Coumarin thioester photoinitiator

Abstract

The present invention relates to coumarin thioester compounds, to methods for their preparation and to their use as photoinitiators, preferably as photoinitiators which are activatable under irradiation with light in the range from 250 to 550 nm, in particular from 250 to 460 nm, in particular for the curing of formulations comprising one or more ethylenically unsaturated compounds.

Description

Technical Field

[0001] This invention relates to coumarin thioester compounds, their preparation methods, and their use as photoinitiators, preferably as photoinitiators that can be activated under light irradiation of 250 to 550 nm, particularly 250 to 460 nm, especially for curing formulations containing one or more olefinically unsaturated compounds. Background Technology

[0002] The increasing use of UV-Vis curing technology in fields such as high-speed printing, surface coating, and additive manufacturing places high demands on the parameters of the polymer networks formed in these processes. In particular, reactive photoinitiators are needed that are thermally and chemically stable and, upon activation by light or UV radiation, can act as catalysts for various anionic and / or free radical-initiated polymerization reactions.

[0003] The most common photoinitiators are active under UV-B and UV-C light sources, but as the industry shifts to using LED curing, there is a growing demand for photoinitiators that are active at longer wavelengths.

[0004] There is a need for photoinitiators that can be effectively activated by low-energy light sources such as LEDs without the need for additional sensitizers, but which exhibit high thermal stability in the formulation prior to exposure.

[0005] Some common photoinitiators used for curing LEDs (above 365 nm) at longer wavelengths, such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide (SpeedCure TPO), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-but-1-one (SpeedCure BDMB), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(morpholino-4-yl)phenyl]but-1-one (Omnirad 379), and 2-hydroxy-2-methyl-1-phenylpropanone (SpeedCure 97), have been reclassified.

[0006] The commercially available Esacure 3644 (IGM) is a coumarin ketone that can be cured at LED wavelengths, but since it is a type II photoinitiator, it requires an amine to abstract hydrogen.

[0007] Another serious drawback of common free radical photoinitiators (such as phosphine oxides, like 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO)) is their sensitivity to oxygen inhibition and subsequent inability to surface cure. This results in tacky coatings and excessive yellowing within the coating due to the additional passage under lamps.

[0008] Therefore, there is a need for photoinitiators that can cure olefinic unsaturated monomers without additional components, enabling non-sticky surface curing and / or exhibiting a degree of photobleaching.

[0009] A suitable initiation system is also needed, which is active at LED wavelengths and preferably not subject to oxygen inhibition.

[0010] In addition, photoinitiators and their photoproducts need to impart minimal coloration to the finished product and exhibit low volatility and low toxicity.

[0011] CN 116693487 discloses a coumarin-based thioester photoinitiator having aryl or heteroaryl side chains. The photoinitiator is disclosed as suitable for LED photopolymerization; however, the curing method disclosed in the reference is carried out under an inert atmosphere.

[0012] Therefore, photoinitiators with sufficient redshift are required, which exhibit satisfactory curing in olefinic unsaturated monomer formulations under LED light over a wide wavelength range, some of which also show reduced or no oxygen inhibition. Summary of the Invention

[0013] The first object of the present invention is to provide a photoinitiator according to formula (I):

[0014] (I)

[0015] Where n and R 1 R 2 R 3 R 4 R 5 X and R are as defined in this paper.

[0016] A second object of the present invention is to provide a method for preparing a compound of formula (I), comprising reacting a compound of formula (III) with a compound of formula (IV) or (V):

[0017] (III)

[0018] (IV) (V)

[0019] Where n and R 1 R 2 R 3 R 4 R 5 R, X, and G are as defined in this paper.

[0020] In a third objective, the present invention also provides a curable composition comprising:

[0021] - One or more compounds of formula (I) as defined herein; and

[0022] - One or more olefinically unsaturated compounds.

[0023] In a fourth objective, the present invention also provides the use of compounds of formula (I) as defined herein as photoinitiators, particularly as photoinitiators having photobleaching properties.

[0024] In its fifth objective, the present invention provides a method for curing one or more olefinically unsaturated compounds, the method comprising:

[0025] - Mixing one or more olefinically unsaturated compounds with a compound of formula (I) as defined herein; and

[0026] - Irradiate the mixture with at least one light source, preferably at least one LED light source, more preferably at least one LED light source with a maximum output wavelength range of 250 to 550 nm, particularly 250 to 460 nm, and even more particularly 340 to 430 nm. Detailed Implementation Plan

[0027] The invention will now be described in more detail without limitation in the following description, but is not limited thereto.

[0028] definition

[0029] In this application, the term "comprising one / a" means "comprising one or more".

[0030] Unless otherwise stated, the weight percentage of compounds or compositions is expressed based on the weight of the compounds or compositions.

[0031] The term "halogen" refers to an atom selected from Cl, Br, F, and I.

[0032] The term "alkyl" refers to the formula -C n H 2n+1 The monovalent saturated acyclic hydrocarbon group, where n is 1 to 200. The alkyl group can be straight-chain or branched. "(C1-C 20 "alkyl" refers to an alkyl group having 1 to 20 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, 2-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 2,2-dimethylbutyl, n-heptyl, 2-ethylhexyl, etc.

[0033] The term "halogenated alkyl" refers to an alkyl group as defined above, wherein at least one hydrogen atom is replaced by a halogen atom (i.e., Cl, Br, I or F).

[0034] The term "perfluoroalkyl" refers to an alkyl group as defined above, in which all hydrogen atoms are replaced by fluorine atoms.

[0035] The term "alkylene" refers to a linker derived from an alkyl group by removing one hydrogen atom from each linker point.

[0036] The term "alkenyl" refers to a monovalent acyclic hydrocarbon group containing one or more carbon-carbon double bonds. Alkenyl groups can be straight-chain or branched. Examples of alkenyl groups include vinyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, etc.

[0037] The term "aryl" refers to an optionally substituted polyunsaturated aromatic group. An aryl group may contain a single ring (i.e., a phenyl group) or more than one ring, wherein at least one ring is aromatic. When an aryl group contains more than one ring, the rings may be fused together, linked by covalent bonds (e.g., biphenyl). The aromatic ring may optionally contain one or two additional fused rings. The term "aryl" also encompasses aromatic groups containing one or more heteroatoms independently selected from N, O, and S as ring atoms. The term "aryl" also includes partially hydrogenated derivatives of carbocyclic systems as described above. Examples of aryl groups include phenyl, naphthyl, biphenyl, phenanthrene, pyrene, tetraphenyl, pyrimidinyl, pyrazinyl, pyridazinyl, pyridinyl (including 2-aminopyridine), triazinyl, furanyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, thiophene, imidazolyl, thiazolyl, indole (e.g., indole-3-yl), pyrroleyl, oxazolyl, benzofuranyl, benzothiophene, benzopyranyl, benzopyranone, and benzodiphenyl. Oxycyclopentenyl, pyrazolyl, benzothiazolyl, isoxazolyl, triazolyl (including 1,2,4-triazole, 1,2,3-triazole and 5-amino-1,2,4-triazole), tetrazolyl, indazole, isothiazolyl, 1,2,4-thiadiazolyl, purine, carbazole, isoxazolyl, benzimidazolyl, dihydroindolyl, pyranyl, pyrazolyl, triazolyl, oxadiazolyl (including 1,2,3-oxadiazole, 1,2,4-triazole), 4-Oxadiazole, 1,2,5-Oxadiazole, 3-amino-1,2,4-Oxadiazole, 1,3,4-Oxadiazole), thiaanthryl, indazinyl, isoindolyl, isobenzofuranyl, pyrrolyl, benzoxazolyl, xanthonyl, 2H-pyrrolyl, 3H-indolyl, 4H-quinolinyl, phthalazinyl, acridineyl, naphthidyl, quinazolinyl, phenanthridineyl, pyridinyl, (o-) Phenophenolyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazolyl, phenothiazinyl, xanthonyl, thioxanthyl, thioxanthyl, dibenzofuranyl, dibenzothiophenyl, acridineyl, acridineyl, phenothiazinyl, chromanyl, isochoryl, anthraquinoneyl, naphthoquinoneyl, dibenzodioxinyl, etc.

[0038] The term "aryl" refers to a linker derived from an aryl group by removing one hydrogen atom from each linker site.

[0039] The term "cycloalkyl" refers to a monovalent non-aromatic alicyclic group comprising one or more rings. The term cycloalkyl also encompasses non-aromatic cyclic groups comprising one or more heteroatoms independently selected from N, O, and S as ring atoms. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, isoborneol, 1-decahydronaphthalene, norborneol, adamantyl, ethylene oxide, oxacyclobutyl, tetrahydrofuranyl, tetrahydropyranyl, dioxalyl, pyrroliyl, piperidinyl, piperazine, morpholinyl, imidazoalkyl, oxazolyl, dioxopentyl, etc.

[0040] The term "cycloalkylene" refers to a linker derived from a cycloalkyl group by removing one hydrogen atom from each linker point.

[0041] The term "alkoxy" refers to a group of the formula -O-alkyl, wherein the alkyl group is as defined above.

[0042] The term "aryloxy group" refers to a group of the formula -O-aryl, where the aryl group is as defined above.

[0043] The term "linker" refers to a multivalent group. A linker can connect at least two parts of a compound together, particularly two to 16 parts of a compound. For example, a linker that connects two parts of a compound is called a divalent linker, a linker that connects three parts of a compound is called a trivalent linker, and so on.

[0044] The term "hydrocarbon linker" refers to a linker having a carbon backbone, which may optionally be interrupted by one or more heteroatoms selected from N, O, S, Si, and mixtures thereof. Hydrocarbon linkers may be aliphatic, alicyclic, or aromatic. Hydrocarbon linkers may be saturated or unsaturated. Hydrocarbon linkers may be optionally substituted.

[0045] The term "aliphatic" refers to non-aromatic acyclic compounds. They can be straight-chain or branched, saturated or unsaturated. They can be substituted with one or more groups, selected from alkyl, hydroxyl, halogens (Br, Cl, I, F), isocyanates, carbonyl, amines, carboxylic acids, -C(=O)-OR', -C(=O)-OC(=O)-R', where each R' is independently C1-C2. 20 Alkyl group. It may contain one or more bonds selected from ethers, esters, amides, carbamates, ureas, and mixtures thereof.

[0046] The term "acyclic" refers to a compound that does not contain any rings.

[0047] The term "alicyclic" refers to a non-aromatic cyclic compound. It can be substituted by one or more groups as defined by the term "alicyclic". It can contain one or more bonds as defined by the term "alicyclic".

[0048] The term "aromatic" refers to a compound containing an aromatic ring, meaning it adheres to Hückel's rules of aromaticity, particularly for compounds containing a phenyl group. It can be substituted by one or more groups as defined by the term "aliphatic." It can contain one or more bonds as defined by the term "aliphatic."

[0049] The term "saturated" refers to a compound that does not contain any carbon-carbon double or triple bonds.

[0050] The term "unsaturated" refers to compounds containing carbon-carbon double or triple bonds, especially (double) carbon-carbon double bonds.

[0051] The term "polyether linker" refers to a linker that contains at least two ether bonds.

[0052] The term "polysulfide linker" refers to a linker that contains at least two sulfide bonds.

[0053] The term "polyester linker" refers to a linker containing at least two ester bonds.

[0054] The term "polyorganosiloxane linker" refers to a linker containing at least two organosiloxane bonds. Organosiloxanes can be, for example, dimethylsiloxane bonds.

[0055] The term "polybutadiene linker" refers to a linker comprising at least two units derived from butadiene polymerization, particularly at least two units selected from -CH2-CH=CH-CH2- and CH2-CH(CH=CH2)-.

[0056] The term "isocyanate group" refers to the -N=C=O group.

[0057] The term "isocyanurate linker" refers to a linker that includes an isocyanurate moiety, specifically the portion of the following formula:

[0058]

[0059] As used herein, “optionally substituted” means an unsubstituted group or a group substituted by one or more identical or different substituents.

[0060] Unless otherwise stated, the optional substituents of alkyl and alkenyl groups may be independently selected from: -OH, -SH, halogens, straight-chain or branched -O (C1-C2). 20 )alkyl, straight-chain or branched -S(C1-C 20 )alkyl, -(C3-C 12)cycloalkyl, -(C5-C 12 )Aryl, -O(C5-C 12 )Aryl, -S(C5-C 12 )Aryl, -(C5-C 12 )-Aspartic-(C1-C 20 Alkyl groups, -NO2, -CN, -C(=O)OR a -OC(=O)R b -C(=O)R c -NR d R e and -C(=O)NR d R e , where R a R b R c R d and R e Independently selected from H, straight chain or branched -(C1-C 20 )alkyl and optionally substituted -(C5-C 12 Aryl.

[0061] Unless otherwise stated, the optional substituents of the aryl and cycloalkyl groups may be independently selected from: -OH, -SH, halogen, straight-chain or branched -(C1-C) groups. 20 )alkyl, straight-chain or branched -(C1-C 20 ) Haloalkyl, -(C1-C 20 Perfluoroalkyl, straight-chain or branched -(C2-C) 20 Alkenyl, straight-chain or branched -O(C1-C) 20 )alkyl, straight-chain or branched -S(C1-C 20 )alkyl, -S(C1-C 20 )alkyl, -(C3-C 12 )cycloalkyl, -(C5-C 12 )Aryl, -O(C5-C 12 )Aryl, -S(C5-C 12 )Aryl, -(C1-C 20 )-alkylene-(C5-C 12 )Aryl, -(C5-C 12 )-Aspartic-(C1-C 20 Alkyl, -NO2, -CN, -C(=O)OR a -OC(=O)R b -C(=O)R c -NR d R e and -C(=O)NR d R e , where Ra R b R c R d and R e Independently selected from H, straight chain or branched -(C1-C 20 )alkyl and optionally substituted -(C5-C 12 Aryl.

[0062] Compound of formula (I)

[0063] This invention relates to compounds of formula (I):

[0064] (I)

[0065] in

[0066] n is 1 or 2;

[0067] X represents S, Se, or Te;

[0068] Each R 1 R 2 R 3 R 4 and R 5 Independently selected from H, -OH, -SH, halogen, straight-chain or branched -(C1-C) 20 )alkyl, straight-chain or branched -(C1-C 20 ) Haloalkyl, straight-chain or branched (C1-C 20 - Perfluoroalkyl, straight-chain or branched - (C2-C 20 Alkenyl, straight-chain or branched -O(C1-C) 20 )alkyl, straight-chain or branched -S(C1-C 20 )alkyl, -(C3-C 12 )cycloalkyl, -(C5-C 12 )Aryl, -O(C5-C 12 )Aryl, -S(C5-C 12 )Aryl, -(C1-C 20 )-alkylene-(C5-C 12 )Aryl, -(C5-C 12 )-Aspartic-(C1-C 20 Alkyl, -NO2, -CN, -C(=O)OR a -OC(=O)R b -C(=O)R c -NR d R e and -C(=O)NR d R e ; or two adjacent R2 R 3 R 4 and R 5 The groups can form 3- to 12-membered aliphatic rings or 5- to 12-membered aromatic rings together with the carbon atoms they are attached to; wherein R a R b R d and R e Same or different, independently selected from H and straight or branched -(C1-C 20 )alkyl; and R c Selected from straight or branched -(C1-C 20 )alkyl and -(C5-C 12 )aryl group, optionally surrounded by -OH, -SH, halogen, straight-chain or branched -(C1-C 20 )alkyl, straight-chain or branched -(C1-C 20 ) Haloalkyl, straight-chain or branched -(C1-C 20 Perfluoroalkyl, straight-chain or branched -(C2-C) 20 Alkenyl, straight-chain or branched -O(C1-C) 20 )alkyl, straight-chain or branched -S(C1-C 20 )alkyl, -NR d R e One or more substitutions of -NO2 and -CN;

[0069] R can be chosen freely from the following:

[0070] -Straight chain or branched chain-(C1-C) 20 Alkyl groups, wherein the alkyl group is optionally interrupted by one or more groups selected from -O-, -C(=O)- and -S-, and wherein the alkyl group is optionally selected from -OH, -SH, halogens, straight-chain or branched -O(C1-C) groups. 20 )alkyl, straight-chain or branched -S(C1-C 20 )alkyl, -(C3-C 12 )cycloalkyl, -(C5-C 12 )Aryl, -O(C5-C 12 )Aryl, -S(C5-C 12 )Aryl, -NO2, -CN, -CF3, -C(=O)OR a -OC(=O)R b -C(=O)R c -NR d R e and -C(=O)NR d R e One or more groups are substituted, wherein R is a group that is substituted for R. a R bR c R d and R e As defined above;

[0071] -Straight chain or branched chain-(C2-C) 20 An alkenyl group, wherein the alkenyl group is optionally interrupted by one or more groups selected from -O- and -C(=O)-, and the alkenyl group is optionally selected from -OH, -SH, halogen, straight-chain or branched -O(C1-C)-. 20 )alkyl, straight-chain or branched -S(C1-C 20 )alkyl, -(C3-C 12 )cycloalkyl, -(C5-C 12 )Aryl, -O(C5-C 12 )Aryl, -S(C5-C 12 )Aryl, -NO2, -CN, -CF3, -C(=O)OR a -OC(=O)R b -C(=O)R c -NR d R e and -C(=O)NR d R e One or more groups are substituted, wherein R is a group that is substituted for R. a R b R c R d and R e As defined above;

[0072] -(C3-C 12 ) cycloalkyl group, wherein the cycloalkyl group is optionally interrupted by one or more heteroatoms independently selected from O, N, and S, and the cycloalkyl group is optionally selected from: -OH, -SH, halogen, straight-chain or branched -(C1-C 20 )alkyl, straight-chain or branched -(C1-C 20 ) Haloalkyl, -(C1-C 20 Perfluoroalkyl, straight-chain or branched -(C2-C) 20 Alkenyl, straight-chain or branched -O(C1-C) 20 )alkyl, straight-chain or branched -S(C1-C 20 )alkyl, -(C5-C 12 )Aryl, -O(C5-C 12 )Aryl, -S(C5-C 12 )Aryl, -NO2, -CN, -C(=O)OR a -OC(=O)R b -C(=O)R c -NR d Re and -C(=O)NR d R e One or more groups are substituted, wherein R is a group that is substituted for R. a R b R c R d and R e As defined above; and

[0073] - Groups of formula (II):

[0074] (II)

[0075] Where X and R 1 R 2 R 3 R 4 R 5 and n are as defined above;

[0076] L is a (m+1) valence connector;

[0077] m can be 1 to 10, preferably 1 to 6.

[0078] The preferred embodiments described below can be considered individually or in combination where applicable, and can be applied to any of equation (I) and the equations described below:

[0079] According to one implementation plan, R 1 For H, and R 2 R 3 R 4 and R 5 Independently selected from H, straight-chain or branched -O(Cl-C) 20 )alkyl and -NR d R e , where R d and R e Independently, either straight or branched -(C1-C) 20 )alkyl.

[0080] According to one implementation plan, R 1 R 3 and R 5 For H, and R 2 and R 4 Independently selected from H, straight-chain or branched -O(Cl-C) 20 )alkyl and -NR d R e , where R d and R e Independently, either straight or branched -(C1-C) 20 )alkyl.

[0081] According to one implementation plan, R 1 R 2 R 3 R 4 and R 5 For H.

[0082] According to one implementation plan, R 1 R 2 R 3 and R 5 It is H and R 4 Is it a straight-chain or branched -O(C1-C) 20 Alkyl groups, preferably methoxy groups.

[0083] According to one implementation plan, R 1 R 2 R 3 and R 5 It is H and R 4 Yes -NR d R e , where R d and R e Independently, it can be either straight or branched -(C1-C 20 Alkyl groups, preferably methyl or ethyl.

[0084] According to one implementation plan, R 2 R 3 and R 5 For H, and R 1 and R 4 Each can be independently either straight-chain or branched -O(C1-C) 20 Alkyl groups, preferably methoxy groups.

[0085] According to one implementation plan, R 1 R 3 and R 5 For H, and R 2 and R 4 Each can be independently either straight-chain or branched -O(C1-C) 20 Alkyl groups, preferably methoxy groups.

[0086] According to one implementation scheme, R can be selected from straight chains or branches as defined above -(C1-C 20 )alkyl, as defined above, straight-chain or branched -(C2-C 20 )alkenyl and -(C3-C as defined above 12 )cycloalkyl.

[0087] Specifically, R can be selected from straight or branched -(C1-C) 20alkyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl, methyltetrahydrofuranyl, and tetrahydropyranyl, wherein the alkyl group is optionally interrupted by one or more groups selected from -O- and -S-, and wherein the alkyl group is optionally interrupted by one or more groups selected from -(C5-C60) 12 )Aryl, -C(=O)OR a and -NR d R e The group is substituted, wherein R is a group that is substituted for R. a R d and R e As defined above, the cyclohexyl group is optionally substituted by one or more groups selected from: -OH, -SH, halogen, straight-chain or branched -(C1-C2) groups. 20 )alkyl, straight-chain or branched -(C1-C 20 ) Haloalkyl, - Straight-chain or branched (C1-C 20 Perfluoroalkyl, straight-chain or branched -(C2-C) 20 Alkenyl, straight-chain or branched -O(C1-C) 20 )alkyl, straight-chain or branched -S(C1-C 20 )alkyl, -(C5-C 12 )Aryl, -O(C5-C 12 )Aryl, -S(C5-C 12 )Aryl, -NO2, -CN, -C(=O)OR a -OC(=O)R b -C(=O)R c -NR d R e and -C(=O)NR d R e , where R a R b R c R d and R e As defined above.

[0088] More specifically, R can be a residue of a monothiol (i.e., a residue obtained by removing the SH group from a monothiol). A suitable monothiol (also referred to herein as M) SHExamples of ) include methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, sec-butyl mercaptan, tert-butyl mercaptan, n-pentyl mercaptan, n-hexyl mercaptan, 2-ethylhexyl mercaptan, n-octyl mercaptan, n-nonyl mercaptan, tert-nonyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexadecyl mercaptan, poly(ethylene glycol) methyl ether mercaptan, 2-(dimethylamino)ethyl mercaptan, allyl mercaptan, cyclohexyl mercaptan, cyclohexylmethyl mercaptan, tetrahydro-2H-pyran-4-thiol, furan-2-ylmethyl mercaptan, tetrahydrofuran-3-thiol, 2- Methyltetrahydrofuran-3-thiol, benzylthiol, 1-phenylethylthiol, 2-phenylethylthiol, methyl mercaptoacetate, ethyl mercaptoacetate, butyl mercaptoacetate, 2-ethylhexyl mercaptoacetate, isooctyl mercaptoacetate, isothiazines of mercaptoacetate, methyl 3-mercaptopropionate, ethyl 2-mercaptopropionate, ethyl 3-mercaptopropionate, ethyl 3-mercaptobutyrate, isopropyl 3-mercaptopropionate, butyl 3-mercaptopropionate, 3-methoxybutyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, isothiazines of 3-mercaptopropionate, octadecyl 3-mercaptopropionate, and mixtures thereof.

[0089] According to an alternative implementation, R is determined according to equation (II):

[0090] (II)

[0091] Where X and R 1 R 2 R 3 R 4 R 5 and n are as defined above;

[0092] L is a (m+1) valence connector;

[0093] m can be 1 to 10, preferably 1 to 6.

[0094] Specifically, L can be a divalent, trivalent, tetravalent, pentavalent, hexavalent, heptavalent, octavalent, nonavalent, or decavalent linker. More specifically, L can be a divalent, trivalent, tetravalent, pentavalent, or hexavalent linker. Even more specifically, L can be a divalent, trivalent, or tetravalent linker.

[0095] More specifically, L can be selected from aromatic linkers, aliphatic linkers, alicyclic linkers, polyether linkers, polysulfide linkers, polyester linkers, polyorganosiloxane linkers, polybutadiene linkers, and combinations thereof.

[0096] More specifically, L can be an aliphatic carbon atom directly bonded to X, preferably sp. 3 A linker of hybrid carbon atoms.

[0097] Even more specifically, L can be selected from:

[0098] -The divalent part of any one of equations (L0) to (L7):

[0099] -CH2-CH2-O-CH2-O-CH2-CH2-[SS-CH2-CH2-O-CH2-O-CH2-CH2] a -(L0)

[0100] -(CR 6 R 7 ) a - (L1)

[0101] -[(CR 8 R 9 ) b -W] c -(CR 8 R 9 ) b - (L2)

[0102] -[(CR 10 R 11 ) d -W] e -(CR 12 R 13 ) f -[W-(CR 10 R 11 ) d ] e - (L3)

[0103] -[(CR 14 R 15 ) g -OC(=O)-(CR 16 R 17 ) h -C(=O)-O] i -(CR 14 R 15 ) g - (L4)

[0104] -(CR 18 R 19 ) j -C(=O)-O-(CR 20 R 21 ) k -OC(=O)-(CR 18 R 19 ) j - (L5)

[0105] -(CR 22 R23 ) l -Cy-[A-Cy] o -(CR 22 R 23 ) l - (L6)

[0106]

[0107] in:

[0108] in:

[0109] - R 6 R 7 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 22 and R 23 It is independently H or alkyl;

[0110] - R 8 R 9 R 10 and R 11 It is either H or methyl independently;

[0111] - Each R 24 It is independently alkyl, haloalkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkylaryl, alkoxy, or aryloxy;

[0112] - Each W is independently O or S;

[0113] - Each Cy is an optionally substituted ring, particularly an optionally substituted arylene or optionally substituted cycloalkylene;

[0114] - A is a bond or linker, such as -O-, -S-, Alk, -C(=O)-, -C(=O)-O-Alk-OC(=O)-, -SO-, -SO2-, -C(=CCl2)- and -Alk-Ph-Alk-;

[0115] - Each Alk is independently an optionally substituted alkylene group;

[0116] - Ph is an optionally substituted phenylene;

[0117] - Each B is independently a bond or hydrocarbon linker, which is optionally interrupted by one or more functional groups selected from -O-, -(C=O)-, -(C=O)-O- and -O-(C=O)-;

[0118] - a Integers from 1 to 50;

[0119] - a, f, g, h, and k are independent integers from 2 to 20;

[0120] - Each l is an independent integer from 0 to 20;

[0121] - b and d are independent integers from 2 to 4;

[0122] - o is an integer equal to 0 or 1;

[0123] - c, i, and j are independent integers from 1 to 20;

[0124] - Each e is an independent integer from 0 to 20, provided that at least one e is not 0;

[0125] - p is 0 to 100;

[0126] - The trivalent part of any one of equations (L8) to (L11):

[0127] (L8)

[0128] (L9)

[0129] (L10) (L11)

[0130] in:

[0131] - Each R 25 and R 26 Independently alkylene;

[0132] - R 27 It is H, alkyl or alkoxy, preferably R. 27 It is H or alkyl;

[0133] - Each R 28 Independently alkylene;

[0134] - Each q is an independent integer equal to 0 or 1;

[0135] - Each r is an independent integer from 0 to 2, provided that no more than one r is equal to 0, preferably each r is equal to 1 or one r is equal to 0 and the other two r are equal to 1;

[0136] - According to the tetravalent part of equation (L12) or (L13):

[0137] (L12)

[0138] (L13)

[0139] in:

[0140] - Each R 29 and R 31 Independently alkylene;

[0141] - Each R 30 Independently H, alkyl or alkoxy, preferably R 30 It is an alkyl group;

[0142] - Each s is an independent integer from 0 to 2, provided that no more than one s is equal to 0, preferably each f is equal to 1;

[0143] - According to the hexavalent part of equation (L14):

[0144] (L14)

[0145] Each R 32 Alkylenes that are either straight-chain or branched;

[0146] in

[0147] Alkyl refers to a straight-chain or branched -(C1-C2) group. 20 )alkyl,

[0148] Alkylene refers to straight-chain or branched -(C1-C2) alkylene groups. 20 )alkylene-,

[0149] Alkyl groups refer to straight-chain or branched -O (C1-C2) groups. 20 )alkyl;

[0150] Aryl refers to -(C5-C 12 aryl;

[0151] Alkenyl refers to a straight-chain or branched -(C2-C) group. 20 alkenyl;

[0152] Cycloalkyl refers to -(C3-C 12 )cycloalkyl;

[0153] Alkyl aryl refers to -(C5-C 12 )-Aspartic-(C1-C 20 )alkyl;

[0154] Aryl groups refer to -(C1-C 20)-alkylene-(C5-C 12 aryl;

[0155] "Optionally substituted" means that there is no substituent or one or more substituents selected from the following: -OH, -SH, halogen, straight-chain or branched -(C1-C2) substituents. 20 )alkyl, straight-chain or branched -(C1-C 20 ) Haloalkyl, -(C1-C 20 Perfluoroalkyl, straight-chain or branched -(C2-C) 20 Alkenyl, straight-chain or branched -O(C1-C) 20 Alkyl, straight-chain or branched -S(C1-C) 20 )alkyl, -(C3-C 12 )cycloalkyl, -(C5-C 12 )Aryl, -O(C5-C 12 )Aryl, -S(C5-C 12 )Aryl, -(C1-C 20 )-alkylene-(C5-C 12 )Aryl, -(C5-C 12 )-Aspartic-(C1-C 20 Alkyl, -NO2, -CN, -C(=O)OR a -OC(=O)R b -C(=O)R c -NR d R e and -C(=O)NR d R e , where R a R b R c R d and R e As defined above.

[0156] More specifically, L can be a residue of a polythiol (i.e., a residue obtained by removing the SH group from the polythiol). A suitable polythiol (also referred to as P in this paper) SHExamples include ethane-1,2-dithiol, propane-1,3-dithiol, butane-1,4-dithiol, hexane-1,6-dithiol, octane-1,8-dithiol, decane-1,10-dithiol, 1,8-dimercapto-3,6-dioxaoctane (DMDO), di-, tri-, or polyethylene glycol di(ethanethiol), polyols, and thiol-functionalized carboxylic acids such as mercaptoacetic acid, 3-mercaptopropionic acid, or 3-mercaptobutyric acid (available as Thiocure® from Bruno Bock or as Karenz® MT from Showa). Denko obtained, for example, ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), 1,2-propanediol bis(thioglycolate), 1,2-propanediol bis(3-mercaptopropionate), 1,2-propanediol bis(3-mercaptobutyrate), 1,3-propanediol bis(thioglycolate), 1,3-propanediol bis(3-mercaptopropionate), 1,4-butanediol bis(thioglycolate). 1,4-Butanediol bis(3-mercaptopropionate), 1,4-Butanediol bis(3-mercaptobutyrate), 1,6-Hexanediol bis(mercaptoacetate), 1,6-Hexanediol bis(3-mercaptopropionate), 1,6-Hexanediol bis(3-mercaptobutyrate), di-, tri- or polyethylene glycol bis(mercaptoacetate), di-, tri- or polyethylene glycol bis(3-mercaptopropionate), di-, tri- or polyethylene glycol bis(3-mercaptobutyrate), di-, tri- or polyethylene glycol bis(mercaptoacetate), di-, tri- or polyethylene glycol bis(mercaptoacetate), di-, Tri- or polypropylene glycol bis(3-mercaptopropionate), di-, tri- or polypropylene glycol bis(3-mercaptobutyrate), trimethylolpropane tri(mercaptoacetate), trimethylolpropane tri(3-mercaptopropionate), trimethylolpropane tri(3-mercaptobutyrate), glyceryl tri(mercaptoacetate), glyceryl tri(3-mercaptopropionate), glyceryl tri(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(mercaptoacetate) Pentaerythritol hexa(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptobutyrate), and pentaerythritol tetra(mercaptoacetate), cyclohexanedithiol, cyclohexyldimethylthiol, dipentenedithiol, tris(3-mercaptopropyl)isocyanurate, tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tris[2-(3-mercaptobutyryloxy)ethyl]isocyanurate, mercapto-terminated polymers (such as Capcure® 3-800 (BASF), GPM-800 (Gabriel Performance Products), Capcure® LOF (BASF), GPM-800LO (Gabriel Performance Products)),Thiol-functionalized polyorganosiloxanes (e.g., Silmer SH JO, Silmer SH Q20, and Silmer SH 208-30Q from Siltech), polysulfide polymers (e.g., Thiokol® LP from Toray), and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives, and combinations thereof.

[0157] According to one embodiment, X can be S. Preferably, X is not directly bonded to an aromatic carbon atom. In other words, the linker L may not have an aromatic carbon atom directly bonded to X.

[0158] In a particularly preferred embodiment, the compound of formula (I) is based on one of the following structures:

[0159] (5) (6)

[0160] (7) (8)

[0161] (9) (10)

[0162] (11) (12)

[0163] (13)

[0164]

[0165]

[0166]

[0167]

[0168] Each z is independently between 0 and 20.

[0169] In the above formula, one or more oxyethylidene (ethylene oxide) units can be indiscriminately replaced by oxypropylidene (propylene oxide) units.

[0170] In equations (13) to (22) above, the coumarin ring may optionally be replaced by one or more substituents R as defined above. 1 R 2 R 3 R 4 and R 5 replace.

[0171] Advantageously, the compounds of formula (I) according to the invention can be synthesized from readily available commercial reagents. They have been shown to be stable in formulation and to have excellent solubility in organic solvents and a variety of monomers.

[0172] While not wishing to be bound by any particular theory, compounds of formula (I) according to the present invention are capable of initiating the curing of compositions containing (meth)acrylate-functionalized compounds (by free radical polymerization), cyanoacrylate-functionalized compounds (by anionic polymerization), and mixtures of the two types of compounds.

[0173] This capability enables a wide range of formulations, and is particularly advantageous when formulating for applications requiring specific physical properties of the cured material.

[0174] Methods for preparing compounds of formula (I)

[0175] The present invention also relates to a method for preparing a compound of formula (I) according to the invention, the method comprising reacting a compound of formula (III) with a compound of formula (IV) or (V):

[0176] (III)

[0177] (IV) (V)

[0178] in

[0179] n, R 1 R 2 R 3 R 4 and R 5 As defined above;

[0180] G is an OH atom, a halogen atom, or -OC(=O)-J;

[0181] J is alkyl or aryl, especially tert-butyl;

[0182] R is a straight chain or a branch as defined above -(C1-C 20 )alkyl or -(C3-C 12 )cycloalkyl;

[0183] X is defined above;

[0184] L is as defined above;

[0185] m is as defined above.

[0186] According to one implementation scheme, when R in equation (I) represents the -(C1-C) of a straight chain or a branched chain... 20)alkyl, straight-chain or branched -(C2-C 20 )alkenyl or -(C3-C 12 When cycloalkyl is involved, compounds of formula (III) react with compounds of formula (IV). Compounds of formula (IV) can in particular be monothiols, such as those mentioned above in M. SH The monothiols listed in the table.

[0187] Typically, the reaction of a compound of formula (III), where G is a halogen, with a compound of formula (IV) can be carried out in an organic solvent, preferably a nonpolar aprotic solvent such as THF, in the presence of a base, preferably a weak organic base such as triethylamine.

[0188] The reaction can be carried out over a wide temperature range from -20°C to the reflux temperature of the reaction mixture.

[0189] According to an alternative embodiment, when R is a group of formula (II) in formula (I), the compound of formula (III) is reacted with the compound of formula (V). The compound of formula (V) can be, in particular, a polythiol, such as those mentioned above in P. SH The polythiols listed in the document.

[0190] Typically, the reaction of compound (III), where G is OH, with compound (V) can be carried out in an organic solvent, preferably a nonpolar aprotic solvent such as dichloromethane, in the presence of a carboxylic acid activator such as N,N′-dicyclohexylcarbodiimide (DCC), and in the presence of a nucleophilic catalyst such as 4-dimethylaminopyridine (DMAP).

[0191] The reaction can be carried out over a wide temperature range from -20°C to the reflux temperature of the reaction mixture.

[0192] According to one embodiment, the method of the present invention may further include the step of preparing an intermediate of formula (III).

[0193] According to one embodiment, a compound of formula (III) in which G is a halogen atom can typically be prepared by halogenating a corresponding compound of formula (III) in which G is OH.

[0194] As an illustrative example, a compound (III) in which G is Cl can be obtained by reacting a compound (III) in which G is OH with thionyl chloride.

[0195] According to another embodiment, a compound of formula (III) in which n=2 can typically be prepared by reacting a compound of formula (III) in which n is 1 and G is CH3 with an oxidizing agent such as selenium oxide (SeO2) in the presence of a base such as pyridine.

[0196] Typically, the starting product (III) and reagents (IV) and (V) are commercially available or can be synthesized by applying or modifying known methods. For example, reagent (IV) can be as described above for P. SH The defined polythiols, and the reagent (V) can be as described above for P. SH The defined polythiols.

[0197] This method may include, for example, a step of purifying the obtained compound of formula (I) by column chromatography.

[0198] Alternatively, the compound of formula (I) can be prepared by reacting the compound of formula (VI) with the compound of formula (IV) or (V):

[0199] (VI)

[0200] (IV) (V)

[0201] Where n and R 1 R 2 R 3 R 4 R 5 R, X, L and m are defined as above.

[0202] According to one implementation scheme, when R in equation (I) represents the straight chain or branched chain -(C1-C1) 20 )alkyl, straight-chain or branched -(C2-C 20 )alkenyl or -(C3-C 12 When cycloalkyl is involved, compounds of formula (VI) react with compounds of formula (IV). Compounds of formula (IV) can be, in particular, monothiols, such as those mentioned above in M. SH The monothiols listed in the table.

[0203] According to an alternative embodiment, when R is a group of formula (II) in formula (I), the compound of formula (VI) is reacted with the compound of formula (V). The compound of formula (V) can be, in particular, a polythiol, such as those mentioned above in P. SH The polythiols listed in the document.

[0204] Typically, the reaction of a compound of formula (VI) with a compound of formula (IV) or (V) can be carried out in an organic solvent, preferably a nonpolar organic solvent such as benzene, toluene or dialkyl ether, in the presence of an acid, preferably a strong acid such as HCl.

[0205] Alternatively, compounds of formula (I) can be prepared by reacting a compound of formula (VI) with hydrogen sulfide (H2S) and a compound of formula (VII) or (VIII):

[0206] (VI)

[0207] (VII) (VIII)

[0208] in

[0209] R 1 R 2 R 3 R 4 R 5 m, R, and L are defined as above;

[0210] Hal is a halogen atom selected from Cl, Br, and I.

[0211] According to one embodiment, when R represents a straight-chain or branched alkyl-(C1-C1) group in formula (I), 20 )alkyl, straight-chain or branched -(C2-C 20 )alkenyl or -(C3-C 12 When cycloalkanes are used, compounds of formula (VI) react with hydrogen sulfide and compounds of formula (VII) as radicals.

[0212] According to an alternative embodiment, when R is a group of formula (II) in formula (I), the compound of formula (VI) is reacted with hydrogen sulfide and the compound of formula (VIII).

[0213] Typically, the reaction of compounds of formula (VI) with hydrogen sulfide and compounds of formula (VII) or (VIII) can be carried out in water or an organic solvent, preferably a polar organic solvent such as dimethylformamide or acetone, in the presence of a base, preferably a weak organic base such as pyridine.

[0214] The reaction can be carried out over a wide temperature range from -20 °C to the reflux temperature of the reaction mixture, preferably at 50-80 °C.

[0215] Curable Composition

[0216] The present invention also relates to curable (or polymerizable) compositions comprising one or more compounds of formula (I) and one or more olefinically unsaturated compounds.

[0217] Based on the total weight of the curable composition, the curable composition may contain 0.05% to 10% by weight, particularly 0.1% to 5% by weight, and even more particularly 0.15% to 2% by weight of the compound of formula (I). If the curable composition contains a mixture of compounds of formula (I), the above weight percentages can be calculated using the weight of the mixture of compounds of formula (I).

[0218] Based on the total weight of the curable composition, the curable composition may include 20% to 99.95%, preferably 30% to 98%, more preferably 40% to 97% of an olefinically unsaturated compound. If the composition contains a mixture of olefinically unsaturated compounds, the above weight percentages can be calculated using the weight of the mixture of olefinically unsaturated compounds.

[0219] The curable composition of the present invention may further comprise one or more compounds selected from the following:

[0220] -Anionic synergist;

[0221] - Free radical photoinitiators;

[0222] -Acid stabilizer;

[0223] -Free radical stabilizers

[0224] - Additives; and

[0225] - Solvent.

[0226] olefinic unsaturated compounds

[0227] The curable composition contains one or more olefinically unsaturated compounds.

[0228] As used herein, the term "olefinic unsaturated compound" refers to a compound containing a polymerizable carbon-carbon double bond. A polymerizable carbon-carbon double bond is a carbon-carbon double bond that can react with another carbon-carbon double bond in a polymerization reaction. Polymerizable carbon-carbon double bonds are typically contained in groups selected from acrylates, methacrylates, cyanoacrylates, acrylamide, methacrylamide, styrene, maleate, fumarate, itaconic acid, methylene malonate, methylene acetylated pyruvate, methylene β-diketone, allyl, propenyl, vinyl, and combinations thereof, preferably selected from acrylates, methacrylates, cyanoacrylates, allyl, and vinyl, and more preferably selected from acrylates, methacrylates, and cyanoacrylates. Carbon-carbon double bonds on a benzene ring are not considered polymerizable carbon-carbon double bonds.

[0229] According to some preferred embodiments, one or more olefinically unsaturated compounds include at least one of cyanoacrylate-functionalized compounds, (meth)acrylate-functionalized compounds, and mixtures thereof.

[0230] Curable compositions may contain cyanoacrylates. Curable compositions may contain mixtures of cyanoacrylates.

[0231] As used herein, the term "cyanoacrylate" refers to an organic compound containing a carbon-carbon double bond in which one carbon atom involved in the carbon-carbon double bond is replaced by a cyano (-CN) group and an ester group.

[0232] Examples of suitable cyanoacrylates include methyl cyanoacrylate, ethyl cyanoacrylate, n-propyl cyanoacrylate, isopropyl cyanoacrylate, n-butyl cyanoacrylate, sec-butyl cyanoacrylate, isobutyl cyanoacrylate, tert-butyl cyanoacrylate, n-pentyl cyanoacrylate, 1-methylbutyl cyanoacrylate, 1-ethylpropyl cyanoacrylate, neopentyl cyanoacrylate, n-hexyl cyanoacrylate, 1-methylpentyl cyanoacrylate, n-heptyl cyanoacrylate, n-octyl cyanoacrylate, 2-octyl cyanoacrylate, 2-ethylhexyl cyanoacrylate, n-nonyl cyanoacrylate, n-decyl cyanoacrylate, and n-undecane cyanoacrylate. Acrylates, n-dodecyl cyanoacrylate, n-octadecyl cyanoacrylate, allyl cyanoacrylate, cyclohexyl cyanoacrylate, 2-methoxyethyl cyanoacrylate, 2-ethoxyethyl cyanoacrylate, phenoxyethyl cyanoacrylate, 2-(1-alkoxy)propyl cyanoacrylate (e.g., 2-(1-methoxy)propyl cyanoacrylate), 2-(2'-alkoxy)-methoxyethyl-2"-cyanoacrylate (e.g., 2-(2'-methoxy)-ethoxyethyl-2"-cyanoacrylate), 2-(2'-alkoxy)-ethoxyethyl-2"-cyanoacrylate (e.g., 2-(2'-methoxy) 2-(2'-ethoxy)-ethoxyethyl-2"-cyanoacrylate, 2-(2'-propoxy)-ethoxyethyl-2"-cyanoacrylate, 2-(2'-butoxy)-ethoxyethyl-2"-cyanoacrylate, 2-(2'-pentoxy)-ethoxyethyl-2"-cyanoacrylate or 2-(2'-hexyloxy)-ethoxyethyl-2"-cyanoacrylate, 2-(2'-alkoxy)-propoxypropyl-2"-cyanoacrylate (e.g., 2-(2'-methoxy)-propoxypropyl-2"-cyanoacrylate, 2-(2'- 2-(2'-propoxy)-propoxypropyl-2'-cyanoacrylate, 2-(2'-butoxy)-propoxypropyl-2'-cyanoacrylate, 2-(2'-pentoxy)-propoxypropyl-2'-cyanoacrylate, 2-(2'-hexoxy)-propoxypropyl-2'-cyanoacrylate, 2-(2'-alkoxy)-butoxybutyl-2'-cyanoacrylate (e.g., 2-(2'-methoxy)-butoxybutyl-2''-cyanoacrylate, 2-(2'-ethoxy)-butoxybutyl-2''-cyanoacrylate)2-(2'-butoxy)-butoxybutyl-2''-cyanoacrylate, 2-(3'-alkoxy)-propoxyethyl-2''-cyanoacrylate (e.g., 2-(3'-methoxy)-propoxyethyl-2''-cyanoacrylate), 2-(3'-alkoxy)-butoxyethyl-2''-cyanoacrylate (e.g., 2-(3'-methoxy)-butoxyethyl-2''-cyanoacrylate), 2-(3'-alkoxy)-propoxypropyl-2''-cyanoacrylate (e.g., 2-(3'-methoxy)-propoxypropyl-2''-cyanoacrylate), 2-(3'-alkoxy)-butoxypropyl-2''-cyanoacrylate (e.g., 2-(3'-methoxy)-butoxypropyl-2''-cyanoacrylate), 2-(3'-methoxy)-butoxypropyl-2''-cyanoacrylate (e.g., 2-(3'-methoxy)-butoxypropyl-2''-cyanoacrylate), 2-(3'-methoxy)-butoxypropyl-2''-cyanoacrylate (e.g., 2-(3'-methoxy)-butoxypropyl-2''-cyanoacrylate), 2-(2′-alkoxy)-ethoxypropyl-2″-cyanoacrylate, 2-(2′-alkoxy)-ethoxypropyl-2″-cyanoacrylate (e.g., 2-(2′-methoxy)-ethoxypropyl-2″-cyanoacrylate), 2-(2′-alkoxy)-ethoxybutyl-2″-cyanoacrylate (e.g., 2-(2′-methoxy)-ethoxybutyl-2″-cyanoacrylate), trimethylsilyl ethyl cyanoacrylate, trimethylsilyl propyl cyanoacrylate, tetrahydrofurfuryl cyanoacrylate, 1,6-hexanediol dicyanoacrylate, trimethylsilyloxyethyl cyanoacrylate, triethylsilyloxyethyl cyanoacrylate, phenyl ethyl cyanoacrylate, and mixtures thereof.

[0233] More preferably, the cyanoacrylate is a monofunctional cyanoacrylate, and more preferably is selected from 2-methoxyethyl cyanoacrylate, 2-ethoxyethyl cyanoacrylate, methyl cyanoacrylate, ethyl cyanoacrylate, n-propyl cyanoacrylate, n-heptyl cyanoacrylate, n-octyl cyanoacrylate, isopropyl cyanoacrylate, or mixtures thereof.

[0234] When the curable composition contains cyanoacrylate, the amount of cyanoacrylate may be from 70% to 99% by weight, preferably from 75% to 95% by weight, and more preferably from 70% to 90% by weight, based on the total weight of the curable composition.

[0235] The curable composition may contain (meth)acrylate-functionalized compounds. The curable composition may contain a mixture of (meth)acrylate-functionalized compounds.

[0236] As used herein, the term "(meth)acrylate-functionalized compound" refers to a compound containing a (meth)acrylate group, particularly an acrylate group. The term "(meth)acrylate-functionalized compound" herein encompasses compounds containing more than one (meth)acrylate group, such as 2, 3, 4, 5, or 6 (meth)acrylate groups, commonly referred to as "oligomers" containing (meth)acrylate groups. The term "(meth)acrylate group" includes acrylate groups (-O-CO-CH=CH2) and methacrylate groups (-O-CO-C(CH3)=CH2).

[0237] In one embodiment, the curable composition may comprise 40% to 99%, 45% to 90%, 50% to 85%, or 50% to 80% of a (meth)acrylate functionalized compound based on the total weight of the curable composition.

[0238] Alternatively, based on the total weight of the curable composition, the curable composition may contain 5% to 50% by weight, 10% to 45% by weight, 15% to 40% by weight, or 15% to 30% by weight of (meth)acrylate-functionalized compounds.

[0239] (Meth)acrylate-functionalized compounds can be selected from (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, and mixtures thereof.

[0240] As used herein, the term "(meth)acrylate-functionalized monomer" refers to a monomer containing a (meth)acrylate group, particularly an acrylate group. The term "(meth)acrylate-functionalized oligomer" refers to an oligomer containing a (meth)acrylate group, particularly an acrylate group.

[0241] In one embodiment, the olefinically unsaturated compound comprises a (meth)acrylate-functionalized monomer. The olefinically unsaturated compound may comprise a mixture of (meth)acrylate-functionalized monomers.

[0242] The molecular weight of (meth)acrylate-functionalized monomers can be less than 600 g / mol, particularly 100 to 550 g / mol, and even more particularly 200 to 500 g / mol.

[0243] (Meth)acrylate functionalized monomers may have 1 to 6 (meth)acrylate groups, particularly 1 to 3 (meth)acrylate groups.

[0244] (Meth)acrylate-functionalized monomers may comprise mixtures of (meth)acrylate-functionalized monomers with different degrees of functionality. For example, (meth)acrylate-functionalized monomers may comprise mixtures of (meth)acrylate-functionalized monomers containing a single acrylate or methacrylate group per molecule (referred to herein as "mono(meth)acrylate-functionalized compounds") and (meth)acrylate-functionalized monomers containing two or more, preferably two or three acrylate and / or methacrylate groups per molecule.

[0245] In one embodiment, the (meth)acrylate-functionalized monomer comprises a mono(meth)acrylate-functionalized monomer. The mono(meth)acrylate-functionalized monomer can advantageously be used as a reactive diluent and to reduce the viscosity of the compositions of the present invention.

[0246] Examples of suitable mono(meth)acrylate functionalized monomers include, but are not limited to, mono(meth)acrylates of aliphatic alcohols (wherein the aliphatic alcohol may be linear, branched, or alicyclic, and may be a monohydric, dihydric, or polyhydric alcohol, provided that only one hydroxyl group is (meth)acrylated); mono(meth)acrylates of aromatic alcohols (such as phenols, including alkylated phenols); mono(meth)acrylates of alkylaryl alcohols (such as benzyl alcohol); and mono(meth)acrylates of oligomeric glycols and polymeric glycols (such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol). (Meth)acrylates; mono(meth)acrylates of monoalkyl ethers of glycols and oligomeric glycols; mono(meth)acrylates of alkoxylated (e.g., ethoxylated and / or propoxylated) aliphatic alcohols (wherein the aliphatic alcohol may be linear, branched or alicyclic, and may be a monohydric alcohol, dihydric alcohol or polyhydric alcohol, provided that only one hydroxyl group of the alkoxylated aliphatic alcohol is (meth)acrylated); mono(meth)acrylates of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (such as alkoxylated phenols); caprolactone mono(meth)acrylates; etc.

[0247] The following compounds are specific examples of mono(meth)acrylate functionalized monomers suitable for the curable compositions of the present invention: methyl methacrylate; ethyl methacrylate; n-propyl methacrylate; n-butyl methacrylate; isobutyl methacrylate; n-hexyl methacrylate; 2-ethylhexyl methacrylate; n-octyl methacrylate; isooctyl methacrylate; n-decyl methacrylate; n-dodecyl methacrylate; tridecyl methacrylate; tetradecyl methacrylate; hexadecyl methacrylate; 2-hydroxyethyl methacrylate; 2- and 3-hydroxypropyl methacrylate; 2-methoxyethyl methacrylate; 2-ethoxyethyl methacrylate; 2- and 3-ethoxypropyl methacrylate; tetrahydrofurfuryl methacrylate; alkoxylated tetrahydrofurfuryl(meth)acrylate; 2-(2-ethylhexyl)methacrylate ethyl methacrylate; cyclohexyl methacrylate; glycidyl methacrylate; isodecanyl methacrylate; lauryl methacrylate; 2-phenoxyethyl methacrylate; alkoxylated phenol (meth)acrylate; alkoxylated nonylphenol (meth)acrylate; cyclic trimethylolpropane acetal (meth)acrylate; isobornyl methacrylate; tricyclodecane methanol (meth)acrylate; tert-butylcyclohexanol (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; methoxy polyethylene glycol (meth)acrylate; hydroxyethyl-butylcarbamate (meth)acrylate; 3-(2-hydroxyalkyl)azolidinone (meth)acrylate; and combinations thereof.

[0248] In one embodiment, the (meth)acrylate-functionalized monomer may comprise a (meth)acrylate-functionalized monomer containing two or more (meth)acrylate groups per molecule.

[0249] Examples of suitable (meth)acrylate-functionalized monomers containing two or more (meth)acrylate groups per molecule include acrylates and methacrylates of polyols (organic compounds containing two or more, for example, 2 to 6 hydroxyl groups per molecule). Specific examples of suitable polyols include C2-20 alkylene glycols (diols having C2-10 alkylene groups are preferred, wherein the carbon chain may be branched; for example, ethylene glycol, trimethylene glycol, 1,2-propanediol, 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-diethanol, bisphenol and hydrogenated bisphenol and their derivatives, as well as their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives, diethylene glycol, glycerol, alkoxylated glycerol, triethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, alkoxylated trimethylolpropane, bis(trimethylolpropane), alkoxylated bis(trimethylolpropane), Pentaerythritol, alkoxylated pentaerythritol, dipentaerythritol, alkoxylated dipentaerythritol, cyclohexanediol, alkoxylated cyclohexanediol, cyclohexanediethanol, alkoxylated cyclohexanediethanol, norbornenediethanol, alkoxylated norbornenediethanol, norbornenediethanol, alkoxylated norbornenediethanol, aromatic ring-containing polyols, cyclohexane-1,4-diethanol ethylene oxide adducts, bisphenol ethylene oxide adducts, hydrogenated bisphenol ethylene oxide adducts, bisphenol propylene oxide adducts, hydrogenated bisphenol propylene oxide adducts, cyclohexane-1,4-diethanol propylene oxide adducts, sugar alcohols, and alkoxylated sugar alcohols. These polyols can be completely or partially esterified (using (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.), provided that each molecule contains at least two (meth)acrylate functional groups.

[0250] Exemplary (meth)acrylate-functionalized monomers containing two or more (meth)acrylate groups per molecule may include bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; Acrylic esters; 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-diethanol di(meth)acrylate; Tricyclodecanediethanol di(meth)acrylate; Metallic di(meth)acrylates; Modified metallic di(meth)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 Tetraol 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; tri(2-hydroxyethyl) isocyanurate tri(meth)acrylate; and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives; and combinations thereof.

[0251] The curable compositions of the present invention may contain 0 to 99.5% by weight, particularly 5 to 90% by weight, more particularly 10 to 80% by weight, even more particularly 15 to 75% by weight, still more particularly 20 to 70% by weight, of (meth)acrylate-functionalized monomers, based on the total weight of the curable composition. Specifically, the curable compositions of the present invention may contain 5 to 50%, 10 to 50%, 15 to 50%, 20 to 50%, 25 to 50%, or 30 to 50% by weight of (meth)acrylate-functionalized monomers based on the total weight of the curable composition. Alternatively, the curable compositions of the present invention may contain 50 to 99.5%, 55 to 99.5%, 60 to 99.5%, 65 to 99.5%, or 70 to 99.5% by weight of (meth)acrylate-functionalized monomers based on the total weight of the curable composition.

[0252] In one embodiment, the olefinically unsaturated compound comprises (meth)acrylate-functionalized oligomers. The olefinically unsaturated compound may comprise a mixture of (meth)acrylate-functionalized oligomers.

[0253] (Meth)acrylate-functionalized oligomers can be selected to enhance properties such as flexibility, strength, and / or modulus of the cured polymers prepared using the curable compositions of the present invention.

[0254] (Meth)acrylate-functionalized oligomers may have 1 to 18 (meth)acrylate groups, particularly 2 to 6 (meth)acrylate groups, and even more particularly 2 to 6 acrylate groups.

[0255] (Meth)acrylate-functionalized oligomers can have a number average molecular weight equal to or greater than 600 g / mol, particularly 800 to 15,000 g / mol, and even more particularly 1,000 to 5,000 g / mol.

[0256] In particular, the (meth)acrylate-functionalized oligomers may be selected from epoxy (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, (meth)acrylated poly(meth)acrylates, and mixtures thereof.

[0257] Non-limiting examples of epoxy (meth)acrylates are reaction products of epoxides (e.g., glycidyl ethers, glycidyl esters, alicyclic epoxides, or epoxides obtained by epoxidation of mono- and / or polyunsaturated compounds) with (meth)acrylate esterifying agents (e.g., (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, or combinations thereof). The epoxide can be selected from 1,2,3,4-diepoxybutane; 1,2,4,5-diepoxypentane; 1,2,5,6-diepoxyhexane; 1,2,7,8-diepoxyoctane; 1,2,9,10-diepoxydecane; 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 phenolic varnish resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxy Cyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,4-dioxane, 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′-methylcyclohexane carboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexane) -Epoxycyclohexylmethyl ether, ethylene bis(3,4-epoxycyclohexane carboxylate), ethylene glycol diglycidyl ether, 1,2- or 1,3-propanediol diglycidyl ether, 1,2-, 1,3- or 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,7-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 2-methyl-1,3-propanediol diglycidyl ether Diol diglycidyl ether, neopentyl glycol diglycidyl ether, 2,2-diethyl-1,3-propanediol diglycidyl ether, 3-methyl-1,5-pentanediol diglycidyl ether, 3,3-dimethyl-1,5-pentanediol diglycidyl ether, 2,4-diethyl-1,5-pentanediol diglycidyl ether, 3,3-butylethyl-1,5-pentanediol diglycidyl ether, di, tri, or tetra(ethylene glycol) diglycidyl ether, di, tri, or tetra(1,2-propanediol) diglycidyl ether, di, tri, or tetra(1,3-propanediol) diglycidyl ether, di, tri, or tetra(1,3-propanediol) diglycidyl ether, di, tri, or tetra(1,3-propanediol) diglycidyl ether, 1,4-Butanediol) diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytrimethylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, poly(ethylene glycol-co-propylene glycol) diglycidyl ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane triglycidyl ether Di(trimethylolpropane)tetraglycidyl ether, pentaerythritol tetraglycidyl ether, cyclohexanedicarboxylic acid diglycidyl ester, cyclohexane diglycidyl ether, cyclohexane-1,4-diethanol diglycidyl ether, tricyclodecanediethanol diglycidyl ether, isosorbide diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, cardol diglycidyl ether, phloroglucinol triglycidyl ether Oil ethers, pyrogallol triglycidyl ether, tris(hydroxyphenyl)methane triglycidyl ether, tris(hydroxyphenyl)ethane triglycidyl ether, diglycidyl phthalate, diglycidyl terephthalate, diglycidyl isophthalate, polyglycidyl ethers of polyether polyols obtained by adding one or more epoxides to aliphatic polyols (such as ethylene glycol, propylene glycol, and glycerol), diglycidyl esters of aliphatic long-chain (C6-C22) diacids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of phenol, cresol, and butylphenol, or polyether alcohols obtained by adding epoxides to these compounds, glycidyl esters of higher fatty acids, epoxidized vegetable oils (such as epoxidized soybean oil and epoxidized linseed oil), epoxidized butyl stearic acid, epoxidized octyl stearic acid, epoxidized polybutadiene, triglycidyl isocyanurate, etc.

[0258] Non-limiting examples of polyester (meth)acrylates are the reaction products of hydroxyl-terminated polyester polyols with (meth)acrylate esterifying agents (e.g., (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, or combinations thereof). The reaction process can be carried out such that a significant concentration of residual hydroxyl groups is retained in the polyester (meth)acrylate, or the reaction process can be carried out such that all or substantially all of the hydroxyl groups of the polyester polyol have been (meth)acrylated. Polyester polyols can be prepared by polycondensation of a polyhydroxy functional component (particularly a diol) and a polycarboxylic acid functional compound (particularly a dicarboxylic acid or anhydride). To prepare polyester (meth)acrylates, the hydroxyl groups of the polyester polyol are then partially or completely esterified by reaction with a (meth)acrylate esterifying agent. Polyester (meth)acrylates can also be synthesized by reacting a hydroxyl-containing (meth)acrylate, such as a hydroxyalkyl (meth)acrylate (e.g., hydroxyethyl acrylate), with a polycarboxylic acid. The polyhydroxy and polycarboxylic acid functional components can each have straight-chain, branched, alicyclic, or aromatic structures, and can be used alone or as a mixture.

[0259] Non-limiting examples of polyether (meth)acrylates are the products of condensation reactions of polyether polyols with (meth)acrylate esterifying agents (e.g., (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, or combinations thereof). Suitable polyether polyols can be straight-chain or branched substances containing ether bonds and terminal hydroxyl groups. Polyether polyols can be prepared by ring-opening polymerization of epoxides and other oxygen-containing heterocyclic compounds (e.g., ethylene oxide, 1,2-epoxypropane, epoxide, tetrahydrofuran, or combinations thereof) with initiator molecules. Suitable initiator molecules include water, hydroxyl-functionalized materials, polyester polyols, and amines. Polyether alcohols can also be obtained by condensation of glycols such as ethylene glycol.

[0260] Non-limiting examples of urethane (meth)acrylates are condensation reaction products of at least one polyisocyanate (e.g., diisocyanate, triisocyanate), at least one polyol (e.g., polyether polyol or polyester polyol), and a hydroxyl-functionalized (meth)acrylate (e.g., 2-hydroxyethyl (meth)acrylate or 3-hydroxypropyl (meth)acrylate) to provide terminal (meth)acrylate groups. For example, each molecule of urethane (meth)acrylate may contain two, three, four, or more (meth)acrylate groups. The order of addition of the components in preparing urethane (meth)acrylates is well known in the art. For example, a hydroxyl-functionalized (meth)acrylate may first react with a polyisocyanate to obtain an isocyanate-functionalized (meth)acrylate, and then react it with a polyol. In yet another embodiment, the polyisocyanate may first react with a polyol to obtain an isocyanate-functionalized polyol, and then react it with a hydroxyl-functionalized (meth)acrylate. Alternatively, all components may be combined and reacted simultaneously.

[0261] Non-limiting examples of (meth)acrylated poly(meth)acrylates are substances having an oligomeric (meth)acrylate backbone functionalized with one or more (meth)acrylate groups (which may be terminal or side-attached to the acrylic backbone of the oligomer). The (meth)acrylate backbone may be a homopolymer, random copolymer, or block copolymer comprising repeating units of (meth)acrylate monomers. The (meth)acrylate monomers may be any monomeric (meth)acrylate, such as C1-C6 alkyl (meth)acrylates, and functionalized (meth)acrylates, such as (meth)acrylates with hydroxyl, carboxylic acid, and / or epoxy groups. (Meth)acrylate-esterified poly(meth)acrylates can be prepared using any procedure known in the art, for example by functionalizing at least a portion of an oligomeric (meth)acrylate monomer with hydroxyl, carboxylic acid, and / or epoxy groups (e.g., hydroxyalkyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate) to obtain a functionalized poly(meth)acrylate, which is then reacted with one or more (meth)acrylate-containing reactants to introduce the desired (meth)acrylate functional groups.

[0262] Anionic synergist

[0263] The curable composition may further comprise anionic synergists. When the curable composition comprises a cyanoacrylate-functionalized compound, the anionic synergist may be present, particularly to increase the curing rate of the cyanoacrylate-functionalized compound.

[0264] In particular, the anionic synergist can be a metallocene.

[0265] Preferred metallocenes used in this invention include those in which each aromatic electron system ligand is a π-aromatic, indenyl, or n-5-cyclopentadienyl ligand. The metallocenes may be based on transition metals selected from iron, osmium, and ruthenium. In some aspects of this invention, iron-containing metallocenes, i.e., ferrocene, are used. However, in other embodiments, the metallocene compound may be osmium dicene or ruthenium dicene. Combinations of two or more different metallocene compounds may be used.

[0266] More specifically, the anionic synergist can be ferrocene.

[0267] Ferrocene can be determined according to the following formula (VI):

[0268] (VI)

[0269] Each R is independently hydrogen or a straight-chain or branched C1-C4 alkyl group.

[0270] Specific examples of metallocenes that can be used in this invention are disclosed in US 6503959, which is incorporated herein by reference.

[0271] The amount of anionic synergist in the curable composition can be from 50 to 1000 ppm, depending on the weight of the curable composition.

[0272] acid stabilizers

[0273] The curable composition may further include an acid stabilizer. When the curable composition contains a cyanoacrylate-functionalized compound, the acid stabilizer may be present, particularly to enhance the storage stability of the curable composition and prevent premature curing.

[0274] In particular, the acid stabilizer can be a Lewis acid. Examples of suitable Lewis acids include boron trifluoride, boron trifluoride ether complexes (e.g., boron trifluoride diethyl ether complexes), boron trifluoride dihydrate, trimethylsilyl trifluoromethanesulfonate, sulfur dioxide, sulfur trioxide, nitrogen oxides, and mixtures thereof, with boron trifluoride ether complexes being the most preferred.

[0275] Other suitable types of acid stabilizers include protic acids, such as hydrogen halides (e.g., hydrogen fluoride) and sulfonic acids (e.g., p-toluenesulfonic acid).

[0276] The amount of acid stabilizer in the curable composition can be from 1 to 1000 ppm, for example from 10 to 100 ppm, based on the total weight of the curable composition.

[0277] Free radical photoinitiators

[0278] The curable composition may also contain a free radical photoinitiator, particularly a free radical photoinitiator having Norrish type I activity and / or Norrish type II activity, and more particularly a free radical photoinitiator having Norrish type I activity. The free radical photoinitiator differs from the compound of formula (I).

[0279] Non-limiting types of free radical photoinitiators suitable for curable compositions include, for example, benzoin, benzoin ether, acetophenone, α-hydroxyacetophenone, benzoinyl, benzoinyl ketal, phosphine oxide, acylphosphine oxide, α-hydroxy ketone, phenyl glyoxylate, α-amino ketone, benzoyl carbamate, acyl germanium compounds, their polymeric derivatives, and mixtures thereof, but not limited to benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-phenylbenzoin, michidone, 1-hydroxyphenyl ketone, acetophenone, 2,2-diethoxyacetophenone, benzoinyl, α-hydroxy ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2,2-dimethoxy-1,2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone, 2-hydroxy-2-methyl-1-phenylacetone. Oligomeric α-hydroxy ketones, benzoylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphine ester, anisolein, benzoin isobutyl ether, 4-benzoylbiphenyl, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 4,4'-dimethylbenzoyl, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide / 2-hydroxy-2-methylphenylacetone 50 / 50 blend, 4'-ethoxyacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, methylbenzoylcarbamate, 4'-phenoxyacetophenone, their polymer derivatives and combinations thereof.

[0280] Preferred free radical photoinitiators are acetophenone, α-hydroxyacetophenone, phosphine oxide and acylphosphine oxide, more preferably acetophenone and acylphosphine oxide.

[0281] Specifically, the free radical photoinitiator may be selected from acetophenone, such as SpeedCure® BKL (2,2-dimethoxy-1,2-phenylacetophenone); acylphosphine oxides such as SpeedCure® XKM (phenyl(2,4,6-trimethylbenzoyl)phosphine oxide), SpeedCure® BPO (phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide), SpeedCure® TPO (2,4,6-trimethylbenzoyl diphenylphosphine oxide) or SpeedCure® TPO-L ((2,4,6-trimethylbenzoyl)phenylphosphine oxide); and mixtures thereof.

[0282] The amount of free radical photoinitiator can vary appropriately depending on factors such as the selected free radical photoinitiator, the amount and type of polymerizable material present in the curable composition, the radiation source used, and the radiation conditions. However, typically, the amount of free radical photoinitiator can be 0% to 10% of the total weight of the curable composition, for example, 0.05% to 10%, particularly 0.1% to 5%, and more particularly 0.5% to 2%. For example, based on the total weight of the curable composition, the amount of free radical photoinitiator can be 0.01% to 5% by weight, 0.02% to 3% by weight, 0.05% to 2% by weight, 0.1% to 1.5% by weight, or 0.2% to 1% by weight. In another example, the amount of free radical photoinitiator can be 1% to 5%, 1.5% to 5%, 2% to 5%, 2.5% to 5%, or 3% to 5% of the total weight of the curable composition.

[0283] Free radical stabilizers

[0284] The curable composition may also contain a free radical stabilizer.

[0285] Free radical stabilizers are free radical polymerization inhibitors. They are preferably hindered phenols or polyphenol compounds; more preferably selected from hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, 2,5-di-tert-butyl-hydroquinone, p-methoxyphenol, hydroxyanisole, butylated hydroxyanisole, hydroxyanisole butyl ether, 2,6-di-tert-butyl-p-cresol, 2,2'-methylene-bis-(6-tert-butyl-4-methylphenol), p-tert-butylcatechol, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, hydroxytoluene butyl ether, and mixtures thereof; more preferably selected from hydroquinone monomethyl ether, 2,2'-methylene-bis-(6-tert-butyl-4-methylphenol), and mixtures thereof.

[0286] Based on the total weight of the curable composition, the curable composition may contain 0.01 to 0.7% by weight, preferably 0.01 to 0.5% by weight, more preferably 0.01 to 0.4% by weight of a free radical stabilizer.

[0287] solvent

[0288] Advantageously, the curable composition can be formulated as solvent-free, i.e., free of any non-reactive volatile substances. However, in some other embodiments of the invention, the curable composition may contain one or more solvents, particularly one or more organic solvents, which may be non-reactive organic solvents. In various embodiments, the solvent may be relatively volatile, for example, a solvent with a boiling point not exceeding 150 °C at atmospheric pressure. In other embodiments, the solvent may have a boiling point of at least 40 °C at atmospheric pressure.

[0289] Solvents can be selected to dissolve one or more components of the curable composition and / or to adjust the viscosity or other rheological properties of the curable composition.

[0290] However, the curable composition can alternatively be formulated to contain little or no non-reactive solvent, for example, less than 10%, less than 5%, or even 0% of non-reactive solvent based on the total weight of the curable composition. Such solvent-free or low-solvent compositions can be formulated using a variety of components, including, for example, low-viscosity reactive diluents, selected such that the viscosity of the curable composition is low enough, even in the absence of solvent, that the curable composition can be readily applied to a substrate surface at a suitable application temperature to form a relatively thin, uniform layer.

[0291] Suitable solvents may include, for example, organic solvents such as: ketones; esters; carbonates; alcohols; aromatic solvents such as xylene, benzene, toluene and ethylbenzene; alkanes; glycol ethers; ethers; amides; and combinations thereof.

[0292] In various embodiments of the invention, the curable compositions described herein are formulated to have viscosities 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, with a 27-rotor (rotor speed typically varies between 20 and 200 rpm, depending on the viscosity). In an advantageous embodiment of the invention, the viscosity of the curable composition is 200 to 1000 cPs at 25 °C.

[0293] additive

[0294] In lieu of or in addition to the ingredients described above, the curable composition may optionally contain one or more additives. Such additives include, but are not limited to, free radical chain transfer agents, antioxidants, UV absorbers, light blockers, light stabilizers, foam inhibitors, flow or leveling agents, fillers, colorants, fluorophores, pigments, dispersants (wetting agents), slip additives, plasticizers, thixotropic agents, matting agents, impact modifiers, adhesion promoters, thermoplastics such as acrylic resins without any free radical polymerizable functional groups, waxes, or other various additives, including any additives conventionally used in the fields of coatings, sealants, adhesives, molding, 3D printing, or inks.

[0295] use

[0296] The present invention also relates to the use of compounds of formula (I) as photoinitiators as described above. In particular, compounds of formula (I) can be used as photoinitiators with photobleaching properties.

[0297] The compound of formula (I) can be used as a photoinitiator, which can be activated by irradiation with an LED light source, preferably with a maximum output wavelength in the range of 250 to 550 nm, particularly 250 to 460 nm, and even more particularly 340 to 430 nm.

[0298] The photoinitiator of this invention has potential applications in photocurable inks, coatings, adhesives, advanced materials, electronics, and additive manufacturing (3D printing).

[0299] This invention particularly relates to the use of a compound of formula (I) as a photoinitiator for curing formulations comprising one or more olefinically unsaturated compounds that can be polymerized by free radical, anionic, and mixed anionic / free radical polymerization. The olefinically unsaturated compounds may be as described above for curable compositions.

[0300] Surprisingly, the compounds of formula (I) are not subject to oxygen inhibition. They advantageously exhibit high curing speed, low yellowing and / or photobleaching properties, and high thermal stability in formulations. Yellowing properties can be measured by the color index "b" value on the cured film.

[0301] Curing methods and cured products

[0302] The present invention also relates to a method for curing one or more olefinically unsaturated compounds, the method comprising:

[0303] Mixing one or more olefinically unsaturated compounds with a compound of formula (I) according to the invention; and

[0304] The mixture is irradiated with at least one light source.

[0305] The light source is typically an LED (light-emitting diode) light source, or a broadband lamp with a filter that limits the emission to wavelengths in the range of 250 to 550 nm, particularly 250 to 460 nm.

[0306] Preferably, the light source is an LED light source, more preferably an LED light source with a maximum output wavelength in the range of 250 to 550 nm, particularly 250 to 460 nm. The maximum output wavelength of the LED light source can be 350 to 450 nm, particularly 340 to 430 nm, and even more preferably 250 nm, 365 nm, 385 nm or 405 nm.

[0307] Since the photoactivity of the compound of formula (I) is not altered by oxygen, no specific precautions are required to prevent contact with oxygen during the curing process. According to one embodiment, irradiation can be carried out in air or in an inert atmosphere, preferably in air.

[0308] The present invention also relates to a method for preparing a cured product, comprising curing a curable composition as defined above, preferably by irradiating the composition with at least one light source.

[0309] The light source can be defined as described above for the curing process.

[0310] When exposed to a light source, the curable composition may be stationary. Alternatively, when exposed to a light source, the curable composition may be in motion (e.g., on a conveyor belt).

[0311] Curing can be accelerated or promoted by providing energy to the curable composition, for example, by heating the curable composition. Therefore, the cured product can be considered as the reaction product of the curable composition formed through curing. The curable composition can be partially cured by exposure to photochemical radiation, wherein further curing is achieved by heating the partially cured article. For example, a product formed from a curable composition can be heated at a temperature of 40 °C to 120 °C for a period of 5 minutes to 12 hours.

[0312] Prior to curing, the curable composition can be applied to the substrate surface in any known conventional manner, such as by spraying, jetting, scraping, rolling, casting, drum coating, dipping, and combinations thereof. Indirect application using a transfer process can also be used. The substrate can be any commercially relevant substrate, such as a high surface energy substrate or a low surface energy substrate, for example, a metal substrate or a plastic substrate, respectively. The substrate can include metals, paper, cardboard, glass, thermoplastics such as polyolefins, polycarbonates, acrylonitrile butadiene styrene (ABS) and blends thereof, composite materials, wood, leather, and combinations thereof. When used as an adhesive, the curable composition can be placed between two substrates and then cured, thereby bonding the substrates together to provide an adhered article. The curable composition according to the invention can also be formed or cured in bulk (e.g., the curable composition can be cast into a suitable mold and then cured).

[0313] The cured product obtained by the method of the present invention can be an ink, coating, sealant, adhesive, molded product or 3D printed product.

[0314] The following embodiments and accompanying drawings illustrate the present invention. Attached Figure Description

[0315] Figure 1 The concentration of 10 in dichloromethane is shown.-4 UV absorption in dichloromethane by M-based thioester coumarin photoinitiator.

[0316] Figure 2 This shows a concentration of 10 under 385 nm LED exposure. -4 Photolysis of M’s thioester-based coumarin photoinitiator in dichloromethane.

[0317] Figure 3 The conversion rates of photopolymerization of TMPTA at 385 nm using comparative photoinitiators (coumarins with aliphatic or aromatic substituents and the prior art Speedcure TPO-L) are shown.

[0318] Figure 3 a shows the reactivity of the photoinitiator in the laminated material.

[0319] Figure 3 b shows the reactivity of the photoinitiator in air.

[0320] Figure 4 The photobleaching ability of photoinitiators (coumarins with aliphatic or aromatic substituents and the prior art Speedcure TPO-L) compared with SR454 (ethoxylated TMPTA) at 385 nm is shown.

[0321] Figure 4 a shows the reactivity of the photoinitiator in the laminated material.

[0322] Figure 4 b shows the reactivity of the photoinitiator in air.

[0323] Example

[0324] Example 1: Preparation of compound (I)

[0325] Example 1a: S-5,7-dimethoxy-2-oxo-2H-chromene-3-thiocarbonate cyclohexyl ester

[0326]

[0327] 5,7-Dimethoxy-2-oxo-2H-chromene-3-carboxylic acid (200 mg, 0.79 mmol, 1 eq.) was dissolved in thionyl chloride (0.8 mL) and DMF (4 drops) in a round-bottom flask and stirred at 80°C for 2 hours under nitrogen. The mixture was evaporated to dryness to give crude acylchlorocoumarin. This solid was dissolved in anhydrous THF (2 mL). Meanwhile, anhydrous THF (4 mL) was placed in a three-necked flask, thoroughly rinsed with nitrogen, and cooled at 0°C. Triethylamine (0.33 mL, 2.39 mmol, 3 eq.), cyclohexanethiol (0.20 mL, 1.59 mmol, 2 eq.), and the acyl chloride were added, and the mixture was gradually warmed to room temperature and stirred overnight. The reaction was then slowly quenched in ice / water, and the resulting solid was filtered and washed with water. The solid was then placed in a flask and suspended in dichloromethane (50 mL) with stirring. The organic phase was extracted with water (50 mL) / 1M HCl (10 mL) (pH 3), then with NaHCO3 solution (50 mL), and finally with water (50 mL). The product was dried over MgSO4, filtered, and the solvent was removed under reduced pressure to give a solid. Diethyl ether (25 mL) was added to the solid and the mixture was stirred for 3 hours to remove residual thiols. The solid was filtered, washed with diethyl ether (5 mL), and dried to give S-5,7-dimethoxy-2-oxo-2H-chromene-3-thiocarbonate, a pale yellow solid (98 mg, 35%).

[0328] Example 1b: S-5,7-dimethoxy-2-oxo-2H-chromene-3-thiopropyl carbonate

[0329]

[0330] 5,7-Dimethoxy-2-oxo-2H-chromene-3-carboxylic acid (200 mg, 0.79 mmol, 1 eq.) was dissolved in thionyl chloride (0.8 mL) and DMF (4 drops) in a round-bottom flask and stirred at 80°C for 2 hours under nitrogen. The mixture was evaporated to dryness to give crude acylchlorocoumarin. This solid was dissolved in anhydrous THF (2 mL). Meanwhile, anhydrous THF (4 mL) was placed in a three-necked flask, thoroughly rinsed with nitrogen, and cooled at 0°C. Triethylamine (0.33 mL, 2.39 mmol, 3 eq.), 1-propanethiol (0.15 mL, 1.59 mmol, 2 eq.), and the acyl chloride were added, and the mixture was gradually warmed to room temperature and stirred overnight. The reaction was then slowly quenched in ice / water, and the resulting solid was filtered and washed with water. The solid was then placed in a flask and suspended in dichloromethane (50 mL) with stirring. The organic phase was extracted with water (50 mL) / 1M HCl (10 mL) (pH 3), followed by extraction with NaHCO3 solution (50 mL), and finally with water (50 mL). The product was dried over MgSO4, filtered, and the solvent was removed under reduced pressure to obtain a solid. Diethyl ether (25 mL) was added to the solid and the mixture was stirred for 3 hours to remove residual thiols. The solid was filtered, washed with diethyl ether (5 mL), and dried to give S-5,7-dimethoxy-2-oxo-2H-chromene-3-thiopropyl carbonate as a yellow solid (94 mg, 38%).

[0331] Example 1c: S,S'-(oxybis(ethane-2,1-diyl))bis(2-oxo-2H-chromene-3-thiocarbonate)

[0332]

[0333] Coumarin-3-carboxylic acid (500 mg, 2.63 mmol, 1 eq.) was dissolved in 0.96 mL of thionyl chloride in a round-bottom flask and stirred at 80 °C for 4 hours under nitrogen. The mixture was evaporated to dryness to give crude acylchlorocoumarin.

[0334] The product was dissolved in anhydrous dichloromethane (7 mL). Under nitrogen atmosphere, bis(2-mercaptoethyl) ether (0.16 mL, 1.32 mmol, 0.5 eq.) and K₂CO₃ (1.10 g) were added to the mixture and stirred for 24 hours. The reaction mixture was filtered and evaporated under reduced pressure. The residue was purified by silica gel column chromatography (cyclohexane / ethyl acetate 10:1 to 10:5) to give S,S'-(oxybis(ethane-2,1-diyl))bis(2-oxo-2H-chromene-3-thiocarbonate) as a white solid (104 mg, 16%).

[0335] Reference Example Ref 1: S-(4-isopropylphenyl)5,7-dimethoxy-2-oxo-2H-chromene-3-thiocarbonate

[0336]

[0337] 5,7-Dimethoxy-2-oxo-2H-chromene-3-carboxylic acid (102 mg, 0.41 mmol, 1 eq.) was dissolved in thionyl chloride (0.41 mL) and DMF (2 drops) in a round-bottom flask and stirred at 80°C for 2 hours under nitrogen. The mixture was evaporated to dryness to give crude acylchlorocoumarin. This solid was dissolved in anhydrous THF (1 mL). Meanwhile, anhydrous THF (2 mL) was placed in a three-necked flask, thoroughly rinsed with nitrogen, and cooled at 0°C. Triethylamine (0.17 mL, 1.23 mmol, 3 eq.), 4-isopropylphenylthiol (0.13 mL, 0.82 mmol, 2 eq.), and the acyl chloride were added, and the mixture was gradually warmed to room temperature and stirred overnight. The reaction was then slowly quenched in ice / water, and the resulting solid was filtered and washed with water. The solid was then placed in a flask and suspended in dichloromethane (50 mL) with stirring. The organic phase was extracted with water (50 mL) / 1M HCl (10 mL) (pH 3), followed by extraction with NaHCO3 solution (50 mL), and finally with water (50 mL). The product was dried over MgSO4, filtered, and the solvent was removed under reduced pressure to obtain a solid. Diethyl ether (25 mL) was added to the solid and the mixture was stirred for 3 hours to remove residual thiols. The solid was filtered, washed with diethyl ether (5 mL), and dried to give S-(4-isopropylphenyl)-5,7-dimethoxy-2-oxo-2H-chromene-3-thiopropyl carbonate as a yellow solid (52 mg, 33%).

[0338] Example 2: Properties of Exemplary Compounds

[0339] 2.1 UV absorption

[0340] Figure 1 The figure shows a concentration of 10 in dichloromethane. -4 UV absorption in dichloromethane by M-based thioester coumarin photoinitiators (Examples 1a, 1b and Reference Example Ref 1).

[0341] Figure 1 Coumarin-based photoinitiators with aliphatic substituents were shown to have good absorbance at up to 425 nm. This makes them suitable and sufficiently reactive for use in formulations cured under LED conditions.

[0342] 2.2 Photolysis

[0343] Figure 2 The diagram shows a concentration of 10 under 385 nm LED exposure. -4 The photolysis results of M's thioester coumarin-based photoinitiator (Examples 1a, 1b and Reference Example Ref 1) in dichloromethane.

[0344] Figure 2 It was shown that coumarin-based photoinitiators with aliphatic substituents can undergo significant photodegradation after irradiation at LED wavelengths.

[0345] Example 3: Curing properties of the compound from Example 1

[0346] The curing properties of thioester-based coumarin-based photoinitiators (Examples 1a, 1b and Reference Example Ref 1) and the prior art Speedcure TPO-L, measured using real-time FTIR, are shown in the figure. Figure 3 and Figure 4 middle.

[0347] Dissolve the photoinitiator at 1% in trimethylolpropane triacrylate (TMPTA) or ethoxylated trimethylolpropane triacrylate (SR454) at room temperature and stir overnight.

[0348] The photosensitive formulation was deposited on a polypropylene film, and the sample thickness was controlled using calibration rods (24 µm, 12 µm, or 6 µm). A 385 nm (I0 = 160 mW·cm⁻¹) solution was used at room temperature. -2 The exposed LEDs polymerize the sample in air or in a laminate (between two polypropylene films).

[0349] For free radical polymerization, for thin samples, real-time Fourier transform infrared (FTIR) spectroscopy (JASCO FTIR6600) was used at approximately 1630 cm⁻¹. -1 The evolution of acrylate functional groups or double bond content will be continuously tracked.

[0350] Conversion rate was measured over time. Results are shown in... Figure 3 and Figure 4 middle.

[0351] Figure 3 a shows the reactivity of Examples 1a and 1b in TMPTA at 385 nm under lamination, compared to Reference Example 1 and Speedcure TPO-L. Figure 3 b shows the reactivity of Examples 1a and 1b in TMPTA at 385 nm in air compared to Reference Example 1 and Speedcure TPO-L.

[0352] Among laminated materials, TPO-L is the best performer with the highest acrylate conversion rate, followed by aromatic coumarins.

[0353] However, in the air ( Figure 3 b) Coumarins with aliphatic substituents (Examples 1a and 1b) were unexpectedly superior to Reference Example 1 and TPO-L.

[0354] When moved from the laminate to the air, TPO-L reduces the conversion rate of acrylates (i.e., is inhibited by oxygen), while the aliphatic coumarins of the present invention exhibit the opposite effect.

[0355] Figure 4 a-4b illustrates the use of SR454 (ethoxylated TMPTA) instead of TMPTA as an olefinically unsaturated compound. Figure 3 The same information as a-3b.

[0356] Ethoxylation of TMPTA did reveal some differences. TPO-L showed the best performance across all wavelengths in the laminate, with the highest acrylate conversion, followed by aromatic coumarins. Also in air, the acrylate conversion of TPO-L decreased, while aliphatic coumarins exhibited the highest acrylate conversion after 200 s of irradiation.

[0357] In transmission experiments, a spectrophotometer from Thorlabs was used to measure the L of the photosensitizing formulation before and after photopolymerization. a b Values. The photobleaching ability of each coumarin relative to TPO-L at 385 nm was also investigated. The values ​​are detailed in Table 1 below.

[0358]

[0359] These results demonstrate that, unlike the prior art Speedcure TPO-L, the photoinitiators according to the present invention are effective photoinitiators under LED lighting conditions and are not inhibited by oxygen. Furthermore, they exhibit photobleaching properties and achieve higher acrylate conversion rates compared to aromatic coumarin thioesters.

Claims

1. A compound of formula (I): (I) in n is 1 or 2; X represents S, Se, or Te; Each R 1 R 2 R 3 R 4 and R 5 Independently selected from H, -OH, -SH, halogen, straight-chain or branched -(C1-C) 20 )alkyl, straight-chain or branched -(C1-C 20 ) Haloalkyl, -(C1-C 20 Perfluoroalkyl, straight-chain or branched -(C2-C) 20 Alkenyl, straight-chain or branched -O(C1-C) 20 )alkyl, straight-chain or branched -S(C1-C 20 )alkyl, -(C3-C 12 )cycloalkyl, -(C5-C 12 )Aryl, -O(C5-C 12 )Aryl, -S(C5-C 12 )Aryl, -(C1-C 20 )-alkylene-(C5-C 12 )Aryl, -(C5-C 12 )-Aspartic-(C1-C 20 Alkyl, -NO2, -CN, -C(=O)OR a -OC(=O)R b -C(=O)R c -NR d R e and -C(=O)NR d R e Or two adjacent R 2 R 3 R 4 and R 5 The groups can form 3- to 12-membered aliphatic rings or 5- to 12-membered aromatic rings with the carbon atoms they are attached to; wherein R a R b R d and R e Same or different, independently selected from H and straight or branched -(C1-C 20 )alkyl; and R c Selected from straight or branched -(C1-C 20 )alkyl and -(C5-C 12 )aryl group, optionally surrounded by -OH, -SH, halogen, straight-chain or branched -(C1-C 20 )alkyl, straight-chain or branched -(C1-C 20 ) Haloalkyl, -(C1-C 20 Perfluoroalkyl, straight-chain or branched -(C2-C) 20 Alkenyl, straight-chain or branched -O(C1-C) 20 )alkyl, straight-chain or branched -S(C1-C 20 )alkyl, -NR d R e One or more substitutions of -NO2 and -CN; R can be chosen freely from the following: -Straight chain or branched chain-(C1-C) 20 Alkyl groups, wherein the alkyl group is optionally interrupted by one or more groups selected from -O-, -C(=O)- and -S-, and wherein the alkyl group is optionally selected from -OH, -SH, halogens, straight-chain or branched -O(C1-C) groups. 20 )alkyl, straight-chain or branched -S(C1-C 20 )alkyl, -(C3-C 12 )cycloalkyl, -(C5-C 12 )Aryl, -O(C5-C 12 )Aryl, -S(C5-C 12 )Aryl, -NO2, -CN, -CF3, -C(=O)OR a -OC(=O)R b -C(=O)R c -NR d R e and -C(=O)NR d R e One or more groups are substituted, wherein R is a group that is substituted for R. a R b R c R d and R e As defined above; -Straight chain or branched chain-(C2-C) 20 An alkenyl group, wherein the alkenyl group is optionally interrupted by one or more groups selected from -O- and -C(=O)-, and the alkenyl group is optionally selected from -OH, -SH, halogen, straight-chain or branched -O(C1-C)-. 20 )alkyl, straight-chain or branched -S(C1-C 20 )alkyl, -(C3-C 12 )cycloalkyl, -(C5-C 12 )Aryl, -O(C5-C 12 )Aryl, -S(C5-C 12 )Aryl, -NO2, -CN, -CF3, -C(=O)OR a -OC(=O)R b -C(=O)R c -NR d R e and -C(=O)NR d R e One or more groups are substituted, wherein R is a group that is substituted for R. a R b R c R d and R e As defined above; -(C3-C 12 ) cycloalkyl group, wherein the cycloalkyl group is optionally interrupted by one or more heteroatoms independently selected from O, N, and S, and wherein the cycloalkyl group is optionally selected from -OH, -SH, halogen, straight-chain or branched -(C1-C 20 )alkyl, straight-chain or branched -(C1-C 20 ) Haloalkyl, -(C1-C 20 Perfluoroalkyl, straight-chain or branched -(C2-C) 20 Alkenyl, straight-chain or branched -O(C1-C) 20 )alkyl, straight-chain or branched -S(C1-C 20 )alkyl, -(C5-C 12 )Aryl, -O(C5-C 12 )Aryl, -S(C5-C 12 )Aryl, -NO2, -CN, -C(=O)OR a -OC(=O)R b -C(=O)R c -NR d R e and -C(=O)NR d R e One or more groups are substituted, wherein R is a group that is substituted for R. a R b R c R d and R e As defined above; and - Group of formula (II) (II) Where X and R 1 R 2 R 3 R 4 R 5 and n are as defined above; L is a (m+1) valence connector; m can be 1 to 10, preferably 1 to 6.

2. The compound according to claim 1, wherein R 1 It is H, and R 2 R 3 R 4 and R 5 Independently selected from H, straight-chain or branched -O(Cl-C) 20 )alkyl and -NR d R e , where R d and R e Independently, it can be either straight or branched -(C1-C 20 )alkyl.

3. The compound according to claim 1 or 2, wherein R 1 R 2 R 3 and R 5 It is H, and R 4 Is it a straight-chain or branched -O(C1-C) 20 Alkyl groups, preferably methoxy groups.

4. The compound according to any one of claims 1 to 3, wherein R 1 R 3 and R 5 It is H, and R 2 and R 4 Each of them is independently a straight-chain or branched -O(C1-C) 20 Alkyl groups, preferably methoxy groups.

5. The compound according to any one of claims 1 to 4, wherein R is selected from straight-chain or branched -(C1-C1) compounds. 20 alkyl, cyclopentyl, cyclohexyl, tetrahydrofuranyl, methyltetrahydrofuranyl, and tetrahydropyranyl, wherein the alkyl group is optionally interrupted by one or more groups selected from -O- and -S-, and wherein the alkyl group is optionally selected from -(C5-C60) 12 )Aryl, -C(=O)OR a and -NR d R e One or more groups are substituted, wherein R is a group that is substituted for R. a R d and R e As defined above, the cyclohexyl group is optionally selected from -OH, -SH, halogen, straight-chain or branched -(C1-C) groups. 20 )alkyl, straight-chain or branched -(C1-C 20 ) Haloalkyl, -(C1-C 20 Perfluoroalkyl, straight-chain or branched -(C2-C) 20 Alkenyl, straight-chain or branched -O(C1-C) 20 )alkyl, straight-chain or branched -S(C1-C 20 )alkyl, -(C5-C 12 )Aryl, -O(C5-C 12 )Aryl, -S(C5-C 12 )Aryl, -NO2, -CN, -C(=O)OR a -OC(=O)R b -C(=O)R c -NR d R e and -C(=O)NR d R e One or more groups are substituted, wherein R is a group that is substituted for R. a R b R c R d and R e As defined in claim 1.

6. The compound according to any one of claims 1 to 4, wherein R is according to formula (II): (II) L is selected from aromatic linkers, aliphatic linkers, alicyclic linkers, polyether linkers, polysulfide linkers, polyester linkers, polyorganosiloxane linkers, polybutadiene linkers, and combinations thereof.

7. The compound according to claim 6, wherein L is selected from: - Based on the divalent part of any one of equations (L0) to (L7): -CH2-CH2-O-CH2-O-CH2-CH2-[S-S-CH2-CH2-O-CH2-O-CH2-CH2] a -(L0) -(CR 6 R 7 ) a - (L1) -[(CR 8 R 9 ) b -W] c -(CR 8 R 9 ) b - (L2) -[(CR 10 R 11 ) d -W] e -(CR 12 R 13 ) f -[W-(CR 10 R 11 ) d ] e - (L3) -[(CR 14 R 15 ) g -O-C(=O)-(CR 16 R 17 ) h -C(=O)-O] i -(CR 14 R 15 ) g - (L4) -(CR 18 R 19 ) j -C(=O)-O-(CR 20 R 21 ) k -O-C(=O)-(CR 18 R 19 ) j - (L5) -(CR 22 R 23 ) l -Cy-[A-Cy] o -(CR 22 R 23 ) l - (L6) in: in: - R 6 R 7 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 22 and R 23 It is independently H or alkyl; - R 8 R 9 R 10 and R 11 It is either H or methyl independently; - Each R 24 It is independently alkyl, haloalkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkylaryl, alkoxy, or aryloxy; - Each W is independently O or S; - Each Cy is an optionally substituted ring, particularly an optionally substituted arylene or optionally substituted cycloalkylene; - A is a bond or linker, such as -O-, -S-, Alk, -C(=O)-, -C(=O)-O-Alk-OC(=O)-, -SO-, -SO2-, -C(=CCl2)- and -Alk-Ph-Alk-; - Each Alk is independently an optionally substituted alkylene group; - Ph is an optionally substituted phenylene; - Each B is independently a bond or hydrocarbon linker, which is optionally interrupted by one or more functional groups selected from -O-, -(C=O)-, -(C=O)-O- and -O-(C=O)-; - a Integers from 1 to 50; - a, f, g, h, and k are independent integers from 2 to 20; - Each l is an independent integer from 0 to 20; - b and d are independent integers from 2 to 4; - o is an integer equal to 0 or 1; - c, i, and j are independent integers from 1 to 20; - Each e is an independent integer from 0 to 20, provided that at least one e is not 0; - p is between 0 and 100; - The trivalent part of any one of equations (L8) to (L11): (L8) (L9) (L10) (L11) in: - Each R 25 and R 26 Independently alkylene; - R 27 It is H, alkyl or alkoxy, preferably R. 27 It is H or alkyl; - Each R 28 Independently alkylene; - Each q is an independent integer equal to 0 or 1; - Each r is an independent integer from 0 to 2, provided that no more than one r is equal to 0, preferably each r is equal to 1 or one r is equal to 0 and the other two r are equal to 1; - According to the tetravalent part of equation (L12) or (L13): (L12) (L13) in: - Each R 29 and R 31 Independently alkylene; - Each R 30 Independently H, alkyl or alkoxy, preferably R 30 It is an alkyl group; - Each s is an independent integer from 0 to 2, provided that no more than one s is equal to 0, preferably each f is equal to 1; - According to the hexavalent part of equation (L14): (L14) Each R 32 Alkylenes that are independently straight-chain or branched; in Alkyl refers to a straight-chain or branched -(C1-C2) group. 20 )alkyl, Alkylene refers to straight-chain or branched -(C1-C2) alkylene groups. 20 )alkylene-, Alkyl groups refer to straight-chain or branched -O (C1-C2) groups. 20 )alkyl; Aryl refers to -(C5-C 12 aryl; Alkenyl refers to a straight-chain or branched -(C2-C) group. 20 alkenyl; Cycloalkyl refers to -(C3-C 12 )cycloalkyl; Alkyl aryl refers to -(C5-C 12 )-Aspartic-(C1-C 20 )alkyl; Aryl groups refer to -(C1-C 20 )-alkylene-(C5-C 12 aryl; "Optionally substituted" means that there is no substituent or one or more substituents selected from the following: -OH, -SH, halogen, straight-chain or branched -(C1-C2) substituents. 20 )alkyl, straight-chain or branched -(C1-C 20 ) Haloalkyl, -(C1-C 20 Perfluoroalkyl, straight-chain or branched -(C2-C) 20 Alkenyl, straight-chain or branched -O(C1-C) 20 )alkyl, straight-chain or branched -S(C1-C 20 )alkyl, -(C3-C 12 )cycloalkyl, -(C5-C 12 )Aryl, -O(C5-C 12 )Aryl, -S(C5-C 12 )Aryl, -(C1-C 20 )-alkylene-(C5-C 12 )Aryl, -(C5-C 12 )-Aspartic-(C1-C 20 Alkyl, -NO2, -CN, -C(=O)OR a -OC(=O)R b -C(=O)R c -NR d R e and -C(=O)NR d R e , where R a R b R c R d and R e As defined above.

8. The compound according to any one of claims 1 to 7, wherein X is S.

9. A method for preparing a compound according to any one of claims 1 to 8, the method comprising reacting a compound having formula (III) with a compound having formula (IV) or (V): (III) (IV) (V) in n, R 1 R 2 R 3 R 4 and R 5 As defined in any one of claims 1 to 4; G is an OH atom, a halogen atom, or -OC(=O)-J; J is alkyl or aryl, especially tert-butyl; R is a straight chain or branched chain as defined in claim 1 or 5 -(C1-C) 20 )alkyl or -(C3-C 12 )cycloalkyl; X is as defined in claim 1 or 8; L is defined as in any one of claims 1, 6, and 7; m is defined in claim 1.

10. A curable composition comprising: - One or more compounds of formula (I) according to any one of claims 1 to 8; and - One or more olefinically unsaturated compounds.

11. The curable composition according to claim 10, wherein the one or more olefinically unsaturated compounds include at least one of cyanoacrylate-functionalized compounds, (meth)acrylate-functionalized compounds, and mixtures thereof.

12. The curable composition according to claim 10 or 11, wherein the curable composition further comprises an anionic synergist, particularly a metallocene, and more particularly a ferrocene.

13. Use of the compound according to any one of claims 1 to 8 as a photoinitiator, particularly as a photoinitiator having photobleaching properties.

14. The use according to claim 13, wherein the photoinitiator can be activated by irradiation with an LED light source, preferably an LED light source with a maximum output wavelength in the range of 250 to 550 nm, particularly 250 to 460 nm, and more particularly 340 to 430 nm.

15. A method for curing one or more olefinically unsaturated compounds, the method comprising: - mixing one or more olefinically unsaturated compounds with a compound as defined in any one of claims 1 to 9; and - Irradiate the mixture with at least one light source, preferably at least one LED light source, more preferably at least one LED light source with a maximum output wavelength in the range of 250 to 550 nm, particularly 250 to 460 nm, and even more particularly 340 to 430 nm.

16. The method of claim 15, wherein the irradiation is performed in air or in an inert atmosphere, preferably in air.

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