphatic epoxide compounds of the present invention contain multiple epoxide groups that are separated from one another and available for curing.

[0054] In a preferred but non-limiting illustrative example of an alkoxylated cycloaliphatic epoxide of the present invention, the alkoxylated cycloaliphatic epoxide has the following structure: TIFF2025501280000006.tif144170.

[0055] The preferred hexafunctional molecule is derived from (HO-CH2-)3C-CH2)2O. The latter polyol is commercially available as polyol R6405 from Perstorp AB and has the systematic name poly(oxy-1,2-ethanediyl), α-hydro-ω-hydroxy-, ether (6:1) with 2,2'-[oxybis(methylene)]bis[2-(hydroxymethyl)-1,3-propanediol]. Its CAS number is 50977-32-7.

[0056] Generally speaking, among the preferred alkoxylated alicyclic epoxides of the present invention, those included in the above general formula (I) are those where a is 2, and the alkoxylated alicyclic epoxides are represented by the following formula (Ia): TIFF2025501280000007.tif36170 (in the formula, L, b and c are as defined in claim 1; Each R1 and R'1 is independently selected from H and Me. This is due to.

[0057] Another type of preferred alkoxylated alicyclic epoxide of the present invention falling within the scope of general formula (I) above is shown where a is 4, and R1 and R2 are both H.

[0058] In preferred alkoxylated cycloaliphatic epoxides of the invention, according to the different choices above for a, and for R1 and R'1, or R1 and R2, each b is independently 1 to 20, in particular 1 to 10, more in particular 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 at least 8, more in particular at least 10, even more in particular at least 12.

[0059] In preferred alkoxylated alicyclic epoxides of the present invention, c is 3-10, particularly 3-8, more particularly 4-6.

[0060] In preferred alkoxylated alicyclic epoxides of the present invention, c is 4 to 10, particularly 4 to 8, more particularly 4 to 6, and even more particularly c may be equal to 6. Alternatively, c may be equal to 3.

[0061] In preferred alkoxylated alicyclic epoxides of the present invention, c is 3 and L is of formula (II): TIFF2025501280000008.tif33170 (in the formula, R3 is selected from H, alkyl and alkoxy, in particular R3 is alkyl, more particularly R3 is ethyl; d, d' and d'' are independently 0 to 2, with the proviso that at least two of d, d' and d'' are not 0, and in particular d, d' and d'' are all 1 or d is 0 and d' and d'' are 1. It is a trivalent linker based on

[0062] In other preferred alkoxylated alicyclic epoxides of the present invention, c is 4 and L has the following formula (IIIa), (IIIb) or (IIIc): TIFF2025501280000009.tif61170 (in the formula, e, e', e'' and e''' are independently 0 to 2, with the proviso that at least three of e, e', e'' and e''' are not 0, and in particular, e, e', e'' and e'''' are all 1). is a tetravalent linker according to one of the following:

[0063] In other preferred alkoxylated alicyclic epoxides of the present invention, c is 5 and L is represented by the following formula (IV): Pentavalent linker from TIFF2025501280000010.tif19170.

[0064] In other preferred alkoxylated alicyclic epoxides of the present invention, c is 6 and L is represented by the following formula (Va), (Vb) or (Vc): Hexavalent linker from TIFF2025501280000011.tif65170.

[0065] In the process according to the invention, an esterification is carried out to form an ester of an alkoxylated polyol with a cyclohexene having a carboxylic acid, which is then reacted with an epoxidizing agent in an epoxidation step to convert the multiple cyclohexene C=C groups to epoxide groups.

[0066] Thus, in the process for the preparation of an alkoxylated cycloaliphatic epoxide of formula (I) of the invention as defined above, the process comprises the following steps: a) reacting a cyclohexene of formula (VI) with an alkoxylated polyol of formula (VII) to obtain an alkoxylated cyclohexene of formula (VIII); b) epoxidation of the alkoxylated cyclohexene of formula (VIII) to obtain an alkoxylated cycloaliphatic epoxide of formula (I) as defined above; TIFF2025501280000012.tif79170 (in the formula, L, R1, R2, a, b and c are as defined above for the alkoxylated alicyclic epoxide compounds of the present invention; X is OH, O-Alk or Cl; Alk is C1-C6 alkyl. Includes.

[0067] As mentioned above, the alkoxylated polyols of formula (VII) can be linked to form the esters (VIII) by direct esterification with 3-cyclohexene-1-carboxylic acid or via an intermediate such as the acid chloride cyclohex-3-ene-1-carbonyl chloride. The latter acid chloride can be obtained by reaction of 3-cyclohexene-1-carboxylic acid with agents such as thionyl chloride, phosphorus trichloride, phosphorus(V) oxychloride and oxalyl chloride.

[0068] The epoxidation step (b) may be carried out using peracids such as 3-chloroperbenzoic acid, peracetic acid, or other epoxidizing agents such as hydrogen peroxide, t-butyl hydroperoxide and sodium hypochlorite.

[0069] Compositions of the Invention The composition of the present invention comprises: 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). The present invention is not limited to compositions comprising:

[0070] Component b) may in particular be selected from the group consisting of oxetanes, oxolanes, cyclic acetals, cyclic lactones, thiiranes, thietanes, spiro orthoesters, spiro orthocarbonates, vinyl ethers, vinyl esters, derivatives thereof and mixtures thereof. Oxetanes are particularly preferred examples of component (b). Component (b), such as oxetanes, can act as reactive diluents and can provide high cure rates and high solvent resistance in compositions having at least one alkoxylated cycloaliphatic epoxide of formula (a) (I).

[0071] The weight ratio between components a) and b) may be from 20:80 to 80:20, in particular from 30:70 to 70:30, more in particular from 40:60 to 60:40.

[0072] In this first type of preferred composition according to the present invention comprising a) at least one alkoxylated cycloaliphatic epoxide of formula (I) as defined above, and b) at least one cationically polymerizable compound, such as an oxetane, the composition preferably comprises at least one cationic photoinitiator, in particular an onium salt or a metallocene salt, more in particular 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 mixtures thereof.

[0073] Cationic 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 a polyol c) The composition of the invention may comprise a mixture of cationically polymerizable compounds b) and c).

[0074] When the composition includes a cationically polymerizable compound, the composition may be a hybrid free radical / cationic composition, ie, a composition that is cured by both free radical and cationic polymerization.

[0075] The term "cationically polymerizable compound" refers to a compound containing a polymerizable functional group, such as a carbon-carbon double bond substituted with a heterocyclic group or an electron donating group, that polymerizes via a cationic mechanism in which a cationic initiator forms a Bronsted or Lewis acid species that binds to the cationically polymerizable compound and then becomes reactive, resulting in chain growth by reaction with another cationically polymerizable compound.

[0076] The cationically polymerizable compound may be selected from epoxy-functionalized compounds, oxetanes, oxolanes, cyclic acetals, cyclic lactones, thiiranes, thietanes, spiroorthoesters, ethylenically unsaturated compounds other than (meth)acrylates, derivatives thereof and mixtures thereof.

[0077] In a preferred embodiment, the cationically polymerizable compound may be selected from epoxy-functionalized compounds, oxetanes, and mixtures thereof. In particular, oxetanes are preferred cationically polymerizable compounds in the compositions of the present invention.

[0078] Suitable epoxy-functionalized compounds capable of cationically polymerizing are glycidyl ethers, particularly mono-, di-, tri- and polyglycidyl ether compounds, as well as cycloaliphatic epoxy compounds, including those containing the residue of a carboxylic acid, such as an alkyl carboxylic acid residue, an alkylcycloalkyl carboxylic acid residue and an alkylene dicarboxylic acid residue. For example, epoxy-functionalized compounds 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, epoxy novolac resins, 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, 4-vinylcyclohexene dioxide, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl)ether of ethylene glycol, ethylene bis(3,4-epoxycyclohexanecarboxylate), epoxy hexahydrodioctyl phthalate, epoxy hexahydro-di-2-ethylhexyl phthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycol The polyglycidyl ether may be a polyglycidyl ether of a polyether polyol obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol such as glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol, propylene glycol, or glycerol, a diglycidyl ester of an aliphatic long-chain dibasic acid, a monoglycidyl ether of an aliphatic higher alcohol, a monoglycidyl ether of a phenol, cresol, butylphenol, or polyether alcohol obtained by adding an alkylene oxide to these compounds, a glycidyl ester of a higher fatty acid, an epoxidized soybean oil, an epoxy butyl stearic acid, an epoxy octyl stearic acid, an epoxidized linseed oil, or an epoxidized polybutadiene.

[0079] Suitable oxetanes capable of cationically polymerizing include trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-ethyl-3-phenoxymethyloxetane, and bis(3-ethyl-3-methyloxy)butane, 3-ethyl-3-oxetanemethanol.

[0080] Suitable cationically polymerizable oxolanes include tetrahydrofuran and 2,3-dimethyltetrahydrofuran.

[0081] Suitable cationically polymerizable cyclic acetals include trioxane, 1,3-dioxolane, and 1,3,6-trioxacyclooctane.

[0082] Suitable cationically polymerizable cyclic lactones include β-propiolactone and ε-caprolactone.

[0083] Suitable cationically polymerizable thiiranes include ethylene sulfide, 1,2-propylene sulfide, and thioepichlorohydrin.

[0084] Suitable cationically polymerizable thietanes include 3,3-dimethylthietan.

[0085] Suitable cationically polymerizable spiroorthoesters are compounds obtainable by reaction of an epoxy compound with a lactone.

[0086] Suitable ethylenically unsaturated compounds other than cationically polymerizable (meth)acrylates include vinyl ethers such as ethylene glycol divinyl ether, triethylene glycol divinyl ether, and trimethylolpropane trivinyl ether.

[0087] In a preferred embodiment, component b) comprises at least one oxetane, in particular a compound of the following formula (IX): TIFF2025501280000013.tif23170, where R4 is selected from H, alkyl, aryl, alkylaryl, (meth)acryloyl, -CH2-oxetanyl-CH2-CH3, -L1-O-CH2-oxetanyl-CH2-CH3; L1 is a divalent linker, in particular -CH2-Ph-Ph-CH2 or -CH2-Ph-CH2-[O-CH2-Ph-CH2] f - and Ph is phenylene; f is 0 to 10) The compound contains at least one oxetane according to the formula:

[0088] In particular, component b) is a compound of formula (IX) in which R4 is H, benzyl or -CH2-oxetanyl-CH2-CH3, Preferably, R4 may contain at least one oxetane, such as H or -CH2-oxetanyl-CH2-CH3.

[0089] The curable composition of the present invention may contain 10 to 80% by weight, particularly 15 to 75% by weight, and more particularly 20 to 70% by weight of a cationically polymerizable compound, based on the total weight of the curable composition.

[0090] Hybrid free radical / cationic compositions In a further preferred composition option of the present invention, the composition may be cured by both free radical polymerization and cationic polymerization. In a preferred embodiment, using (a) an alkoxylated cycloaliphatic epoxide according to formula (I) cited above, and optionally further (b) an oxetane on the one hand, and a monomer capable of participating in C=C addition polymerization on the other hand, such as a (meth)acrylate group-containing compound, typically results in an interpenetrating (entangled) network of separate polyepoxides and poly(meth)acrylates without covalent bonds between them. However, it may be advantageous to have a composition containing a monomer component that contains both an epoxide / oxetane group and a (meth)acrylate group. In that case, a covalent bond is formed between the two networks, which may provide further improvements in physical properties. Examples or such commercially available compounds include UViCure S170 (3-ethyl-3-(methacryloyloxy)methyloxetane) and glycidyl (meth)acrylate.

[0091] Thus, in a preferred composition of the second type of the present invention, the composition comprises: a) at least one alkoxylated cycloaliphatic epoxide of formula (I) above, or a composition comprising at least one alkoxylated cycloaliphatic epoxide of formula (I) and b) at least one cationically polymerizable compound other than component a), in particular an oxetane, oxolane, cyclic acetal, cyclic lactone, thiiranes, thietanes, spiroorthoesters, spiroorthocarbonates, vinyl ethers, vinyl esters, derivatives thereof and mixtures thereof, and c) at least one (meth)acrylate-functionalized compound, in particular a (meth)acrylate-functionalized compound having at least two or at least three (meth)acrylate groups.

[0092] In this second type of preferred composition of the invention, the cationically curable oxetane is an optional component, but may be used in the preferred embodiment. Other optional components are cationically curable vinyl ethers, polyols or polyfunctional alcohols, which may function as chain transfer agents.

[0093] As used herein, the term "(meth)acrylate-functionalized compound" refers to a monomer that contains a (meth)acrylate group, particularly an acrylate group. The term "(meth)acrylate-functionalized compound" herein includes compounds that contain more than one (meth)acrylate group, for example, 2, 3, 4, 5 or 6 (meth)acrylate groups, and are generally referred to as "oligomers" that contain (meth)acrylate groups. The term "(meth)acrylate group" includes acrylate groups (-O-CO-CH=CH2) and methacrylate groups (-O-CO-C(CH3)=CH2).

[0094] Preferably, the (meth)acrylate functionalized compound does not contain any amino groups.

[0095] As used herein, the term "amino group" refers to a primary, secondary, or tertiary amine group, but does not include any other type of nitrogen-containing group, such as an amide, carbamate (urethane), urea, or sulfonamide group.

[0096] The (meth)acrylate functionalized compound may have a molecular weight of less than 600 g / mol, in particular from 100 to 550 g / mol, more in particular from 200 to 500 g / mol.

[0097] The (meth)acrylate functionalized compound may have 1 to 6 (meth)acrylate groups, particularly 1 to 5 (meth)acrylate groups, and more particularly 1 to 3 (meth)acrylate groups.

[0098] The (meth)acrylate-functionalized compound may comprise a mixture of (meth)acrylate-functionalized monomers having different functionalities. For example, the (meth)acrylate-functionalized compound may comprise a mixture of (meth)acrylate-functionalized compounds containing a single acrylate or methacrylate group per molecule (referred to herein as "mono(meth)acrylate-functionalized compounds") and (meth)acrylate-functionalized compounds containing two or more, preferably two or three, acrylate and / or methacrylate groups per molecule. In another example, the (meth)acrylate-functionalized compound may comprise a mixture of at least one mono(meth)acrylate-functionalized compound and at least one (meth)acrylate-functionalized compound containing three or more, preferably four or more, (meth)acrylate groups per molecule.

[0099] The (meth)acrylate-functionalized compound may include a mono(meth)acrylate-functionalized compound, which may advantageously function as a reactive diluent and reduce the viscosity of the composition of the present invention.

[0100] Examples of suitable mono(meth)acrylate functionalized compounds include, but are not limited to, mono-(meth)acrylate esters of aliphatic alcohols, where the aliphatic alcohol may be linear, branched, or alicyclic, and may be a mono-, di-, or polyalcohol, provided that only one hydroxyl group is esterified with (meth)acrylic acid; mono-(meth)acrylate esters of aromatic alcohols (e.g., phenols, including alkylated phenols); mono-(meth)acrylate esters of alkylaryl alcohols (e.g., benzyl alcohol); oligomers and copolymers of diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol, and the like. mono-(meth)acrylate esters of monoalkyl ethers of glycols and oligoglycols; mono-(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) fatty alcohols, where the fatty alcohol may be linear, branched or alicyclic and may be a mono-, di- or polyalcohol, provided that only one hydroxyl group of the alkoxylated fatty alcohol is esterified with (meth)acrylic acid; mono-(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (e.g., alkoxylated phenols); and caprolactone mono(meth)acrylate.

[0101] The following compounds are illustrative of mono(meth)acrylate functionalized compounds suitable for use in the curable 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; trimethylol (meth)acrylate; Decyl (meth)acrylate;Tetradecyl (meth)acrylate;Hexadecyl (meth)acrylate;2-Hydroxyethyl (meth)acrylate;2- and 3-Hydroxypropyl (meth)acrylate;2-Methoxyethyl (meth)acrylate;2-Ethoxyethyl (meth)acrylate;2- and 3-Ethoxypropyl (meth)acrylate;Tetrahydrofurfuryl (meth)acrylate;Alkoxylated tetrahydrofurfuryl (meth)acrylate;2-(2-Ethoxyethoxy)ethyl (meth)acrylate acrylate;cyclohexyl (meth)acrylate;glycidyl (meth)acrylate;isodecyl (meth)acrylate;lauryl (meth)acrylate;2-phenoxyethyl (meth)acrylate;alkoxylated phenol (meth)acrylate;alkoxylated nonylphenol (meth)acrylate;cyclic trimethylolpropane formal (meth)acrylate;isobornyl (meth)acrylate;tricyclodecane methanol (meth)acrylate;tert-butyl cyclohexanol (meth)acrylate; Trimethylcyclohexanol (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; diethylene glycol monoethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; ethoxylated lauryl (meth)acrylate; methoxypolyethylene glycol (meth)acrylate; 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate; and combinations thereof.

[0102] The (meth)acrylate-functionalized compound may include a (meth)acrylate-functionalized compound that contains two or more (meth)acrylate groups per molecule.

[0103] Examples of suitable (meth)acrylate-functionalized compounds containing two or more (meth)acrylate groups per molecule include acrylate and methacrylate esters of polyhydric alcohols (organic compounds containing two or more, e.g., 2 to 6, hydroxyl groups per molecule). Specific examples of suitable polyhydric alcohols include C 2~20 Alkylene glycol (carbon chain may be branched, C 2~10Glycols having alkylene groups may be preferred; for example, 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, 1,8-octanediol, 1,9-nonanediol, 1,12-dodecanediol, cyclohexane-1,4-dimethanol, bisphenols and hydrogenated bisphenols and their alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives), diethylene glycol, glycerin, alkoxylated glycerin, triethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, alkoxylated trimethylolpropane, ditrimethylolpropane, alkoxylated glycerin, dipropylene glycol, tri ... alkoxylated ditrimethylolpropane, pentaerythritol, alkoxylated pentaerythritol, dipentaerythritol, alkoxylated dipentaerythritol, cyclohexanediol, alkoxylated cyclohexanediol, cyclohexanedimethanol, alkoxylated cyclohexanedimethanol, norbornene dimethanol, alkoxylated norbornene dimethanol, norbornane dimethanol, alkoxylated norbornane dimethanol, polyols containing aromatic rings, cyclohexane-1,4-dimethanol ethylene oxide adducts, bis-phenol ethylene oxide adducts, hydrogenated bisphenol ethylene oxide adducts, bisphenol propylene oxide adducts, hydrogenated bisphenol propylene oxide adducts, cyclohexane-1,4-dimethanol propylene oxide adducts, 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, etc.) so long as they contain at least two (meth)acrylate functional groups per molecule. As used herein, the term "alkoxylated" refers to compounds that contain one or more oxyalkylene moieties (e.g., oxyethylene and / or oxypropylene moieties).The oxyalkylene moiety corresponds to the general structure -RO-, where R is a divalent aliphatic moiety such as -CH2CH2- or -CH2CH(CH3)-. For example, the alkoxylated compound may contain from 1 to 30 oxyalkylene moieties per molecule.

[0104] Exemplary (meth)acrylate functionalized compounds containing two or more (meth)acrylate groups per molecule 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. Acrylates;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;1,4-Butanediol di(meth)acrylate;1,5-Pentanediol di(meth)acrylate;1,6-Hexanediol di(meth)acrylate;1 ,8-Octanediol di(meth)acrylate;1,9-Nonanediol di(meth)acrylate;1,10-Nonanediol di(meth)acrylate;1,12-Dodecanediol di(meth)acrylate;Neopentyl glycol di(meth)acrylate;2-Methyl-2,4-pentanediol di(meth)acrylate;Polybutadiene di(meth)acrylate;Cyclohexane-1,4-dimethanol di(meth)acrylate;Tricyclodecane dimethanol di(meth)acrylate;Metal di(meth)acrylates;Modified metal di(meth)acrylates Acrylates;Glyceryl di(meth)acrylate;Glyceryl tri(meth)acrylate;Trimethylolethane tri(meth)acrylate;Trimethylolethane di(meth)acrylate;Trimethylolpropane tri(meth)acrylate;Trimethylolpropane di(meth)acrylate;Pentaerythritol di(meth)acrylate;Pentaerythritol tri(meth)acrylate;Pentaerythritol tetra(meth)acrylate;Di(trimethylolpropane) diacrylate;Di(trimethylolpropane) triacrylate;Di(trimethylolpropane) tetraacrylate, sorbitol penta(meth)acrylate; di(pentaerythritol) tetraacrylate; di(pentaerythritol) pentaacrylate; di(pentaerythritol) hexa(meth)acrylate; tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate; and its alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives; and combinations thereof.

[0105] The curable composition of the present invention may comprise 10 to 80 wt. %, particularly 15 to 75 wt. %, more particularly 20 to 70 wt. % of the (meth)acrylate-functionalized compound, based on the total weight of the curable composition.

[0106] The (meth)acrylate-functionalized compound in oligomeric form may be selected to enhance, among other attributes, the flexibility, strength and / or modulus of the cured polymer prepared using the curable composition of the present invention, where the (meth)acrylate-functionalized oligomer may have up to 18 (meth)acrylate groups, in particular 2 to 6 (meth)acrylate groups, more in particular 2 to 6 acrylate groups. The (meth)acrylate-functionalized compound in oligomeric form may have a number average molecular weight of 600 g / mol or more, in particular 800 to 15,000 g / mol, more in particular 1,000 to 5,000 g / mol.

[0107] In particular, the (meth)acrylate-functionalized compound in the form of an oligomer may be selected from the group consisting of (meth)acrylate-functionalized epoxy oligomers (sometimes referred to as "epoxy (meth)acrylate oligomers"), (meth)acrylate-functionalized polyether oligomers (sometimes referred to as "polyether (meth)acrylate oligomers"), (meth)acrylate-functionalized polydiene oligomers (sometimes referred to as "polydiene (meth)acrylate oligomers"), (meth)acrylate-functionalized polycarbonate oligomers (sometimes referred to as "polycarbonate (meth)acrylate oligomers"), and (meth)acrylate-functionalized polyester oligomers (sometimes referred to as "polyester (meth)acrylate oligomers"), and mixtures thereof.

[0108] Exemplary polyester (meth)acrylate oligomers include the reaction products of acrylic acid or methacrylic acid or mixtures or synthetic equivalents thereof with hydroxyl-terminated polyester polyols. The reaction process may be carried out such that all or essentially all of the hydroxyl groups of the polyester polyol are (meth)acrylated, especially when the polyester polyol is difunctional. The polyester polyols can be made by the polycondensation reaction of polyhydroxy-functional components (especially diols) and polycarboxylic acid-functional compounds (especially dicarboxylic acids and anhydrides). The polyhydroxyl-functional and polycarboxylic acid-functional components can each have a linear, branched, alicyclic or aromatic structure and can be used individually or as a mixture.

[0109] Examples of suitable epoxy (meth)acrylates include the reaction products of acrylic acid or methacrylic acid or mixtures thereof with epoxy resins (polyglycidyl ethers or esters). Epoxy resins include, in particular, 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, epoxy novolac resins, 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, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl)ether of ethylene glycol, ethylene bis(3,4-epoxycyclohexanecarboxylate), 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether The glycidyl ether may be selected from polyglycidyl ethers of polyether polyols obtained by addition of one or more alkylene oxides to aliphatic polyhydric alcohols, such as ethylene glycol, propylene glycol, and glycerol, diglycidyl esters of aliphatic long-chain dibasic acids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of polyether alcohols obtained by addition of phenol, cresol, butylphenol, or alkylene oxides to these compounds, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy butyl stearic acid, epoxy octyl stearic acid, epoxidized linseed oil, epoxidized polybutadiene, etc.

[0110] Suitable polyether (meth)acrylate oligomers include, but are not limited to, the condensation reaction products of acrylic or methacrylic acid or synthetic equivalents or mixtures thereof with a polyetherol, which is a polyether polyol (e.g., polyethylene glycol, polypropylene glycol, or polytetramethylene glycol). Suitable polyetherols can be linear or branched materials containing ether linkages and terminal hydroxy groups. Polyetherols can be prepared by ring-opening polymerization of cyclic ethers such as tetrahydrofuran or alkylene oxides (e.g., ethylene oxide and / or propylene oxide) with starter molecules. Suitable starter molecules include water, polyhydroxyl-functional materials, and polyester polyols.

[0111] Suitable acrylic (meth)acrylate oligomers (sometimes referred to in the art as "acrylic oligomers") include oligomers that may be described as materials having an oligomeric acrylic backbone functionalized with one or more (meth)acrylate groups (which may be at the terminus of the oligomer or pendant to the acrylic backbone). The acrylic backbone may be a homopolymer, random copolymer, or block copolymer composed of repeating units of acrylic monomers. The acrylic monomers may be any monomeric (meth)acrylate, such as C1-C6 alkyl (meth)acrylates, as well as functionalized (meth)acrylates, such as (meth)acrylates with hydroxyl, carboxylic acid, and / or epoxy groups. Acrylic (meth)acrylate oligomers may be prepared using any procedure known in the art, such as by oligomerizing monomers, at least a portion of which are functionalized with hydroxy, carboxylic acid and / or epoxy groups (e.g., hydroxyalkyl (meth)acrylates, (meth)acrylic acid, glycidyl (meth)acrylate) to obtain a functionalized oligomeric intermediate, which is then reacted with one or more (meth)acrylate-containing reactants to introduce the desired (meth)acrylate functionality.

[0112] The curable composition of the present invention may comprise 10 to 80 wt. %, particularly 15 to 75 wt. %, more particularly 20 to 70 wt. %, of the (meth)acrylate-functionalized compound, based on the total weight of the curable composition.

[0113] Non-limiting types of radical photoinitiators suitable for use in the curable compositions of the present invention include, for example, benzoin, benzoin ethers, acetophenone, α-hydroxyacetophenone, benzil, benzil ketals, anthraquinones, phosphine oxides, acylphosphine oxides, α-hydroxyketones, phenylglyoxylates, α-aminoketones, benzophenones, thioxanthones, xanthones, acridine derivatives, phenazene derivatives, quinoxaline derivatives, triazine compounds, benzoyl formates, aromatic oximes, metallocenes, acylsilyl or acylgermanyl compounds, camphorquinone, polymeric derivatives thereof, and mixtures thereof.

[0114] Examples of suitable radical photoinitiators include, but are not limited to, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-benzylanthraquinone, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, benzil, benzoin, benzoin ether, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, alpha-methylbenzoin, alpha-phenylbenzoin, Michler's ketone, acetophenone, 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-hydroxyketo (α-hydroxy keto), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzil dimethyl ketal, 2,2-dimethoxy-1,2-diphenylethanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1,2-hydroxy-2-methyl-1-phenyl-propane, oligomeric α-hydroxyketones, benzoylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, anisoin, anthraquinone, anthraquinone -2-Sulfonic acid, sodium salt monohydrate, (benzene)tricarbonylchromium, benzil, benzoin isobutyl ether, benzophenone / 1-hydroxycyclohexyl phenyl ketone, 50 / 50 blend, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4-benzoylbiphenyl, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, camphorquinone, 2-chlorothioxanthen-9-one, dibenzosuberenone, 4,4'-dihydroxybenzophenone, 2,2-Dimethoxy-2-phenylacetophenone, 4-(dimethylamino)benzophenone, 4,4'-dimethylbenzyl, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide / 2-hydroxy-2-methylpropiophenone, 50 / 50 blend, 4'-ethoxyacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ferrocene, 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3-hydroxybenzof phenone, 4-hydroxybenzophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-methylbenzophenone, 3-methylbenzophenone, methylbenzoyl formate, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, phenanthrenequinone, 4'-phenoxyacetophenone, (cumene)cyclopentadienyliron(ii) hexafluorophosphate, 9,10-diethoxy and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, thioxanthen-9-one and combinations thereof.

[0115] In the preferred compositions of the present invention, radical photoinitiators with Norrish Type I activity, such as phosphine oxides, can be used. The acetophenone family photoinitiators are also a preferred choice in hybrid systems containing both cationically polymerizable compounds including alkoxylated cycloaliphatic epoxides of formula (I) and radically polymerizable (meth)acrylate-functionalized compounds.

[0116] The amount of photoinitiator may be 0.01-5 wt%, 0.02-3 wt%, 0.05-2 wt%, 0.1-1.5 wt%, or 0.2-1 wt%, based on the total weight of the curable composition. The amount of photoinitiator may be 0.01-10 wt%, 0.1-9 wt%, 0.2-8 wt%, 0.5-7 wt%, or 1-6 wt%, based on the total weight of the curable composition.

[0117] Additives The curable composition of the present invention may comprise an additive. The curable composition may comprise a mixture of additives.

[0118] In particular, the additives may be selected from sensitizers, amine synergists, antioxidants / light stabilizers, light blockers / absorbers, polymerization inhibitors, foam inhibitors, flow or leveling agents, colorants, pigments, dispersants (wetting agents, surfactants), slip additives, fillers, chain transfer agents, thixotropic agents, matting agents, impact modifiers, waxes, mixtures thereof, and any other additive conventionally used in coatings, sealants, adhesives, molding, 3D printing or ink technology.

[0119] The curable composition may include a sensitizer.

[0120] Sensitizers can be introduced into the curable compositions of the present invention to extend the sensitivity of the photoinitiator to longer wavelengths, for example, the sensitizer can absorb light at a longer or shorter wavelength than the photoinitiator, transfer the energy to the photoinitiator, and return to its ground state.

[0121] Examples of suitable sensitizers include anthracene and carbazole.

[0122] The concentration of the sensitizer in the curable composition will vary depending on the photoinitiator used. Typically, however, the curable composition is formulated to contain from 0 to 5 weight percent, particularly from 0.1 to 3 weight percent, more particularly from 0.5 to 2 weight percent of the sensitizer, based on the total weight of the curable composition.

[0123] The curable composition may include a chain transfer agent.

[0124] Chain transfer agents can be introduced into the curable compositions of the present invention to increase the cure rate. In particular, the chain transfer agent can be a polyol. Polythiols or polyamines can slow down the cationic cure and are not a preferred choice in the present invention.

[0125] The curable composition may include a stabilizer.

[0126] Stabilizers can be introduced into the curable compositions of the present invention to provide sufficient storage stability and shelf life. Advantageously, one or more such stabilizers are present at each stage of the process used to prepare the curable composition to protect against undesired reactions during processing of the ethylenically unsaturated components of the curable composition. As used herein, the term "stabilizer" means a compound or substance that retards or prevents reaction or curing of actinic radiation-curable functional groups present in the composition in the absence of actinic radiation. However, it will be advantageous to select the amount and type of stabilizer such that the composition remains curable when exposed to actinic radiation (i.e., the stabilizer does not prevent radiation curing of the composition). Typically, effective stabilizers for the purposes of the present invention are classified as free radical stabilizers (i.e., stabilizers that function by inhibiting free radical reactions).

[0127] Any of the stabilizers known in the art related to (meth)acrylate functionalized compounds can be utilized in the present invention. Quinones represent a particularly preferred class of stabilizers that can be used in the context of the present invention. As used herein, the term "quinone" includes both quinones and hydroquinones, and their ethers, such as monoalkyl, monoaryl, monoaralkyl, and bis(hydroxyalkyl) ethers of hydroquinone. Hydroquinone monomethyl ether is one example of a suitable stabilizer that can be utilized. Other stabilizers known in the art, such as BHT and derivatives, phosphite compounds, phenothiazine (PTZ), triphenylantimony, and tin(II) salts can also be used.

[0128] The concentration of stabilizer in the curable composition varies depending on the particular stabilizer or combination of stabilizers selected for use, as well as the degree of stabilization desired and the susceptibility of the components in the curable composition to degradation in the absence of the stabilizer. Typically, however, the curable composition is formulated to contain 5 to 5000 ppm of stabilizer. According to certain embodiments of the present invention, the reaction mixture in each stage of the method used to make the curable composition contains at least some stabilizer, for example at least 10 ppm of stabilizer.

[0129] The curable composition may also include a light blocker (sometimes called a light absorber).

[0130] The introduction of a light blocker is particularly advantageous when the curable composition is used as a resin in a three-dimensional printing process involving photocuring of the curable composition. The light blocker may be any such substance known in the art of three-dimensional printing, including, for example, non-reactive pigments and dyes. The light blocker may be, for example, a visible light blocker or a UV light blocker. Examples of suitable light blockers include, but are not limited to, titanium dioxide, carbon black, and organic UV absorbers such as hydroxybenzophenone, hydroxyphenylbenzotriazole, oxanilide, hydroxyphenyltriazine, Sudan I, bromothymol blue, 2,2'-(2,5-thiophenediyl)bis(5-tert-butylbenzoxazole) (sold under the trade name "Benetex OB Plus") and benzotriazole UV absorbers.

[0131] The amount of light blocker can be varied as desired or appropriate for a particular application. Generally speaking, if the hardenable composition contains a light blocker, it is present in a concentration of 0.001 to 10% by weight based on the weight of the hardenable composition.

[0132] Advantageously, the curable compositions of the present invention may be formulated to be solvent-free, i.e., free of any non-reactive volatile materials (materials having a boiling point of 150° C. or less at atmospheric pressure). For example, the curable compositions of the present invention may contain little or no non-reactive solvent, for example less than 10% or less than 5% or less than 1% or even less than 0% non-reactive solvent, based on the total weight of the curable composition. As used herein, the term non-reactive solvent refers to a solvent that does not react when exposed to actinic radiation used to cure the curable compositions described herein.

[0133] According to another advantageous embodiment of the present invention, the curable composition is formulated so that it can be used as a one-component or one-part system, i.e., the curable composition is cured directly and is not combined with another component or second part (e.g., an amine monomer as defined in US 2017 / 0260418) before being cured.

[0134] curable composition In preferred embodiments of the invention, the curable compositions are 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 27 spindle (spindle speed typically varies between 20-200 rpm depending on viscosity). In advantageous embodiments of the invention, the viscosity of the curable composition is from 200 to 5,000 mPa.s (cP), or from 200 to 2,000 mPa.s (cP), or from 200 to 1,500 mPa.s (cP), or from 200 to 1,000 mPa.s (cP) at 25° C. The relatively high viscosity can provide satisfactory performance in applications where the curable composition is heated above 25° C., such as, for example, three-dimensional printing operations using machines with heated resin vats.

[0135] The curable compositions described herein may be compositions that are subjected to curing by free radical polymerization, cationic polymerization or other types of polymerization. In certain embodiments, the curable compositions are photocured (i.e., cured by exposure to actinic radiation such as light, especially visible or UV light).

[0136] The curable composition of the present invention may be an ink, a coating, a sealant, an adhesive, a molding, or a 3D printing composition, in particular a 3D printing composition.

[0137] End uses of the curable composition include, but are not limited to, inks, coatings, adhesives, additive manufacturing resins (e.g., 3D printing resins), molding resins, sealants, composites, antistatic layers, electronic applications, recyclable materials, smart materials that can detect and respond to stimuli, packaging materials, personal care articles, articles for use in agriculture, water or food processing, or animal husbandry, and biomedical materials.Thus, the curable composition of the present invention finds utility in the manufacture of biocompatible articles.Such articles may, for example, exhibit high biocompatibility, low cytotoxicity, and / or low extractability.

[0138] The composition according to the invention can in particular be used to obtain a cured, 3D printed article according to the following method.

[0139] Methods for preparation of cured 3D printed articles The method for preparing a cured product according to the present invention comprises curing the composition of the present invention. In particular, the composition can be cured by exposing the composition to radiation. More particularly, the composition can be cured by exposing the composition to UV, near UV, visible, infrared and / or near infrared radiation or electron beam.

[0140] Curing can be accelerated or facilitated by providing energy to the curable composition, for example by heating the curable composition. Thus, the cured product can be considered a reaction product of the curable composition formed by curing. The curable composition can be partially cured by exposure to actinic radiation, and further curing is achieved by heating the partially cured article. For example, an article (e.g., a 3D printed article) formed from the curable composition can be heated at a temperature of 40°C to 120°C for a period of 5 minutes to 12 hours.

[0141] Prior to curing, the curable composition may be applied to the substrate surface in any known conventional manner, for example, by spraying, knife coating, roller coating, casting, drum coating, dipping, and the like, and combinations thereof. Indirect application using a transfer process may be used. The substrate may be any commercially relevant substrate, such as a high surface energy substrate or a low surface energy substrate, such as a metal substrate or a plastic substrate, respectively. The substrate may include metal, paper, cardboard, glass, thermoplastics, such as polyolefins, polycarbonates, acrylonitrile butadiene styrene (ABS) and blends thereof, composites, wood, leather, and combinations thereof. When used as an adhesive, the curable composition may be placed between two substrates and then cured, whereby the cured composition can bond the substrates together to provide an adhesive article. The curable composition according to the present invention may be formed or cured in a bulk manner (e.g., the curable composition may be poured into a suitable mold and then cured).

[0142] The cured article obtained using the method of the present invention may be an ink, a coating, a sealant, an adhesive, a molded article or a 3D printed article.

[0143] In particular, the cured product may be a 3D printed article, which may be defined as an article obtained with a 3D printer using a computer-aided design (CAD) model or a digital 3D model.

[0144] The 3D printed article can be obtained in particular by using a method for preparing a 3D printed article, which comprises printing the 3D article with the composition of the present invention. In particular, the method may comprise printing the 3D article layer by layer or continuously.

[0145] Multiple layers of a curable composition according to the present invention can be applied to a substrate surface and the multiple layers may be cured simultaneously (e.g., by exposure to a single dose of radiation) or each layer may be cured sequentially before applying an additional layer of the curable composition.

[0146] The curable compositions described herein can be used as resins for three-dimensional printing applications. Three-dimensional (3D) printing, also known as additive manufacturing, is a process in which a 3D digital model is produced by deposition of a construction material. 3D printed objects are created by utilizing computer-aided design (CAD) data of an object through the successive construction of two-dimensional (2D) layers or slices corresponding to cross sections of the 3D object. Stereolithography (SL) is a type of additive manufacturing in which 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 electron beams. The most commonly applied energy sources are UV, near-UV, visible, infrared and / or near-infrared.

[0147] Non-limiting examples of suitable 3D printing processes include stereolithography (SLA); digital light processing (DLP); liquid crystal device (LCD); inkjet head (or multi-jet) printing; continuous liquid interface manufacturing (CLIP); extrusion-type processes such as continuous fiber 3D printing and cast-in-motion 3D printing; and volumetric 3D printing. The build method may be "layer-by-layer" or continuous. The liquid may be in a vat, for example, or deposited with inkjet or gel deposition.

[0148] Stereolithography and other photocurable 3D printing methods typically apply a low intensity light source to irradiate each layer of photocurable resin to form the desired article. As a result, the polymerization rate of the photocurable resin and the green strength of the printed article are important criteria for a particular photocurable resin to polymerize (cure) sufficiently when irradiated and have sufficient green strength to retain its integrity throughout the 3D printing process and post-processing.

[0149] The curable compositions of the present invention are particularly useful as 3D printing resin formulations, i.e., compositions intended for use in producing three-dimensional articles using 3D printing techniques. Such three-dimensional articles may be free-standing / self-supporting or may consist essentially of or consist of the cured compositions according to the present invention. The three-dimensional articles may also be composites comprising at least one component consisting essentially of or consisting of the aforementioned cured compositions, as well as at least one additional component composed of one or more materials other than such cured compositions (e.g., a metal component or a thermoplastic resin component or an inorganic filler or fiber reinforcement). The curable compositions of the present invention are particularly useful in digital light printing (DLP), although other types of three-dimensional (3D) printing methods can also be practiced using the curable compositions of the present invention (e.g., SLA, inkjet, multi-jet printing, piezoelectric printing, chemically cured extrusion, and gel deposition printing). The curable compositions of the present invention can be used in three-dimensional printing operations with another material that serves as a scaffold or support for the article formed from the curable compositions of the present invention.

[0150] Thus, the curable compositions of the present invention are useful for carrying out various kinds of three-dimensional fabrication or printing techniques, including methods in which the construction of a three-dimensional object is carried out stepwise or layer by layer. In such methods, layer formation can be carried out by solidification (curing) of the curable composition under the action of exposure to radiation, such as visible, UV or other actinic radiation. For example, a new layer can be formed on the top surface of a growing object or on the bottom surface of a growing object. The curable compositions of the present invention can also be advantageously used in methods for the manufacture of three-dimensional objects by additive manufacturing, which methods are carried out continuously. For example, the object may be produced from a liquid contact surface. Suitable methods of this kind are sometimes referred to in the art as "continuous liquid interface (or interface) production (or printing)" ("CLIP") methods. Such methods 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 entire disclosures of which are incorporated herein by reference in their entirety for all purposes.

[0151] When stereolithography is performed on an oxygen-permeable build window, the manufacture of articles using the curable composition according to the invention can be made possible in the 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 cured article as it is manufactured. In such a process, a curable composition is used whose cure (polymerization) is inhibited by the presence of molecular oxygen, and such inhibition is typically observed, for example, in curable compositions that can be cured by a free radical mechanism. 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 proceeds by projecting a continuous sequence of actinic (e.g., UV) images (which can be generated, for example, by a digital light processing imaging unit) through an oxygen-permeable actinic (e.g., UV-) transparent window below a bath of the curable composition maintained in liquid form. The liquid contact surface below the advancing (growing) article is maintained by the dead zone created above the window. The hardened article can be continuously withdrawn from the bath of hardenable composition above the dead zone and replenished by supplying additional amounts of hardenable composition into the bath to compensate for the amount of hardenable composition that is hardened and incorporated into the growing article.

[0152] In another embodiment, the curable composition is delivered by ejection from a print head rather than being delivered from a vat. This type of process is commonly referred to as inkjet or multi-jet 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 build surface substrate or a previously applied layer. 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 of different colors or different physical properties can be applied simultaneously to create 3D printed parts of various compositions. In typical usage, support material that is later removed during post-processing is deposited simultaneously with the composition used to create the desired 3D printed part. The print head may operate at temperatures from about 25°C to about 100°C. The viscosity of the curable composition is less than 30 mPa.s at the operating temperature of the print head.

[0153] The method for the preparation of a 3D printed article comprises the following steps: a) providing (e.g. coating) a surface with a first layer of a curable composition according to the present invention; b) at least partially curing the first layer to provide a cured first layer; c) providing (e.g., coating) a second layer of a curable composition on the cured first layer; d) at least partially curing the second layer to provide a cured second layer adhered to the cured first layer; e) repeating steps c) and d) as many times as desired to build a three-dimensional article. may include.

[0154] The curing step may be carried out by any suitable means, depending in some cases on the components present in the curable composition, but in certain embodiments of the present invention, curing is achieved by exposing the layer to be cured to an effective amount of radiation, particularly actinic radiation (e.g., electron beam radiation, UV radiation, visible light, etc.) The three-dimensional article formed may also be heated to effect thermal curing.

[0155] Thus, in various embodiments, the present invention provides a method for producing a pharmaceutical composition comprising the steps of: a) providing (e.g. coating) a surface with a first layer of a curable composition in liquid form according to the present invention; b) imagewise exposing the first layer to actinic radiation to form a first exposed imaged cross-section, the radiation having sufficient intensity and duration to cause at least partial curing of the layer in the exposed areas; c) providing (e.g., coating) an additional layer of a curable composition onto the previously exposed imaged cross-section; d) imagewise exposing the additional layer to actinic radiation to form an additional imaged cross section, the radiation having sufficient intensity and duration to cause at least partial curing of the additional layer in the exposed areas and to cause adhesion of the additional layer to the previously exposed imaged cross section; e) repeating steps c) and d) as many times as desired to build a three-dimensional article. may include.

[0156] Alternatively, the method for the preparation of a 3D printed article comprises the following steps: a) providing an optically transparent member having a carrier and a build surface, the carrier and the build surface defining a build area therebetween; b) filling the build area with the composition defined above; c) continuously or intermittently curing a portion of the composition in the build area according to the method defined above to form a cured composition; d) continuously or intermittently advancing the carrier away from the build surface to form a 3D printed article from the hardened composition. may include.

[0157] After the 3D article has been printed, it may undergo one or more post-treatment steps. The post-treatment steps may be selected from one or more of the steps following removal of any printed support structures, i.e., washing with water and / or organic solvents to remove residual resin, and post-curing using heat treatment and / or actinic radiation, either simultaneously or sequentially. Post-treatment steps may be used to convert the newly printed article into a finished functional article, ready for use in its intended application.

[0158] The cured products and 3D printed articles obtained using the methods of the present invention are described below.

[0159] Cured products, 3D printed products The cured product of the present invention can be obtained by curing the composition of the present invention or according to the method of the present invention.

[0160] The cured product may be an ink, a coating, a sealant, an adhesive, a molded article, or a 3D printed article. In particular, the cured product may be a 3D printed article.

[0161] use The alkoxylated cycloaliphatic epoxides of the present invention can be used to obtain inks, coatings, sealants, adhesives, molded articles or 3D printed articles, in particular 3D printed articles.

[0162] Although the embodiments have been described herein in a manner that enables a clear and concise specification to be written, it is intended, and will be understood, that the embodiments can be combined or separated in various ways without departing from the invention, and for example, it will be understood that all preferred features described herein are applicable to all aspects of the invention described herein.

[0163] In some embodiments, the invention can be construed to exclude any element or process step herein that does not materially affect the basic and novel characteristics of the invention. Further, in some embodiments, the invention can be construed to exclude any element or process step not specified herein.

[0164] Although the invention has been illustrated and described herein with reference to specific embodiments, it is not intended that the invention be limited to the details shown. Rather, various modifications in the details can be made without departing from the invention, within the scope and range of equivalents of the claims.

[0165] The invention is illustrated by the following non-limiting examples. EXAMPLES

[0166] material All materials used in the examples, unless otherwise stated, are readily available from standard commercial sources such as Sigma-Aldrich Company Ltd. and Tokyo Chemical Industry Ltd. Polyol R3215, Polyol 4360 and Polyol R6405 are available from Perstorp AB.

[0167] Example 1: Synthesis of triepoxide derived from Polyol R3215 (E1) Synthesis of cyclohex-3-ene-1-carbonyl chloride TIFF2025501280000014.tif261703-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.

[0168] To the stirred reaction mixture, thionyl chloride (456.0 g; 3.8329 mol) is added over 7 h. HCl and SO2 gases are evolved and the internal temperature is maintained at 15-22 °C during the addition. After the addition is complete, the reaction mixture is stirred under nitrogen at 20 °C for 18 h. The chloroform, DMF and unreacted thionyl chloride are then removed in vacuo. The pale yellow liquid product is then dried in vacuo to constant weight (30 mbar, 30 °C). Any precipitated white solid is removed by filtration. This gives cyclohex-3-ene-1-carbonyl chloride (451.5 g; 98.5% of theory). 1 H NMR (400 MHz, CDCl3): 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).

[0169] Synthesis of trialkenes derived from Polyol R3215 TIFF2025501280000015.tif59170 A reactor is charged with Polyol R3215 (100.0 g; 125.8 mmol) and the material is dried under reduced pressure (20 mbar, 75 °C, 3 h) with stirring. The reactor is then cooled to 20 °C, flushed with nitrogen and charged with dichloromethane (500 mL) and triethylamine (50.91 g, 503.1 mmol).

[0170] The clear solution is then cooled to 5° C. with ice water 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 warmed to 20° C. over 2 h and stirred at this temperature for an additional 18 h.

[0171] The reaction mixture is then poured into a solution of sodium bicarbonate (100 g) in water (1000 mL) and stirred rapidly for 6 hours at 20° C. The organic phase is separated and extracted with water (2×350 mL). The organic phase is collected and all volatiles are removed in vacuo.

[0172] The liquid product is then dried in vacuum (30 mbar, 50° C.) to constant weight, which gives the desired trialkene product (147.6 g). 1 H NMR(400 MHz, CDCl3):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).

[0173] Synthesis of triepoxide derived from Polyol R3215 (E1) TIFF2025501280000016.tif63170 Charge a reactor with Polyol R3215 trialken (147.6 g, 131.9 mmol) and add dichloromethane (1100 mL). Cool the reaction mixture to an internal temperature of 3 °C. Add 3-chloroperbenzoic acid (73.5% active, 99.1 g, 422.1 mmol) over 5 h with vigorous stirring while maintaining the internal temperature at 3-4 °C. Stir the cloudy mixture vigorously for 18 h and warm to 20 °C.

[0174] The reaction mass is then filtered and the white solid is washed with dichloromethane (2 x 50 mL). To the obtained filtrate is added a solution of sodium sulfite (50 g) in water (500 mL) and the biphasic mixture is stirred for 60 minutes. The mixture is phase separated and the organic phase is washed with a solution of sodium bicarbonate (83.6 g) in water (750 mL) and then with water (2 x 500 mL).

[0175] The mixture is allowed to phase separate for 18 hours, the organic phase is collected, dried over sodium sulfate (100 g) and filtered, the filtrate is concentrated in vacuo and the liquid product is then dried to constant weight (30 mbar, 35° C.).

[0176] This gives the desired triepoxide product E1 (141.5 g, 91.9% of theory). 1 H NMR(400 MHz, CDCl3):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,neat):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).

[0177] Example 2: Synthesis of tetraepoxide derived from Polyol 4360 (E2) Synthesis of tetraalkenes derived from Polyol 4360 TIFF2025501280000017.tif60170 A reactor is charged with Polyol 4360 (99.0 g, 157.1 mmol) and the material is dried under reduced pressure (20 mbar, 75 °C, 3 h) with stirring. The reactor is then cooled to 20 °C, flushed with nitrogen and charged with dichloromethane (500 mL) and triethylamine (82 g, 810 mmol).

[0178] The clear solution is then cooled to 5° C. with ice water and cyclohex-3-ene-1-carbonyl chloride (100.0 g, 691.5 mmol) is added over 50 min while maintaining the internal temperature between 5-10° C. (The reaction is exothermic.) The cloudy reaction mixture is then warmed to 20° C. over 2 h and stirred at this temperature for an additional 18 h.

[0179] The reaction mixture is then poured into a solution of sodium bicarbonate (50 g) in water (1000 mL) and stirred rapidly at 20° C. for 1 h.

[0180] 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 water (400 mL).

[0181] The organic phase is collected and all volatiles are removed in vacuum. The liquid product is then dried in vacuum (30 mbar, 50° C.) to constant weight. This gives the desired tetraalkene product (178.7 g). 1 H NMR(400 MHz, CDCl3):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).

[0182] Synthesis of tetraepoxide derived from Polyol 4360 (E2) TIFF2025501280000018.tif61170 A reactor is charged with Polyol 4360 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% activity, 169.3 g, 706.3 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 warmed to 20 °C. The reaction mass is then filtered and the white solid is washed with dichloromethane (2 x 50 mL). A solution of sodium sulfite (50 g) in water (500 mL) is added to the resulting filtrate and the biphasic mixture is stirred for 60 min. The mixture is phase separated and the organic phase is washed with a solution of sodium bicarbonate (50 g) and sodium sulfite (21 g) in water (500 mL), then with water (2×500 mL).

[0183] The mixture is allowed to phase separate for 18 hours, the organic phase is collected, dried over sodium sulfate (220 g) and filtered. The filtrate is concentrated in vacuum, and the liquid product is then dried to constant weight (30 mbar, 35° C.). This gives the desired tetraepoxide product E2 (180.6 g, 95.3% of theory). 1 H NMR (400 MHz, CDCl3): 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,neat):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).

[0184] Example 3: Synthesis of hexaepoxide derived from Polyol R6405 (E3) Synthesis of hexaalkenes derived from Polyol R6405 TIFF2025501280000019.tif69170The reactor is charged with Polyol R6405 (385.0 g, 465.5 mmol) and the material is dried under reduced pressure (20 mbar, 80 °C, 2.5 h) while stirring. The reactor is then cooled to 20 °C, flushed with nitrogen, and charged with dichloromethane (2500 mL) and triethylamine (353.3 g, 3.4915 mol). The clear solution is then cooled to 12 °C with ice water 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 warmed to 20 °C over 2 h and stirred at this temperature for an additional 18 h.

[0185] The reaction mixture is then poured into a solution of sodium bicarbonate (205 g) in water (2300 mL) and stirred rapidly for 4 hours at 20° C. The organic phase is separated and extracted with water (3×1500 mL).

[0186] The organic phase is collected and all volatiles are removed in vacuum. The liquid product is then dried in vacuum (30 mbar, 50° C.) to constant weight. This gives the desired hexaalkene product (701.6 g). 1 H NMR(400 MHz, CDCl3):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,neat):3025(w),2869(m),1729(vs),1303(m),1288(m),1247(m),12 22(s), 1166(s), 1099(vs), 1064(s), 1039(s), 952(m), 919(m), 878(m), 650(s).

[0187] Synthesis of hexaalkenes from Polyol R6405 by direct esterification. Combine Perstorp Polyol R6405 (515.2 g, 622.97 mmol), 3-cyclohexene-1-carboxylic acid (565.8 g, 4.485 mol) and toluene (2500 mL) in a reactor fitted with a condenser and a Dean-Stark trap. Flush the reactor with nitrogen, add methanesulfonic acid (4.2 g) with stirring and heat the reaction mixture to reflux (internal temperature 114-116 °C).

[0188] Water is removed from the reaction by azeotropic distillation over 16.5 hours (replacing any toluene that is recovered). The reaction mixture is cooled to 20° C. and extracted with a solution of sodium bicarbonate (100 g) in water (1500 mL). Additional toluene (1000 mL) and water (400 mL) are added and the mixture is allowed to phase separate. The organic phase is separated and washed with 1% aqueous sodium bicarbonate (2×1000 mL) followed by water (2×750 mL).

[0189] The organic phase is collected and all volatiles are removed in vacuo.

[0190] The liquid product is then dried in vacuum (12 mbar, 55° C.) to constant weight, which gives the desired hexaalkene product (933.5 g).

[0191] Synthesis of hexaepoxide derived from Polyol R6405 (E3) TIFF2025501280000020.tif72170 A reactor is charged 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% activity, 532.96 g, 2.168 mol) is added over a period of 5 h with vigorous stirring while maintaining the internal temperature at 4-6 °C. The cloudy mixture is stirred vigorously for 18 h and warmed to 20 °C. The reaction mass is then filtered and the white solid is washed with dichloromethane (350 mL). A solution of sodium sulfite (100 g) in water (1500 mL) is added to the resulting filtrate and the biphasic mixture is stirred for 30 min. The mixture is phase separated and the organic phase is washed with water (2 x 500 mL). The organic phase is collected and all volatiles are removed in vacuo.

[0192] The liquid product is then dried in vacuum (30 mbar, 40° C.) to constant weight, which gives the desired hexaepoxide product E3 (492.1 g, 92.5% of theory). 1H NMR (400 MHz, CDCl3): 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,neat):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).

[0193] Comparative Example 1 For comparison, the commercially available epoxy resin UviCure S105E and the oxetane UviCure S130 (available from Sartomer) were used.

[0194] The difunctional alicyclic epoxide sold as UviCure® S105 has the following structure: I have TIFF2025501280000021.tif63170.

[0195] Example 4: Curing Experiments The following examples illustrate the UV cure speed of the epoxy resins of the present invention. For all of the following cure tests, the photoinitiator SpeedCure 938 (Sartomer) was used.

[0196] The formulation was incubated at 37 °C for 1 hour at a belt speed of 15 m / min and 50% lamp intensity (UV dose for one pass: UVV: 58 mJ / cm 2 , UVA: 108mJ / cm 2 , UVB: 108mJ / cm 2 , UVC: 20mJ / cm 2The coating was cured at a film thickness of 100 μm under a Hg lamp using a belt curing machine (Jenton International Ltd., model number JA2000VPXI-0000) with a 1000 rpm sintering machine. The substrate used was standard black and white paper (Leneta form 3N-31). Viscosity measurements were performed with a Brookfield viscometer (spindle number 31, 25° C.).

[0197] Each tested epoxy resin, E1, E2 or E3, was mixed with UviCure S130 in different weight ratios ranging from 0 to 100 wt%. Data obtained for the mixtures of UviCure S105E and UviCure S130 were used as controls. The photoinitiator SpeedCure 938 (Sartomer) was used at a loading of 1 wt% in the tested resin mixtures.

[0198] Cure speed was assessed by the number of passes under the lamp required to obtain a surface-cured "tack-free" (TF) coating (determined when the surface of the coating no longer feels tacky when lightly touched) or a deep cure as determined by the "thumb-twist" test (TT) (i.e., until no visible mark is left when a thumb is pressed firmly down on the coating with a twisting motion).

[0199] Cured samples were tested for solvent resistance using the MEK double rub test according to ASTM D4752.

[0200] The results are shown in Tables 1, 2, 3 and 4. TIFF2025501280000022.tif86170TIFF2025501280000023.tif85170TIFF2025501280000024.tif85170TIFF2025501280000025.tif85170

[0201] Example 5: Polymerization of an Alkoxylated Cycloaliphatic Epoxide in the Presence of (Meth)Acrylates material The list of materials used in the examples is detailed in the table below. JPEG2025501280000026.jpg207170

[0202] Formulations and Results Formulations were prepared using the ingredients listed in the table below (amounts are given in parts by weight). JPEG2025501280000027.jpg198170JPEG2025501280000028.jpg160170

[0203] Preparation of Formulations The formulations in Tables 6A and 6B were prepared as follows: 125 mL amber glass bottles were loaded first with the epoxide and oxetane, followed by the photoinitiator. 100 g of the mixture of each sample was sealed in the bottle by securing the lid with white tape. The three glass bottles were then placed on rollers in a 65°C oven for approximately 2 hours until the solution was clear.

[0204] Viscosity measurement Viscosity measurements were performed using a Brookfield DV-II+Pro viscometer. A standard S18 size spindle was used to measure viscosity. Viscosity readings were taken at 25°C and the torque % was between 30-80%.

[0205] Printing thin strip samples with 355nm SLA Viper a. Cut the PET film (approximate size 7.5 inches x 6.5 inches) into a square to fit the shape of the glass (8 inches x 8 inches), and use double-sided tape to attach the PET film to the glass. b. A non-sticky substance (Rust-o-leum Never Wet Coat 1 Spray) was sprayed evenly onto the PET film. c. Selected "elevator motion" on the SLA Viper to set the elevator position to 2.1740. d. A pipette was used to dispense approximately 2 mL of liquid onto the glass. e. The first layer of film was applied using the 5 μm side of the coating applicator. fE c and D p was set to medium (E for all three formulations) c =65, D p =5) and start printing g. Once the first layer of printing was completed, the 10 μm side of the applicator was used to apply a second 5 μm layer of film. h. Repeated printing and thin film application until the 30 μm side was used. i. Thus, three 4 inch by 0.5 inch green thin strips, and one 35 mm by 12 mm DMA strip, were printed, with 6 layers of 5 μm each, per print. j. Drain off any uncured liquid resin, clean with IPA, and allow to dry in air. k. Carefully peel each thin strip off the PET film l. Thin strips after curing according to the conditions detailed in Tables 6A and 6B m. Store at 23±2°C and 50±10% relative humidity for at least 7 days prior to testing.

[0206] Tensile Test Tensile properties were measured using an Instron 5966 with a 10 kN load capacity equipped with a tensile test fixture. Thin strips are prepared for tensile properties. Six specimens were prepared for each sample, and the test speed for tensile testing was set at 5 mm / min. Testing was performed according to ASTM D882 protocol. The results are shown in Tables 6A and 6B and in Figure 1.

[0207] DMA Testing A TA Instruments DMA Q800 was used to observe the change in mechanical properties of each cured DMA strip over the entire temperature range. To study materials within this range, a DMA program running from -150°C to 250°C at 3°C / min with a frequency of 1Hz is used. The resulting storage modulus (G'), loss modulus (G'') and tan (delta) curves were analyzed to understand the changes in polymer behavior. The results are shown in Tables 6A and 6B and Figure 2.

[0208] FTIR Testing Fourier transform infrared (FTIR) with attenuated total reflectance (ATR) settings was used. All polymerization kinetics measurements were performed using a Nicolet iS50 FT-IR spectrometer from Thermo Scientific equipped with a standard DLaTGS detector. For the measurements, a drop of liquid sample was placed in the center of the ATR crystal to collect the IR spectrum, and then the flat surface of the printed and cured thin strip was pressed onto the ATR crystal to collect new IR spectra for both acrylate and epoxy conversion calculations. Measurements were performed at approximately 1720 cm -1 The area under the reference peak was approximately 1407 cm -1 acrylate peak at approximately 790 cm -1 The epoxy peak was also measured at 100° C. The peak area was determined using a baseline technique, where the baseline is chosen to border the absorbance minima on either side of the peak. The area under the peak and above the baseline was then determined. The integration limits for the liquid and cured samples are not identical, but are similar, especially for the reference peak.

[0209] The ratio of the acrylate or epoxy peak area to the reference peak was determined for both the liquid and cured samples. The extent of cure or conversion, expressed as a percentage of acrylate or epoxy reacted, was calculated from the following formula: Conversion rate (%) = [(R liq -R c )×100] / R liq Here, R liqis the area ratio of the liquid sample, and R c is the area ratio of the cured tensile strip. The resulting acrylate and epoxy conversions were tested using the FTIR method described above. The results are shown in Tables 6A and 6B.

[0210] LED-DSC Test Photo-differential scanning calorimetry (DSC) was used with a customized LED lamp setting at 365 nm. All photopolymerization rate measurements were performed using a Q2000 DSC unit from TA Instruments. The lamp holder for the DSC unit can be customized and printed from Arkema N3xtDimention® processing resin N3D-TOUGH784 to ensure precise fit of the 365 nm lamp Accucure ULM-2-365 from Digital Light Labs. LED light was automatically triggered by connecting the "Event" outlet of the DSC unit to an Accure Photo Rheometer Ultraviolet Illumination & Measurement System. LED light exposure can be programmed by using "Event" on or off from the Photo DSC software, while light intensity can be pre-set from the Accure Photo Rheometer Ultraviolet Illumination & Measurement System. For the measurements, approximately 5 mg of liquid sample was placed in the center of a T130522 DSC Tzero pan and subjected to 50 mW / cm 2 irradiation at 50 mL / min N2 flow rate and 45 °C for 5 min. 2 The resulting heat flow (W / g) curves were collected and analyzed for maximum heat flow peak value and maximum peak time. The results are shown in Tables 6A and 6B and in FIG. 3.

[0211] Volumetric shrinkage test A. Determining the density of the formulated resin: a. After resin is formulated and mixed, a pre-weighed 5 mL or 10 mL volumetric flask is filled to the mark with such resin. b. Weigh the entire volumetric flask and calculate the density by dividing the net weight of the compounded resin by the volume. c. Repeat this process three times and take the average value as the density of the compounded resin (D, unit: kg / L).

[0212] B. The shrinkage measurement method is based on the volume measurement principle: a. Carefully dispense a fixed weight of formulated resin (designated as W1) into a pre-weighted aluminum foil weighing boat, filling the boat to a height of approximately 3-5 mm. Make sure there are no air bubbles trapped inside the resin. The volume of the foil weigh boats is limited to approximately 1 mL each to ensure that the pieces of cured resin are narrow enough to pass through the neck of the volumetric flask. b. Curing was carried out under mercury lamp conditions with enough passes to obtain a hardened surface. c. The foil boat was then placed in a 60° C. oven for further deep curing until fully cured. d. Remove the foil boat from the oven and allow it to cool to room temperature. e. Fill a 50 mL or 100 mL volumetric flask to the mark with DI water. The foil is removed and the cured resin is placed in a volumetric flask. The resin should be completely immersed and sink. Shake the flask to remove any air bubbles. f. Place the volumetric flask on the analytical balance and tare to zero. Use a pipette to aspirate excess water and bring the water level back up to the mark. Record the total weight loss of the volumetric flask (as W2). g. At least three replicates are required for each resin formulation. A calculation was then performed to obtain the weight loss into the water volume of the volumetric flask. The calculated water volume should be equal to the final volume of the cured resin as per the test design. The density of the applied water is 0.998 kg / L at 20°C.

[0213] C. The volumetric shrinkage is calculated by the following formula: Shrinkage %=((W1 / D)-(W2 / 0.998)) / (W1 / D)×100%

[0214] Test results and discussion Compared to 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (ECC) in the hybrid system, the results in Table 6A showed that the hexa-epoxide according to the present invention slightly increased the viscosity of the formulation, improved the tensile toughness as shown in FIG. 1, reduced the glass transition temperature from the DMA test in FIG. 2, and slowed the cure rate as characterized by the heat flow from the LED-DSC test in FIG. 3.

[0215] In comparison with 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (ECC) in the hybrid system, the results in Table 6B show that the triepoxide according to the invention also slightly increases the viscosity of the formulation, improves the tensile toughness and reduces the glass transition temperature, as characterized by DMA tests.

Claims

1. Formula (I): (In the formula, Each R １ and R ２ is independently selected from H and Me; L is the residue of a polyol; each a is independently 2 to 4; each b is independently 0 to 20, with the proviso that at least one b is not 0; c is at least 3 Alkoxylated cycloaliphatic epoxides.

2. a is 2 and the alkoxylated cycloaliphatic epoxide has the following formula (Ia): (In the formula, L, b and c are as defined in claim 1; Each R １ and R' １ are independently selected from H and Me 2. The alkoxylated cycloaliphatic epoxide of claim 1, wherein the alkoxylated cycloaliphatic epoxide is

3. The alkoxylated cycloaliphatic epoxide of claim 1, wherein each b is independently 1 to 20, particularly 1 to 10, more particularly 2 to 6.

4. 2. The alkoxylated cycloaliphatic epoxide of claim 1, wherein the alkoxylated cycloaliphatic epoxide has a degree of alkoxylation of at least 6, particularly at least 8, more particularly at least 10, and even more particularly at least 12.

5. 2. The alkoxylated cycloaliphatic epoxide of claim 1, wherein c is 3 to 10, particularly 3 to 8, more particularly 4 to 6.

6. c is 4 and L is a group represented by the following formula (IIIa), (IIIb) or (IIIc): (In the formula, e, e', e'' and e''' are independently 0 to 2, with the proviso that at least three of e, e', e'' and e''' are not 0, and in particular, e, e', e'' and e'''' are all 1.

2. The alkoxylated cycloaliphatic epoxide of claim 1, wherein the linker is a tetravalent linker according to one of the following:

7. c is 5 and L is a group represented by the following formula (IV):

2. The alkoxylated cycloaliphatic epoxide of claim 1, wherein the linker is a pentavalent linker of

8. c is 6, and L is a group represented by the following formula (Va), (Vb), or (Vc):

2. The alkoxylated cycloaliphatic epoxide of claim 1, wherein the hexavalent linker is

9. The following steps: a) reacting a cyclohexene of formula (VI) with an alkoxylated polyol of formula (VII) to obtain an alkoxylated cyclohexene of formula (VIII); b) epoxidation of the alkoxylated cyclohexene of formula (VIII) to obtain an alkoxylated cycloaliphatic epoxide of formula (I); (In the formula, L, R １ , R ２ , a, b and c are as defined in claim 1; X is OH, O-Alk or Cl; Alk is C1-C6 alkyl.

2. A process for the preparation of an alkoxylated cycloaliphatic epoxide of formula (I) as defined in claim 1, comprising:

10. Formula (I): (In the formula, L, R １ , R ２ , a and b are as defined in claim 1; c is at least 2, in particular 2 to 10; At least one of the alkoxylated cycloaliphatic epoxides of formula (I) in the mixture has c that is at least 3, at least 4, or at least 5, or at least 6.

1. A composition comprising a mixture of alkoxylated cycloaliphatic epoxides of the formula:

11. a) at least one alkoxylated cycloaliphatic epoxide of formula (I) according to claim 1 or a composition according to claim 10; and b) at least one cationically polymerizable compound other than component a); A composition comprising:

12. Component b) is at least one oxetane, in particular of the following formula (IX): (In the formula, R ４ is H, alkyl, aryl, alkylaryl, (meth)acryloyl, -CH ２ -oxetanyl-CH ２ -CH ３ , -L １ -O-CH ２ -oxetanyl-CH ２ -CH ３ is selected from L １ is a divalent linker, particularly -CH ２ -Ph-Ph-CH ２ or -CH ２ -Ph-CH ２ -[O-CH ２ -Ph-CH ２ ] ｆ - and Ph is phenylene; f is 0 to 10) The composition of claim 11 comprising at least one oxetane according to

13. 12. The composition according to claim 11, wherein the weight ratio between component a) and component b) is from 20:80 to 80:20, in particular from 30:70 to 70:30, more in particular from 40:60 to 60:

40.

14. 12. The composition of claim 11, comprising at least one cationic photoinitiator, in particular an onium salt or a metallocene salt, more in particular 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 mixtures thereof.

15. a) at least one alkoxylated cycloaliphatic epoxide of formula (I) according to claim 1 or a composition according to claim 10; and c) at least one (meth)acrylate-functionalized compound, in particular a (meth)acrylate-functionalized compound having at least two or at least three (meth)acrylate groups; A composition comprising:

16. 12. A method for the preparation of a cured product, comprising curing a composition according to claim 11, in particular by exposing the composition to radiation such as UV, near UV, visible, infrared and / or near infrared or to an electron beam.

17. 12. A method for the preparation of a cured product, comprising curing a composition according to claim 11, 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, 12. A method for the preparation of a 3D printed article, comprising printing the 3D article with a composition according to claim 11, in particular layer by layer or continuously.

18. A cured product obtained by curing the composition according to claim 11.

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