Polymerizable flame retardants

Abstract

The present invention relates to non-halogen and non-metallic polymerizable flame retardants, their preparations, compositions containing them, and their use. These flame retardants are polymerized with other ethylenically unsaturated compounds and chemically bonded to the resin matrix, thus limiting their migration from the final product. The flame retardants of the present invention are also more environmentally friendly than traditional halogen or metal flame retardants.

Description

[Technical field]

[0001] The present invention relates to non-halogen and non-metallic polymerizable flame retardants, their preparations, compositions containing them, and their use. These flame retardants are polymerized with other ethylenically unsaturated compounds and chemically bonded to the resin matrix, thus limiting their migration from the final product. The flame retardants of the present invention are also more environmentally friendly than traditional halogen or metal flame retardants. [Background technology]

[0002] Electrical and electronic devices have become part of everyday life, with many appliances and electronic devices being used in professional and personal activities. These devices are becoming smaller, more compact and more efficient, but they also create more heat and fire risks. This risk can be mitigated by incorporating flame retardants into coatings and adhesives. Flame retardants can act, for example, by causing rapid extinguishing of the flame or by making the product less likely to catch fire. However, most flame retardants are based on halogens or metals, which are harmful to the environment and human life.

[0003] Phosphorus-containing compounds have also been developed as alternatives to halogen-based and metal-based flame retardants. For example, U.S. Patent No. 6,329,451 discloses a flame-retardant plastic resin composition using surface-coated and stabilized red phosphorus. U.S. Patent No. 6,822,025 discloses a flame-retardant resin composition containing an organic phosphorus additive. U.S. Patent No. 9,714,340 discloses a flame-retardant polyphenylene ether resin containing an organic phosphorus additive.

[0004] However, these phosphorus-containing flame retardants are essentially non-reactive additives that may migrate and / or volatilize from the cured product over time, causing a loss of flame retardant properties. It is therefore desirable to provide a phosphorus-based flame retardant that contains at least one (meth)acrylate group. The (meth)acrylated flame retardants of the present invention can be suitably combined with ethylenically unsaturated compounds, such as (meth)acrylate monomers and / or oligomers, without any compatibility issues, and can be fully integrated into the cured polymer matrix after exposure to radiation, such as UV, near UV and / or visible radiation. Such compounds are particularly useful for the preparation of radiation-curable formulations that have flame retardant properties and low amounts of extractables. Moreover, the incorporation of these compounds does not impair the curing of the composition or the final properties of the cured product. Summary of the Invention

[0005] The first object of the present invention is to provide a polymerizable flame retardant, - 1 or 2 (meth)acrylate-containing moieties, - one phosphorus-containing moiety containing two or more phosphorus atoms, and optionally one or more urethane or ester bonds It is a polymerizable flame retardant comprising:

[0006] Another object of the present invention is a method for preparing a polymerizable flame retardant which is a reaction product of at least one phosphorus-containing compound, at least one (meth)acrylate-containing alcohol, and at least one compound selected from diisocyanates, diisocyanate derivatives, diacids, diesters, and cyclic anhydrides. In particular, the polymerizable flame retardant is a reaction product of at least one phosphorus-containing compound, at least one (meth)acrylate-containing alcohol, and at least one diisocyanate or diisocyanate derivative.

[0007] Another object of the present invention is to provide a) a polymerizable flame retardant according to the invention or prepared according to the process of the invention, b) Ethylenically unsaturated compounds other than a) A polymerizable composition comprising:

[0008] Another object of the present invention is the use of a polymerizable flame retardant according to the invention or prepared according to the process of the present invention in a radiation-curable composition, in particular a UV- or LED-curable composition.

[0009] Another object of the present invention is the use of a polymerizable flame retardant according to the invention or prepared according to the process of the present invention to obtain a cured product having improved flame retardancy and / or improved heat resistance and / or reduced amount of extractables.

[0010] Another object of the present invention is a substrate to which the polymerizable composition according to the present invention has been applied, in particular the substrate being cellulosic materials, wool, fur, silk, leather, metal, natural and / or synthetic stone, ceramic, glass, brick, concrete, drywall, roofing shingles, asphalt, fiberglass, mineral wool, thermoplastic materials, thermoset materials, polymer composites and combinations thereof. [Brief description of the drawings]

[0011] [Figure 1] The flame retardant grades G0, G1, G2, G3, G4, and G5 are visually evaluated and the corresponding ones for each grade G1 to G5 are shown. [Figure 2a] It is shown that the film obtained using the polymerizable flame retardant PRO32403 as the only ethylenically unsaturated compound had good flame retardancy. [Figure 2b] It is shown that the film obtained using the polymerizable flame retardant PRO32351 as the only ethylenically unsaturated compound had good flame retardancy. [Figure 2c] It is shown that the film obtained using the polymerizable flame retardant PRO32362 as the only ethylenically unsaturated compound had good flame retardancy. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

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

[0014] As used herein, terms such as "flame retardant," "flame resistant," "heat retardant," and "heat resistant" refer to the ability to withstand flame or heat without ignition.

[0015] The term "aryl" refers to an optionally substituted polyunsaturated aromatic group. An aryl may contain a single ring (i.e., phenyl) or two or more rings, with at least one ring being aromatic. When an aryl contains two or more rings, the rings may be fused and linked via a covalent bond (e.g., biphenyl). The aromatic ring may optionally contain one to two additional fused rings (i.e., cycloalkyl, heterocycloalkyl, or heteroaryl). Examples include phenyl, naphthyl, biphenyl, phenanthrenyl, and naphthacenyl.

[0016] The term "alkyl" refers to a group of the formula -C n H 2n+1 where n is 1 to 20. The alkyl can be straight or branched chain. C1-C12 alkyl refers to an alkyl having 1 to 12 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, and the like.

[0017] The term "halogen" means an atom selected from Cl, Br, F and I.

[0018] The term "cycloalkyl" means a monovalent saturated alicyclic hydrocarbon group containing a ring. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and isobornyl.

[0019] The term "heterocycloalkyl" means a cycloalkyl having at least one ring atom which is a heteroatom selected from O, N, or S.

[0020] The term "alkoxy" means a group of the formula -O-alkyl, where alkyl is as defined above. C1-C12 alkoxy refers to an alkoxy group having from 1 to 12 carbon atoms.

[0021] The term "aryloxy" means a group of the formula -O-aryl, where aryl is as defined above.

[0022] The term "alkylaryl" means an alkyl substituted with an aryl group. An example of an alkylaryl group is benzyl (-CH2-phenyl).

[0023] The term "alkylaryloxy" means a radical of the formula -O-alkylaryl, where alkylaryl is as defined above.

[0024] The term "heteroaryl" means an aryl having at least one ring atom which is a heteroatom selected from O, N, or S.

[0025] The term "linker" refers to a multivalent group. A linker may connect at least two parts of a compound together, in particular two to six parts of a compound together. For example, a linker that connects two parts of a compound together is called a bivalent linker, a linker that connects three parts of a compound together is called a trivalent linker, etc. The term "(a+1)-valent linker" refers to a linker that has a valency equal to a+1, i.e., a linker that connects a+1 parts of a compound together.

[0026] The term "hydrocarbon linker" refers to a linker having a carbon backbone chain that may be optionally interrupted by one or more heteroatoms selected from N, O, S, Si and mixtures thereof. The hydrocarbon linker may be aliphatic, alicyclic or aromatic. The hydrocarbon linker may be saturated or unsaturated. The hydrocarbon linker may be optionally substituted.

[0027] The term "aliphatic compound" or "aliphatic linker" refers to a compound, respectively a linker, that is non-aromatic. It may be linear or branched, saturated or unsaturated, cyclic or acyclic. It may be substituted with one or more groups selected from, for example, alkyl, hydroxyl, halogen (Br, Cl, I), carbonyl, amine, carboxylic acid, -C(=O)-OR', -C(=O)-OC(=O)-R', each R' being independently C1-C6 alkyl. It may contain one or more bonds selected from ether, ester, amide, urethane, urea, and mixtures thereof.

[0028] The term "alicyclic compound" or "alicyclic linker" refers to a compound, respectively a linker, that contains a non-aromatic ring. The non-aromatic ring may have only carbon atoms as ring atoms (i.e., cyclohexyl) or may contain carbon atoms and one or more heteroatoms selected from N, O and S as ring atoms (i.e., heterocycloalkyl). It may be saturated or unsaturated. It may be substituted by one or more groups as defined for aliphatic compounds and linkers. It may contain one or more bonds as defined for aliphatic compounds and linkers.

[0029] The term "aromatic compound" or "aromatic linker" refers to a compound, respectively a linker, that contains an aromatic ring (i.e., a ring that adheres to Hückel's aromaticity rules). The aromatic ring may have only carbon atoms as ring atoms (i.e., phenyl) or may contain carbon atoms and one or more heteroatoms selected from N, O and S as ring atoms (i.e., heteroaryl). It may be substituted by one or more groups as defined for aliphatic compounds and linkers. It may contain one or more bonds as defined for aliphatic compounds and linkers. Aromatic aliphatic compounds and linkers (i.e., compounds and linkers that contain both aromatic and aliphatic moieties) are included in aromatic compounds and linkers.

[0030] The term "saturated" refers to a compound or linker that does not contain any double or triple carbon-carbon bonds.

[0031] The term "unsaturated" refers to a compound or linker that contains double or triple carbon-carbon bonds, especially double carbon-carbon bonds.

[0032] The term "polyol" means a compound that contains at least two hydroxyl groups.

[0033] The term "polyether polyol" or "polyether linker" refers to a polyol, respectively a linker, that contains at least two ether bonds.

[0034] The term "polyester polyol" or "polyester linker" refers to a polyol, respectively a linker, that contains at least two ester bonds.

[0035] The term "polycarbonate polyol" or "polycarbonate linker" refers to a polyol, respectively a linker, that contains at least two carbonate bonds.

[0036] The term "polyurethane linker" means a linker that contains at least two urethane bonds.

[0037] The term "polyorganosiloxane polyol" or "polyorganosiloxane linker" refers to a polyol, respectively a linker, that contains at least two organosiloxane bonds. The organosiloxane may be, for example, a dimethylsiloxane bond.

[0038] The term "polycaprolactone polyol" or "polycaprolactone linker" refers to a polyol, respectively a linker, comprising at least two units derived from the ring-opening polymerization of ε-caprolactone, in particular at least two -[(CH)-C(=O)O]- units.

[0039] The term "polybutadiene polyol" or "polybutadiene linker" refers to a polyol, respectively a linker, comprising at least two units derived from the polymerization of butadiene, in particular at least two units selected from -CH-CH=CH-CH- and CH-CH(CH=CH)-.

[0040] The term "isocyanurate linker" refers to an isocyanurate moiety, particularly of the formula [5] This means a linker including the TIFF2024519049000001.tif32170 portion.

[0041] The term “alkylene” refers to a group of the formula C m H 2m+2 (m can be from 1 to 100) by removing one hydrogen atom at each attachment point of the linker.

[0042] The term "alkyleneoxyalkylene" means an alkylene interrupted by one oxygen atom. Examples of suitable alkyleneoxyalkylenes are ethyleneoxyethylene (-CH2-CH2-O-CH2-CH2-), propyleneoxypropylene (-CH2-CH(CH3)-O-CH2-CH(CH3)- or -CH(CH3)-CH2-O-CH(CH3)-CH2-), and butyleneoxybutylene (-CH2-CH2-CH2-O-CH2-CH2-CH2-CH2-).

[0043] The term "poly(alkyleneoxyalkylene)" means an alkylene interrupted by two or more oxygen atoms.

[0044] The term "alkoxylated compound" or "alkoxylated linker" refers to one or more oxyalkylene moieties (-O-(CHR'') a3 -, where R'' is H or methyl and a3 is 1 to 10, preferably 2 to 4), in particular a compound containing one or more oxyalkylene moieties selected from oxyethylene (-O-CH2-CH2-), oxypropylene (-O-CH2-CH(CH3)- or -O-CH(CH3)-CH2-), oxybutylene (-O-CH2-CH2-CH2-CH2-) and combinations thereof, respectively a linker. For example, an alkoxylated compound or linker may contain 1 to 30 oxyalkylene moieties.

[0045] The term "arylene" means a linker derived from an arene by removing one hydrogen atom at each attachment point of the linker.

[0046] The term "alkylarylene" refers to a linker that includes an alkylene portion and an arylene portion.

[0047] The term "optionally substituted" refers to a compound, group, or linker that is optionally substituted with one or more groups selected from alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, alkylaryl, hydroxyl, halogen, nitrile, amine, amide, carboxylic acid, oxo(=O), -C(=O)-R'-C(=O)-OR', -C(=O)NH-R', -NH-C(=O)R', -OC(=O)-NH-R', -NH-C(=O)-O-R', -C(=O)-OC(=O)-R' and -SO2-NH-R', where each R' is independently an optionally substituted group selected from alkyl, aryl, and alkylaryl.

[0048] As used herein, a composition that is "substantially free of compound X" means a composition that contains less than 5%, less than 2%, less than 1%, less than 0.5%, less than 0.2%, less than 0.1%, less than 0.05%, less than 0.02%, less than 0.01%, or even 0% compound X, by weight, based on the weight of the composition.

[0049] Polymerizable flame retardants (Meth)acrylate-Containing Moiety The polymerizable flame retardant of the present invention comprises one or two (meth)acrylate-containing moieties. In particular, the polymerizable flame retardant of the present invention comprises two (meth)acrylate-containing moieties, which may be the same or different. Each (meth)acrylate-containing moiety may be located at one end of the polymerizable flame retardant. In particular, the polymerizable flame retardant may comprise two terminal (meth)acrylate-containing moieties, i.e., one (meth)acrylate-containing moiety at each end of the polymerizable flame retardant.

[0050] By (meth)acrylate-containing moiety is meant a moiety that contains at least one (meth)acrylate group corresponding to the formula: TIFF2024519049000002.tif23170In the formula, R1 is H or methyl.

[0051] Each (meth)acrylate-containing moiety can independently have from 1 to 6 (meth)acrylate groups, particularly from 1 to 3 (meth)acrylate groups, and more particularly 1 (meth)acrylate group.

[0052] In particular, all of the (meth)acrylate groups of the polymerizable flame retardant are contained in one or two (meth)acrylate-containing moieties, and thus the phosphorus-containing moiety may not have any (meth)acrylate groups.

[0053] The total number of (meth)acrylate groups in the flame retardant of the present invention may be 1 to 12, in particular 1 to 6, more particularly 1 to 4, even more particularly 1 or 2, more particularly 2.

[0054] Each (meth)acrylate-containing moiety independently has the formula (Ia): TIFF2024519049000003.tif32170 expression R1 is H or methyl; R2 is an (a+1)-valent linker; a is 1 to 6, in particular 1 or 2, more particularly 1; It may include a portion corresponding to:

[0055] In particular, each (meth)acrylate-containing moiety independently has the formula (Ib): TIFF2024519049000004.tif32170, wherein R1, R2 and a are as defined above. It may include a portion corresponding to:

[0056] R2 is an (a+1)-valent linker. In particular, R2 can be a divalent linker (a=1), a trivalent linker (a=2), a tetravalent linker (a=3), a pentavalent linker (a=4), a hexavalent linker (a=5) or a heptavalent linker (a=6). More particularly, R2 can be a divalent, trivalent or tetravalent linker. Even more particularly, R2 can be a divalent linker.

[0057] R2 may be an (a+1)-valent linker selected from an aliphatic or aromatic hydrocarbon linker, a polyether linker, a polyester linker, a polycarbonate linker, a polyurethane linker, a polyorganosiloxane linker, a polycaprolactone linker, a polybutadiene linker, an isocyanurate linker, and combinations thereof. In particular, R2 may be selected from an aliphatic or aromatic hydrocarbon linker, a polyether linker, a polyester linker, and combinations thereof. Even more particularly, R2 may be selected from an alkylene, an alkoxylated linker, and a polyester linker.

[0058] R2 is a polyol P that does not contain an OH group. OH Suitable polyols P OHExamples are ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, 1,3- or 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5- Pentanediol, neopentyl glycol, 2,4-diethyl-1,5-pentanediol, cyclohexanediol, cyclohexane-1,4-dimethanol, norbornene dimethanol, norbornane dimethanol, tricyclodecane dimethanol, tricyclodecane dimethanol, bisphenol A, B, F or S, hydrogenated bisphenol A, B, F or S, trimethylolmethane, trimethylolethane, trimethylolpropane, di(trimethylolpropane) ), triethylolpropane, pentaerythritol, di(pentaerythritol), glycerol, di-, tri- or tetraglycerol, polyglycerol, di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol, di-, tri- or tetrabutylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly(ethylene glycol-co-propylene glycol), sugar alcohols, dianhydrohexitols (i.e., isosorbide, isomannide, isoidide), tris(2-hydroxyethyl)isocyanurate, polybutadiene polyols, polyester polyols, polyether polyols, polyorganosiloxane polyols, polycarbonate polyols as well as their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives and derivatives obtained by ring-opening polymerization of ε-caprolactone initiated with one of the above polyols.

[0059] R2 may be a divalent, trivalent, tetravalent, pentavalent, hexavalent or heptavalent polyester linker corresponding to the residue of a polyester polyol that does not have OH groups. The polyester polyols are obtained by reacting one or more polyhydroxyl-functional compounds (especially polyhydroxyl-functional compounds containing 2 to 4 hydroxy groups) with one or more polycarboxylic acid-functional compounds or their derivatives (especially dicarboxylic acids and cyclic anhydrides). The polyhydroxyl-functional compounds and polycarboxylic acid-functional compounds can each have a linear, branched, alicyclic or aromatic structure and can be used individually or in mixtures. Examples of suitable polyhydroxyl-functional compounds are mentioned above as polyols P. OH The polycarboxylic acid is the same as that defined for . Examples of suitable polycarboxylic acids include adipic acid, succinic acid, oxalic acid, malonic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, eicosane diacid, cyclohexane dicarboxylic acid, hexahydrophthalic acid, itaconic acid, fumaric acid, maleic acid, and the like. Aromatic diacids such as phthalic acid and terephthalic acid can also be utilized. Examples of suitable anhydrides include succinic anhydride, hexahydrophthalic anhydride, maleic anhydride, fumaric anhydride, tetrahydrophthalic anhydride, and phthalic anhydride. Derivatives of polycarboxylic acids are compounds that can be converted into polycarboxylic acids by hydrolysis or transesterification. Suitable examples include dimethyl malonate, diethyl malonate, dimethyl adipate, dimethyl glutarate, and dimethyl succinate.

[0060] R2 is represented by the following formula (II): TIFF2024519049000005.tif33170 R4, R'4, R5, R'5, R6 and R'6 are independently H or methyl; R7 is selected from H, alkyl and alkoxy, in particular R7 is alkyl; c, c' and c'' are independently 0 to 2, with the proviso that at least two of c, c' and c'' are not 0, and in particular, c, c' and c'' are all 1 or c is 0 and c' and c'' are 1; d, d' and d'' are independently 2 to 4, in particular 2; e, e' and e'' may be trivalent linkers, each independently corresponding to 0 to 10, particularly 1 to 6.

[0061] R2 may be a trivalent linker corresponding to formula (III): TIFF2024519049000006.tif40170 expression R 11 , R 12 , R 13 , R 14 , R 15 and R 16 is independently H or methyl, in particular H; l, m and n are independently 1 to 6, in particular 2.

[0062] R2 is represented by the following formula (IV): TIFF2024519049000007.tif45170 R8, R'8, R9, R'9, R 10 , R' 10 , R 11 and R' 11 are independently H or methyl; f, f', f'', and f''' are independently 0 to 2, with the proviso that at least three of f, f', f'', and f''' are not 0, and in particular f, f', f'', and f''' are all 1; g, g', g'' and g''' are independently 2 to 4, in particular 2; h, h', h'' and h''' may be independently tetravalent linkers corresponding to 0 to 10, particularly 1 to 6.

[0063] R2 is represented by the following formula (V): TIFF2024519049000008.tif34170 R 12 , R' 12 , R 13 , R' 13 , R 14 , R' 14 , R 15 and R' 15 are independently H or methyl; i, i', i'' and i'''' are independently 2 to 4, in particular 2; j, j', j'' and j''' may be independently a tetravalent linker corresponding to 0 to 10, particularly 1 to 6.

[0064] R2 is represented by the following formula (VI): TIFF2024519049000009.tif42170 expression R 16 , R' 16 , R 17 , R' 17 , R 18 , R' 18 , R 19 , R' 19 , R 20 , R' 20 , R 21 and R' 21 are independently H or methyl; k, k', k'', k''', k* and k** are independently 2 to 4, in particular 2; l, l', l'', l''', l* and l** may independently be hexavalent linkers corresponding to 0 to 10, in particular 1 to 6.

[0065] R2 is represented by the formula (VII) to (XI), -(CR 22 R' 22 ) m -(VII) -[(CR 23 R' 23 ) n -O] o -(CR 23 R' 23 ) n -(VIII) -[(CR 24 R' 24 ) p -O] q -(CR 25 R' 25 ) r -[O-(CR 26 R' 26 ) p’ ] q’ -(IX) -[(CR 27 R' 27 ) s -C(=O)O] t -(CR 28 R' 28 ) u -*(X) -[(CR 29 R' 29 ) v -OC(=O)-(CR 30 R' 30 ) w -C(=O)-O] x -(CR 29 R' 29 ) v -(XI) During the ceremony R 22 , R' 22 , R 25 , R' 25 , R 29 , R' 29 , R 30 and R' 30 are independently H or alkyl; R 23 , R' 23 , R 24 , R' 24 , R 26 , R' 26 , R 27 , R' 27 , R 28 and R' 28 are independently H or methyl; m is from 2 to 20; n, p and p' are independently 2 to 4; o is from 1 to 20; q and q' are independently 0 to 20, with the proviso that at least one of q and q' is not 0; r is between 2 and 20; s is between 3 and 12, t is from 1 to 20, u is from 2 to 8, v is from 2 to 20, w is from 2 to 30; x is 1 to 20, The symbol * indicates the point of attachment to the (meth)acrylate group.

[0066] In particular, R2 is an alkylene, such as 1,2-ethanediyl, 1,2- or 1,3-propanediyl, 1,2-, 1,3- or 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,8-octanediyl, 1,9-nonanediyl, 1,10-decanediyl, 1,12-decanediyl, 2-methyl-1,3-propanediyl, 2,2-diethyl-1,3-propanediyl, 3-methyl-1,5-pentanediyl, 3,3-dimethyl-1,5-pentanediyl, 2,2-dimethyl-1,3-propanediyl, 2,4-diethyl-1,5-pentanediyl; alkoxylation of the aforementioned alkylenes (in particular ethoxylation). the divalent linker may be selected from: di-, tri-, tetra- or polyoxyalkylene residues without OH groups, such as di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol, di-, tri- or tetrabutylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, poly(ethylene glycol-co-propylene glycol); and the residues of polyester polyols without OH groups.

[0067] In particularly preferred embodiments, R2 is a divalent linker selected from one of formulae (VII), (VIII) or (X) as defined above.

[0068] Phosphorus-containing part The polymerizable flame retardant comprises one phosphorus-containing moiety. In particular, the polymerizable flame retardant comprises only one phosphorus-containing moiety.

[0069] By phosphorus-containing moiety is meant a moiety that contains a phosphorus atom.

[0070] The phosphorus-containing moiety contains two or more phosphorus atoms. In particular, the phosphorus-containing moiety contains two or more phosphorus-containing units, each unit containing a phosphorus atom. The phosphorus-containing units may be the same or different.

[0071] In particular, all of the phosphorus atoms of the polymeric flame retardant are contained in the phosphorus-containing moiety.

[0072] Each phosphorus-containing unit may independently include a phosphate, phosphonate, or phosphinate moiety.

[0073] By phosphate moiety is meant a moiety that comprises a phosphate group, which comprises a phosphorus atom bonded to four oxygen atoms, the phosphorus and oxygen atoms being bonded to each other by one P=O double bond and three PO single bonds.

[0074] By phosphonate moiety is meant a moiety that comprises a phosphonate group, which comprises a phosphorus atom bonded to three oxygen atoms and one carbon atom, the phosphorus, oxygen and carbon atoms being bonded together by one P=O double bond, two PO single bonds and one PC single bond.

[0075] By phosphinate moiety is meant a moiety that comprises a phosphinate group, which comprises a phosphorus atom bonded to two oxygen atoms and two carbon atoms, the phosphorus, oxygen and carbon atoms being bonded to each other by one P=O double bond, two PO single bonds and two PC single bonds.

[0076] In particular, each phosphorus-containing unit may independently include a phosphate moiety or a phosphonate moiety. More particularly, each phosphorus-containing unit may be represented by the following formula (XII): TIFF2024519049000010.tif22170, R 31 may independently contain a phosphate or phosphonate moiety corresponding to OH, alkyl, alkoxy, aryl, aryloxy, alkylaryl, or alkylaryloxy, preferably alkyl or alkoxy.

[0077] R 31 When R is OH, alkoxy, aryloxy, or alkylaryloxy, the moiety of formula (XII) is a phosphate moiety. 31 When is alkyl, aryl, or alkylaryl, the moiety of formula (XII) is a phosphonate moiety.

[0078] In particular, R 31 may be OH, C1-C12 alkyl, C1-C12 alkoxy, optionally substituted phenyl, phenyloxy, benzyl or benzyloxy. More particularly, R 31 can be C1-C4 alkyl or C1-C4 alkoxy.

[0079] The phosphorus-containing units of the phosphorus-containing moiety may be linked to one another by a divalent linker, which preferably contains at least one carbon atom.

[0080] In particular, the phosphorus-containing moiety has the formula (XIII): TIFF2024519049000011.tif29170 expression Each R 31 are independently as defined above for formula (XII); Each R 32 are independently divalent linkers, y may include a moiety represented by: y is 1 to 50, preferably 1 to 10.

[0081] R 32may be a divalent linker selected from optionally substituted alkylene, optionally substituted alkyleneoxyalkylene, optionally substituted poly(alkyleneoxyalkylene), optionally substituted arylene, optionally substituted alkylarylene, preferably alkylene, alkyleneoxyalkylene, or poly(alkyleneoxyalkylene).

[0082] In particular, R 32 may be a C1-C10 alkylene optionally substituted with one or more phenyl groups, a C4-C20 alkyleneoxyalkylene optionally substituted with one or more phenyl groups, or a C6-C100 poly(alkyleneoxyalkylene) optionally substituted with one or more phenyl groups, phenylene, diphenylene, or C7-C20 alkylarylene.

[0083] More specifically, R 32 Formula (XIV) to (XVIII): -(CR 33 R' 33 ) m’ -(XVI) -[(CR 34 R' 34 ) n’ -O] o’ -(CR 34 R' 34 ) n’ -(XV) -Ph-(XVI) -(CR 35 R' 35 ) p’’ -Ph-(CR 36 R' 36 ) q’’ -(XVII) -Ph-(CR 37 R' 37 ) r’’ -Ph-(XVIII) During the ceremony Each R 33 , R' 33 , R 34 and R' 34 is independently selected from H, alkyl and phenyl; Each R35 , R' 35 , R 36 , R' 36 , R 37 and R' 37 is independently selected from H and alkyl; Ph is optionally substituted phenylene; m' is 1 to 10; n' is 2 to 4; o' is from 1 to 50, p'' and q'' are independently 0 to 10, with the proviso that at least one of p'' and q'' is not 0; r'' may be selected from one of the following: 0 to 10.

[0084] In even more detail, R 32 corresponds to formula (XIV) or (XV) defined above.

[0085] The phosphorus-containing moiety may comprise a moiety of formula (XIII) as defined above and an oxyalkylene unit. In particular, the phosphorus-containing moiety may comprise a moiety of formula (XIX): TIFF2024519049000012.tif29170 expression Each R 31 are independently as defined above for formula (XII); Each R 32 are independently as defined above for formula (XIII); Each R 33 and R' 33 is independently alkylene, preferably C2-C4 alkylene; y is as defined above for formula (XIII); z and z' are independently 0 to 20, with the proviso that at least one of z and z' is not 0, and preferably z and z' are independently 1 to 20.

[0086] Urethane and ester bonds The polymerizable flame retardants of the present invention may optionally contain one or more urethane (-NH-C(=O)-O- or -OC(=O)-NH-) or ester (-C(=O)-O- or -OC(=O)-) linkages.

[0087] Any ester linkages are different from the (meth)acrylate groups contained in the (meth)acrylate-containing moiety.

[0088] The atoms in the urethane and ester bonds may be partly contained in the (meth)acryl-containing moiety or the phosphorus-containing moiety and partly contained in the linker.

[0089] The polymerizable flame retardant of the present invention may include at least one linker, L, that connects the (meth)acrylate-containing moiety to the phosphorus-containing moiety. Thus, the linker may be disposed between the (meth)acrylate-containing moiety and the phosphorus-containing moiety.

[0090] The polymerizable flame retardant of the present invention can include two linkers L, each linker L connecting a (meth)acrylate-containing moiety to one end of a phosphorus-containing moiety.

[0091] The linker L has the following formula (XX) or (XXI): TIFF2024519049000013.tif37170 L1 is selected from an aliphatic linker, an alicyclic linker, an aromatic linker, and an araliphatic linker; L2 may be a bond or linker corresponding to one of the following selected from an aliphatic linker, an alicyclic linker, an aromatic linker, and an araliphatic linker.

[0092] In particular, the linker L may correspond to formula (XX):

[0093] L1 may be the residue of a diisocyanate of formula OCN-L1-NCO that does not contain an NCO group, or a derivative thereof. In particular, the diisocyanate of formula OCN-L1-NCO may be selected from aliphatic diisocyanates, cycloaliphatic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates or derivatives thereof.

[0094] The diisocyanate derivative may be a compound capable of generating a diisocyanate in situ, for example a diisocyanate having a blocked NCO group that may be unblocked (i.e., become a free NCO group) under certain conditions, such as heating. The diisocyanate derivative may be an oligomerized diisocyanate (i.e., a dimer, trimer, tetramer, pentamer, hexamer or higher oligomer) or a modified diisocyanate (i.e., having an allophanate, isocyanurate, uretdione, biuret or iminooxadiazinedione structure).

[0095] Examples of suitable diisocyanates are 2,4- and 2,6-toluene diisocyanate (TDI), isophorone diisocyanate (corresponding to IPDI-3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate), tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), 2,2'-, 2,4'- and 4,4'-dicyclohexylmethane diisocyanate (H12MDI), 3,3'-dimethyl-4,4'- These include biphenyl diisocyanate, 1,4-benzene diisocyanate, 1,5-naphthalene diisocyanate (NDI), 1,3- and 1,4-cyclohexane diisocyanate, 1-methyl-2,4-diisocyanatocyclohexane, 1-methyl-2,6-diisocyanatocyclohexane, dodecane diisocyanate, m-tetramethylene xylylene diisocyanate, 4,6-xylylene diisocyanate and derivatives of the above-mentioned diisocyanates (in particular their dimers, trimers and modified forms of the above-mentioned diisocyanates having allophanate, isocyanurate, uretdione, biuret or iminooxadiazinedione structures).

[0096] In one embodiment, the diisocyanate of formula OCN-L1-NCO or derivative thereof may be an aliphatic diisocyanate, a cycloaliphatic diisocyanate or derivative thereof, in particular isophorone diisocyanate, hexamethylene diisocyanate or hexamethylene diisocyanate trimer, more particularly isophorone diisocyanate.

[0097] L2 is COOR 38 having no group, formula R 38 OOC-L2-COOR 38 wherein R 38 is H or alkyl. Alternatively, L2 may correspond to a cyclic anhydride moiety that forms a ring with the -C(=O)-OC(=O)- group.

[0098] In particular, the formula R 38 OOC-L2-COOR 38 The diacid or diester may be an aliphatic diacid or diester, a cycloaliphatic diacid or diester, an aromatic diacid or diester, and an araliphatic diacid or diester, more particularly an aliphatic diacid or diester, and even more particularly a saturated or unsaturated aliphatic diacid or diester.

[0099] Examples of saturated aliphatic diacids include malonic acid, succinic acid, 2-methylsuccinic acid, 2,2-dimethylsuccinic acid, glutaric acid, 3,3-diethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.

[0100] Examples of unsaturated aliphatic diacids include itaconic acid, maleic acid, fumaric acid, glutaconic acid, and muconic acid.

[0101] An example of a saturated alicyclic diacid is cyclohexanedicarboxylic acid.

[0102] Examples of aromatic diacids are phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid and 2,5-furandicarboxylic acid.

[0103] Suitable examples of diesters are the alkyl esters of the aforementioned diacids, in particular the methyl and / or ethyl esters of the aforementioned diacids, more particularly dimethyl malonate, diethyl malonate, dimethyl adipate, dimethyl glutarate, dimethyl succinate.

[0104] Examples of suitable cyclic anhydrides include succinic anhydride, maleic anhydride, fumaric anhydride, phthalic anhydride, hexahydrophthalic anhydride and tetrahydrophthalic anhydride.

[0105] structure The polymerizable flame retardant of the present invention is represented by the formula (XXII) to (XXV): Y-PHOS-ACR(XXII) ACR-PHOS-ACR(XXIII) Y-PHOS-L-ACR(XXIV) ACR-L-PHOS-L-ACR(XXV) During the ceremony ACR is a (meth)acrylate-containing moiety as defined above; PHOS is a phosphorus-containing moiety as defined above; L is a linker as defined above, Y is a terminal group and may correspond to one of the structures:

[0106] Y may be an end group at one end of a phosphorus-containing moiety, especially when the polymerizable flame retardant has only one (meth)acrylate-containing moiety.

[0107] Y may be selected from H, alkyl and aryl. In particular, Y is H or alkyl.

[0108] Preferred structures of the polymerizable flame retardant are according to formula (XXIII), (XXIV) or (XXV). The structures of formula (XXXIII) or (XXV) are particularly preferred. The structures of formula (XXV) are more particularly preferred.

[0109] In particular, the polymerizable flame retardants of the present invention are represented by the formulae (XXVI) to (XXIX): TIFF2024519049000014.tif23170(XXVI) TIFF2024519049000015.tif23170(XXVII) TIFF2024519049000016.tif24170(XXVIII) TIFF2024519049000017.tif24170(XXIX) During the ceremony R1R2, R 31 , R 32 , R 33 , R' 33 , L, Y, a, y, z and z' are as defined above.

[0110] Preferred structures of the polymerizable flame retardant are according to formula (XXVIII) or (XXIX): The structure of formula (XXIX) is particularly preferred.

[0111] In particular, the polymerizable flame retardant of the present invention may correspond to a structure of formula (XXVIII) or (XXIX), more particularly to a structure of formula (XXIX), in which R1 is H or methyl; R2 is a divalent linker, in particular selected from one of the formulae (VII) to (XI) defined above, Each R 31 is independently OH, alkyl, alkoxy, aryl, aryloxy, alkylaryl or alkylaryloxy, in particular C1-C4 alkyl or C1-C4 alkoxy; Each R 32 is independently alkylene, alkyleneoxyalkylene, poly(alkyleneoxyalkylene), arylene or alkylarylene, in particular according to one of the formulae (XIV) to (XVIII) defined above, Each R 33 and R' 33 are independently alkylene, particularly C2-C4 alkylene; L is a linker corresponding to formula (XX) or (XXI) as defined above, in particular L is a linker of formula (XX), Y is H or alkyl; a is 1 to 6, in particular 1 or 2; y is from 1 to 50, in particular from 1 to 10; z and z' are independently 0 to 20, with the proviso that at least one of z and z' is not 0; in particular, z and z' are independently 1 to 20.

[0112] The polymerizable flame retardant of the present invention can be prepared according to the method described below.

[0113] Method for preparing polymerizable flame retardants The polymerizable flame retardant of the present invention may be a reaction product of at least one phosphorus-containing compound, at least one (meth)acrylate-containing compound, and optionally at least one OH-reactive compound.

[0114] The phosphorus-containing compound may be a phosphorus-containing alcohol. In particular, the phosphorus-containing compound may be a phosphorus-containing monoalcohol containing one OH group, or a phosphorus-containing diol containing two OH groups. The phosphorus-containing compound may be represented by the formula (XXX): TIFF2024519049000018.tif29170(XXX) R 31 , R 32 , R 33 , R' 33 , y, z and z' are as defined above; Y and Y' may correspond to independently selected from H, alkyl and aryl, with the proviso that at least one of Y and Y' is H.

[0115] The (meth)acrylate-containing compound may be (meth)acrylic acid or a (meth)acrylate-containing alcohol. The (meth)acrylate-containing compound may be represented by formula (XXXI) or (XXXII): TIFF2024519049000019.tif63170, where R1, R2 and a are as defined above.

[0116] The OH-reactive compound may be selected from diisocyanates, diisocyanate derivatives, diacids, diesters and cyclic anhydrides. The OH-reactive compound may be selected from diisocyanates or derivatives thereof corresponding to formula (XXXIII), diacids or diesters corresponding to formula (XXXIV), and cyclic anhydrides corresponding to formula (XXXV), OCN-L1-NCO(XXXIII) R 34 OOC-L2-COOR 34 (XXXIV) TIFF2024519049000020.tif24170, where L1 and L2 are as defined above; R 34 and R' 34 is independently H or alkyl.

[0117] Examples of suitable diisocyanates, diisocyanate derivatives, diacids, diesters and cyclic anhydrides are described above.

[0118] In a first embodiment, the polymerizable flame retardant of the present invention may be a reaction product of at least one phosphorus-containing alcohol and (meth)acrylic acid. The polymerizable compound obtained in the process of the first embodiment may correspond to the structure of formula (XXII), (XXIII), (XXVI) or (XXVII) defined above.

[0119] In a second embodiment, the polymerizable flame retardant of the present invention may be a reaction product of at least one phosphorus-containing alcohol, at least one (meth)acrylate-containing alcohol, and at least one OH-reactive compound selected from diisocyanates, diisocyanate derivatives, diacids, diesters, and cyclic anhydrides. The polymerizable compound obtained in the process of the second embodiment may correspond to the structure of formula (XXIV), (XXV), (XXVIII) or (XXIX) defined above.

[0120] The process of the second embodiment can be carried out by reacting the different components in one or more steps. In a first alternative, the process comprises mixing and reacting at least one OH-reactive compound, at least one phosphorus-containing alcohol and at least one (meth)acrylate-containing alcohol all together. In a second alternative, the process comprises the following successive steps: reacting at least one OH-reactive compound with at least one phosphorus-containing alcohol, then adding at least one (meth)acrylate-containing alcohol to the resulting product. In a third alternative, the process comprises the following successive steps: reacting at least one OH-reactive compound with at least one (meth)acrylate-containing alcohol, then adding at least one phosphorus-containing alcohol to the resulting product.

[0121] The molar ratio R / OH may be ≧0.95 and ≦1.05. The molar ratio R / OH corresponds to the molar ratio of the OH-reactive groups of the OH-reactive compound to the OH groups of the phosphorus-containing alcohol and the (meth)acrylate-containing alcohol.

[0122] The process may be carried out in the presence of a catalyst, which may be selected from compounds based on Sn, Ti, Zn, Zr, Ba, Bi, Co, Pb, Mn, preferably compounds based on Sn, Bi, Zn, Ti, Zr.

[0123] More particularly, the catalyst may be selected from: - inorganic tin compounds such as stannous octoate, stannous oxalate, stannous stearate, stannous naphthenate or stannous chloride dihydrate; - organic tin compounds, for example dibutyltin (DBT) compounds, in particular DBT bis-O-phenylphenate, DBT bis-(2,3-dihydroxypropyl mercaptide), DBT bis-(2-hydroxyethyl mercaptide), DBT bis-(4-hydroxyphenyl mercaptide), dioctyltin bis-(2-hydroxyethyl mercaptide), dioctyltin bis-(4-hydroxybutyl mercaptide), DBT bis-(4-hydroxyphenyl acetate), DBT bis-[3-(4-hydroxyphenyl)propionatel, DBT S,S-dibutylthiocarbonate, DBT diacetate, DBT diketanoate, DBT dilaurate, DBT dilauryl mercaptide or DBT maleate; dioctyltin (DOT) compounds, in particular DOT bis-(4-hydroxyphenylacetate), DOT bis-(3-hydroxybutyrate), DOT diacetate, DOT di(ethylhexanoate), DOT dithioglycolate, DOT dilaurate, DOT diketanoate, DOT dicarboxylates or DOT stannoxanes; dimethyltin (DMT) compounds, tributyltin (TBT) compounds, trimethyltin (TMT) compounds, triphenyltin (TPhT) compounds, tetrabutyltin (TeBT) compounds, tricyclohexyltin (TCyHT) compounds, trioctyltin (TOT) compounds, tripropyltin (TPT) compounds, monobutyltin (MBT) compounds or monooctyltin (MOT) compounds; bismuth compounds, such as bismuth carboxylates, bismuth neodecanoate, bismuth stannate or bismuth stearate; - zinc compounds such as zinc acetate, zinc acetylacetate, zinc neodecanoate, zinc octoate or zinc oxalate; titanium compounds, such as titanium acetylacetone complex, titanium ethylacetoacetonate complex, titanium tetrabutanolate or titanium triethanolate; - zirconium compounds, for example zirconium ethylacetoacetonate complex or zirconium octanoate; - Some additional organometallic compounds suitable as catalysts, such as potassium octanoate, potassium neodecanoate, amine complexes, copper oleate, copper naphthenate, cerium octanoate, iron acetoacetate, lead stannate, lead stearate, barium nitride.

[0124] polymerizable composition The polymerizable composition of the present invention comprises a polymerizable flame retardant, referred to as component a), and further comprises an ethylenically unsaturated compound other than a), referred to as component b).

[0125] The polymerizable composition of the present invention comprises - 10 to 95%, 20 to 90%, 30 to 85%, 40 to 80%, 50 to 75% or 60 to 70% of component a); - 5 to 90%, 10 to 80%, 15 to 70%, 20 to 60%, 25 to 50% or 30 to 40% of component b); The percentages are by weight based on the total weight of components a) and b).

[0126] The polymerizable composition of the present invention comprises photoinitiators, -amine synergists, - flame retardants other than component a), -additives, -solvent The composition may further comprise one or more compounds selected from:

[0127] Ethylenically unsaturated compounds The polymerizable composition of the present invention comprises an ethylenically unsaturated compound. The polymerizable composition of the present invention may comprise a mixture of ethylenically unsaturated compounds.

[0128] As used herein, the term "ethylenically unsaturated compound" refers to a compound that contains 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. The polymerizable carbon-carbon double bond is generally included in a group selected from acrylate (including cyanoacrylate), methacrylate, acrylamide, methacrylamide, styrene, maleate, fumarate, itaconate, allyl, propenyl, vinyl and combinations thereof, preferably selected from acrylate, methacrylate and vinyl, more preferably selected from acrylate and methacrylate. The carbon-carbon double bond of a phenyl ring is not considered to be a polymerizable carbon-carbon double bond.

[0129] In one embodiment, the ethylenically unsaturated compound may be selected from (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, amine-modified acrylates, and mixtures thereof. In particular, the ethylenically unsaturated compound includes (meth)acrylate-functionalized monomers.

[0130] The total amount of ethylenically unsaturated compounds (including (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, and amine-modified acrylates) in the polymerizable composition can be 1 to 99%, 2 to 90%, 5 to 80%, 10 to 70%, 15 to 60%, 20 to 50%, 25 to 45%, or 30 to 40% based on the weight of the composition. In particular, the polymerizable composition can include 50 to 99%, 50 to 95%, 50 to 90%, 50 to 85%, 50 to 80%, or 50 to 75% ethylenically unsaturated compounds based on the weight of the composition. Alternatively, the polymerizable composition may include 1 to 50%, 5 to 50%, 10 to 50%, 15 to 50%, 20 to 50%, 25 to 50%, or 30 to 50% by weight of ethylenically unsaturated compounds based on the weight of the composition.

[0131] As used herein, the term "(meth)acrylate-functionalized monomer" refers to a monomer that contains a (meth)acrylate group, particularly an acrylate group. The term "(meth)acrylate-functionalized oligomer" refers to an oligomer that contains a (meth)acrylate group, particularly an acrylate group. The term "(meth)acrylate group" encompasses acrylate groups (-O-CO-CH=CH2) and methacrylate groups (-O-CO-C(CH3)=CH2).

[0132] The ethylenically unsaturated compound may comprise a (meth)acrylate-functionalized monomer.The ethylenically unsaturated compound may comprise a mixture of (meth)acrylate-functionalized monomers.

[0133] The (meth)acrylate functionalized monomer may have a molecular weight of less than 600 g / mol, in particular from 100 to 550 g / mol, more particularly from 200 to 500 g / mol.

[0134] The (meth)acrylate functionalized monomer may have 1 to 6 (meth)acrylate groups, especially 1 to 4 (meth)acrylate groups.

[0135] The (meth)acrylate-functionalized monomer may comprise a mixture of (meth)acrylate-functionalized monomers having different functionalities. For example, the (meth)acrylate-functionalized monomer may comprise a mixture 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.

[0136] The (meth)acrylate functionalized monomer may include a mono(meth)acrylate functionalized monomer, which may advantageously function as a reactive diluent to reduce the viscosity of the composition of the present invention.

[0137] Examples of suitable mono(meth)acrylate functionalized monomers include, but are not limited to, mono-(meth)acrylate esters of aliphatic alcohols (wherein the aliphatic alcohol may be linear, branched, or alicyclic and may be a mono-, di-, or polyalcohol, provided that only one hydroxyl group is esterified with (meth)acrylic acid); mono-(meth)acrylate esters of aromatic alcohols (e.g., phenols, e.g., alkylated phenols); mono-(meth)acrylate esters of alkylaryl alcohols (such as benzyl alcohol); oligomeric and polymeric glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol. mono-(meth)acrylate esters of glycols; mono-(meth)acrylate esters of monoalkyl ethers of glycols and oligoglycols; mono-(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) fatty alcohols (wherein the fatty alcohol may be linear, branched or alicyclic and may be a mono-, di- or polyalcohol, provided that only one hydroxyl group of the alkoxylated fatty alcohol is esterified with (meth)acrylic acid); mono-(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (such as alkoxylated phenols); caprolactone mono(meth)acrylates; and the like.

[0138] The following compounds are illustrative of mono(meth)acrylate functionalized monomers suitable for use in the polymerizable compositions of the present invention: methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; n-dodecyl (meth)acrylate; tridecyl (meth)acrylate. ;Tetradecyl (meth)acrylate;Hexadecyl (meth)acrylate;2-Hydroxyethyl (meth)acrylate;2- and 3-Hydroxypropyl (meth)acrylate;2-Methoxyethyl (meth)acrylate;2-Ethoxyethyl (meth)acrylate;2- and 3-Ethoxypropyl (meth)acrylate;Tetrahydrofurfuryl (meth)acrylate;Alkoxylated tetrahydrofurfuryl (meth)acrylate;2-(2-Ethoxyethoxy)ethyl (meth)acrylate;Cyclohexyl (meth)acrylate;Glycol Ricidyl (meth)acrylate;Isodecyl (meth)acrylate;Lauryl (meth)acrylate;2-Phenoxyethyl (meth)acrylate;Alkoxylated phenol (meth)acrylate;Alkoxylated nonylphenol (meth)acrylate;Cyclic trimethylolpropane formal (meth)acrylate;Isobornyl (meth)acrylate;Tricyclodecane methanol (meth)acrylate;tert-Butyl cyclohexanol (meth)acrylate;Trimethylcyclohexanol (meth)acrylate;Ethylene glycol Phenyl ether (meth)acrylate;Diethylene glycol monomethyl ether (meth)acrylate;Diethylene glycol monoethyl ether (meth)acrylate;Diethylene glycol monobutyl ether (meth)acrylate;Triethylene glycol monoethyl ether (meth)acrylate;Ethoxylated lauryl (meth)acrylate;Methoxypolyethylene glycol (meth)acrylate;Hydroxyethyl-butyl urethane (meth)acrylate;3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate;and combinations thereof.;

[0139] Preferred examples of mono(meth)acrylate functionalized monomers suitable for use in the polymerizable compositions of the present invention include tetrahydrofurfuryl acrylate, dodecyl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, ethylene glycol phenyl ether acrylate, isobornyl (meth)acrylate, methoxypolyethylene glycol monoacrylate, lauryl acrylate, alkoxylated phenol acrylates, and combinations thereof.

[0140] The (meth)acrylate-functionalized monomer can include a (meth)acrylate-functionalized monomer containing more than one (meth)acrylate group per molecule, for example, 2, 3, 4, 5 or 6 (meth)acrylate groups per molecule.

[0141] Examples of suitable (meth)acrylate-functionalized monomers containing two or more (meth)acrylate groups per molecule include acrylate and methacrylate esters of polyhydric alcohols (organic compounds containing two or more, e.g., from 2 to 6, hydroxyl groups per molecule). Specific examples of suitable polyhydric alcohols include C 2-20 Alkylene glycol (carbon chain may be branched, C 2-10Glycols having alkylene groups may be preferred; for example, ethylene glycol, trimethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, tetramethylene glycol (1,4-butanediol), 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,12-dodecanediol, cyclohexane-1,4-dimethanol, bisphenols and hydrogenated bisphenols and alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof), diethylene glycol, glycerin, alkoxylated glycerin, triethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, alkoxylated trimethylolpropane, ditrimethylolpropane, alkoxylated alkoxylated ditrimethylolpropane, pentaerythritol, alkoxylated pentaerythritol, dipentaerythritol, alkoxylated dipentaerythritol, cyclohexanediol, alkoxylated cyclohexanediol, cyclohexanedimethanol, alkoxylated cyclohexanedimethanol, norbornene dimethanol, alkoxylated norbornene dimethanol, norbornane dimethanol, alkoxylated norbornane dimethanol, polyols containing aromatic rings, cyclohexane-1,4-dimethanol ethylene oxide adducts, bis-phenol ethylene oxide adducts, hydrogenated bisphenol ethylene oxide adducts, bisphenol propylene oxide adducts, hydrogenated bisphenol propylene oxide adducts, cyclohexane-1,4-dimethanol propylene oxide adducts, sugar alcohols and alkoxylated sugar alcohols. Such polyhydric alcohols may be fully or partially esterified (with (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.) so long as they contain at least two (meth)acrylate functional groups per molecule.

[0142] Exemplary (meth)acrylate functionalized monomers containing two or more (meth)acrylate groups per molecule are ethoxylated bisphenol A di(meth)acrylate; triethylene glycol di(meth)acrylate; ethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; 1,4-butanediol diacrylate; 1,4-butanediol dimethacrylate; diethylene glycol diacrylate; diethylene glycol dimethacrylate, 1,6-hexanediol diacrylate; 1,6-hexanediol dimethacrylate; neopentyl glycol diacrylate; neopentyl glycol di(meth)acrylate; polyethylene glycol (600) dimethacrylate; acrylate (600 refers to the approximate number average molecular weight of the polyethylene glycol portion);polyethylene glycol (200) diacrylate;1,12 dodecanediol dimethacrylate;tetraethylene glycol diacrylate;triethylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, tripropylene glycol diacrylate, polybutadiene diacrylate;methylpentanediol diacrylate;polyethylene glycol (400) diacrylate;ethoxylated 2 bisphenol A dimethacrylate;ethoxylated 3 bisphenol A dimethacrylate;ethoxylated 3 bisphenol A diacrylate;cyclohexane dimethanol dimethacrylate;cyclohexane dimethanol diacrylate;ethoxylated 10 Bisphenol A dimethacrylate (the number following "ethoxylated" is the average number of oxyalkylene moieties per molecule);Dipropylene glycol diacrylate;Ethoxylated 4 Bisphenol A dimethacrylate;Ethoxylated 6 Bisphenol A dimethacrylate;Ethoxylated 8 Bisphenol A dimethacrylate;Alkoxylated Hexanediol Diacrylate;Alkoxylated Cyclohexanedimethanol Diacrylate;Dodecane Diacrylate;Ethoxylated 4 Bisphenol A Diacrylate;Ethoxylated 10Bisphenol A diacrylate;Polyethylene glycol (400) dimethacrylate;Polypropylene glycol (400) dimethacrylate;Metal diacrylates;Modified metal diacrylates;Metal dimethacrylates;Polyethylene glycol (1000) dimethacrylate;Methacrylated polybutadiene;Propoxylated 2-neopentyl glycol diacrylate;Ethoxylated 30 Bisphenol A dimethacrylate; ethoxylated 30 Bisphenol A diacrylate;Alkoxylated neopentyl glycol diacrylate;Polyethylene glycol dimethacrylate;1,3-Butylene glycol diacrylate;Ethoxylated 2 bisphenol A dimethacrylate;Dipropylene glycol diacrylate;Ethoxylated 4 bisphenol A diacrylate;Polyethylene glycol (600) diacrylate;Polyethylene glycol (1000) dimethacrylate;Tricyclodecane dimethanol diacrylate;Propoxylated neopentyl glycol diacrylate, e.g. propoxylated 2 neopentyl glycol diacrylate;Diacrylates of alkoxylated fatty alcohols;Trimethylolpropane trimethacrylate;Trimethylolpropane triacrylate;Tris(2-hydroxyethyl)isocyanurate triacrylate;Ethoxylated 20 Trimethylolpropane triacrylate;Pentaerythritol triacrylate;Ethoxylated 3 trimethylolpropane triacrylate;Propoxylated 3 trimethylolpropane triacrylate;Ethoxylated 6 trimethylolpropane triacrylate;Propoxylated 6 trimethylolpropane triacrylate;Ethoxylated 9 trimethylolpropane triacrylate;Alkoxylated trifunctional acrylate esters;Trifunctional methacrylate esters;Trifunctional acrylate esters;Propoxylated 3 glyceryl triacrylate;Propoxylated 5.5 Glyceryl triacrylate; ethoxylated 15trifunctional phosphate esters; trifunctional acrylic esters; pentaerythritol tetraacrylate; ditrimethylolpropane tetraacrylate; ethoxylated 4 pentaerythritol tetraacrylate; pentaerythritol polyoxyethylene tetraacrylate; dipentaerythritol pentaacrylate; and pentaacrylate esters.

[0143] Preferred examples of (meth)acrylate functionalized monomers containing two or more (meth)acrylate groups per molecule suitable for use in the polymerizable compositions of the present invention include poly(ethylene glycol) di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, trimethylolpropane triacrylate, di(trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and combinations thereof. Dipentaerythritol hexaacrylate is particularly preferred.

[0144] The total amount of (meth)acrylate functionalized monomers in the polymerizable composition can be 0 to 99.5%, 1 to 99%, 2 to 90%, 5 to 80%, 10 to 70%, 15 to 60%, 20 to 50%, 25 to 45%, or 30 to 40% by weight based on the weight of the composition. In particular, the polymerizable composition can include 50 to 99%, 50 to 95%, 50 to 90%, 50 to 85%, 50 to 80%, or 50 to 75% by weight of (meth)acrylate functionalized monomers based on the weight of the composition. Alternatively, the polymerizable composition may include 1 to 50%, 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 weight of the composition.

[0145] The ethylenically unsaturated compound may comprise a (meth)acrylate-functionalized oligomer.The ethylenically unsaturated compound may comprise a mixture of (meth)acrylate-functionalized oligomers.

[0146] (Meth)acrylate-functionalized oligomers may be selected to enhance, among other attributes, the flexibility, strength and / or modulus of cured polymers prepared using the polymerizable compositions of the present invention.

[0147] The (meth)acrylate-functionalized oligomer may have 1 to 18 (meth)acrylate groups, particularly 2 to 6 (meth)acrylate groups, and more particularly 2, 3, 4, 5 or 6 acrylate groups.

[0148] The (meth)acrylate functionalized oligomer may have a number average molecular weight of 600 g / mol or more, particularly from 800 to 15,000 g / mol, and more particularly from 1,000 to 5,000 g / mol.

[0149] In particular, the (meth)acrylate-functionalized oligomers include (meth)acrylate-functionalized urethane oligomers (sometimes referred to as "urethane (meth)acrylate oligomers", "polyurethane (meth)acrylate oligomers" or "carbamate (meth)acrylate oligomers"), (meth)acrylate-functionalized epoxy oligomers (sometimes referred to as "epoxy (meth)acrylate oligomers"), (meth)acrylate-functionalized polyether oligomers (sometimes referred to as "polyether (meth)acrylate oligomers"), ..."), (meth)acrylate-functionalized epoxy oligomers (sometimes referred to as "epoxy (meth)acrylate oligomers"), (meth)acrylate-functionalized polyether oligomers (sometimes referred to as "polyether (meth)acrylate oligomers"), (meth)acrylate-functionalized urethane oligomers (sometimes referred to as "urethane (meth)acrylate oligomers"), (meth)acrylate-functionalized urethane oligomers (sometimes referred to as "urethane (meth)acrylate oligomers"), (meth)acrylate-functionalized urethane oligomers (sometimes referred to as "urethane (meth)acrylate oligomers"), (meth)acrylate-functionalized urethane oligomers (sometimes referred to as "urethane (meth)acrylate oligomers"), (meth)acrylate-functionalized urethane oligomers (sometimes referred to as "urethane (meth)acrylate oligomers"), (meth)acrylate-functionalized urethane oligomers (sometimes referred to as "urethane (meth)acrylate oligomers"), (meth)acrylate- The (meth)acrylate-functionalized polydiene oligomer (sometimes referred to as a "polydiene (meth)acrylate oligomer"), (meth)acrylate-functionalized polycarbonate oligomer (sometimes referred to as a "polycarbonate (meth)acrylate oligomer"), (meth)acrylate-functionalized polyester oligomer (sometimes referred to as a "polyester (meth)acrylate oligomer"), (meth)acrylate-functionalized acrylic oligomer (sometimes referred to as an "acrylic (meth)acrylate oligomer"), and mixtures thereof.

[0150] Preferably, the (meth)acrylate-functionalized oligomer comprises a (meth)acrylate-functionalized urethane oligomer, more preferably an acrylate-functionalized urethane oligomer.

[0151] Advantageously, the (meth)acrylate-functionalized oligomer comprises a (meth)acrylate-functionalized urethane oligomer having two (meth)acrylate groups, more preferably an acrylate-functionalized urethane oligomer having two acrylate groups.

[0152] Exemplary polyester (meth)acrylate oligomers include the reaction products of acrylic or methacrylic acid or mixtures or synthetic equivalents thereof with hydroxyl-terminated polyester polyols. The reaction process may be carried out such that all or essentially all of the hydroxyl groups of the polyester polyol are (meth)acrylated, especially when the polyester polyol is difunctional. The polyester polyols can be produced by the polycondensation reaction of polyhydroxyl-functional components (especially diols) and polycarboxylic acid-functional compounds (especially dicarboxylic acids and anhydrides). The polyhydroxyl-functional and polycarboxylic acid-functional components can each have a linear, branched, alicyclic or aromatic structure and can be used individually or as a mixture.

[0153] Examples of suitable epoxy (meth)acrylate oligomers include the reaction products of acrylic or methacrylic acid, or mixtures thereof, with epoxy resins (polyglycidyl ethers or esters).The epoxy resins are in particular bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resins, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecaprylamide ...hexylmethyl-3',4'-epoxycyclohexylmethyl-3',4'-epoxycyclohexylmethyl-3',4' 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'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxy glycidyl ether, di(3,4-epoxycyclohexylmethyl)ether of ethylene glycol, ethylene bis(3,4-epoxycyclohexanecarboxylate), 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin, diglycidyl esters of aliphatic long-chain dibasic acids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of phenol, cresol, butylphenol, polyether alcohols obtained by adding alkylene oxides to these compounds, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy butyl stearic acid, epoxy octyl stearic acid, epoxidized linseed oil, and epoxidized polybutadiene.

[0154] Suitable polyether (meth)acrylate oligomers include, but are not limited to, the condensation reaction products of acrylic or methacrylic acid or their synthetic equivalents or mixtures with a polyetherol, which is a polyether polyol (e.g., polyethylene glycol, polypropylene glycol, or polytetramethylene glycol). Suitable polyetherols can be linear or branched materials containing ether linkages and terminal hydroxyl groups. Polyetherols can be prepared by ring-opening polymerization of cyclic ethers such as tetrahydrofuran or alkylene oxides (e.g., ethylene oxide and / or propylene oxide) with starter molecules. Suitable starter molecules include water, polyhydroxyl-functional materials, polyester polyols, and amines.

[0155] Suitable polyurethane (meth)acrylate oligomers (sometimes referred to as "urethane (meth)acrylate oligomers") for use in the polymerizable compositions of the present invention include urethanes based on aliphatic, cycloaliphatic and / or aromatic polyester polyols and polyether polyols and aliphatic, cycloaliphatic and / or aromatic polyester diisocyanates and polyether diisocyanates capped with (meth)acrylate end groups. Suitable polyurethane (meth)acrylate oligomers include, for example, aliphatic polyester-based urethane diacrylate oligomers and tetraacrylate oligomers, aliphatic polyether-based urethane diacrylate oligomers and tetraacrylate oligomers, and aliphatic polyester / polyether-based urethane diacrylate oligomers and tetraacrylate oligomers.

[0156] Polyurethane (meth)acrylate oligomers can be prepared by reacting an aliphatic, cycloaliphatic and / or aromatic polyisocyanate (e.g., diisocyanate, triisocyanate) with an OH-terminated polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polyorganosiloxane polyol (e.g., polydimethylsiloxane polyol), or polydiene polyol (e.g., polybutadiene polyol), or a combination thereof, to form an isocyanate-functionalized oligomer, which is then reacted with a hydroxyl-functionalized (meth)acrylate, such as hydroxyethyl acrylate or hydroxyethyl methacrylate, to provide terminal (meth)acrylate groups. For example, polyurethane (meth)acrylate oligomers can contain 2, 3, 4 or more (meth)acrylate functional groups per molecule. As known in the art, other addition sequences can also be implemented to prepare polyurethane (meth)acrylates. For example, a hydroxyl-functionalized (meth)acrylate may be first reacted with a polyisocyanate to obtain an isocyanate-functionalized (meth)acrylate, which may then be reacted with an OH-terminated polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polydimethylsiloxane polyol, polybutadiene polyol, or a combination thereof. In yet another embodiment, a polyisocyanate may first be reacted with a polyol, including any of the aforementioned types of polyols, to obtain an isocyanate-functionalized polyol, which may then be reacted with a hydroxyl-functionalized (meth)acrylate to obtain a polyurethane (meth)acrylate. Alternatively, all components may be combined and reacted simultaneously. Examples of suitable polyurethane (meth)acrylates are available from Arkema under the reference numbers CN9001, CN9010, CN991, CN996, CN989.

[0157] Suitable acrylic (meth)acrylate oligomers include oligomers that can be described as materials having an oligomeric acrylic backbone functionalized with one or more (meth)acrylate groups, which may be terminal to the oligomer and / or pendant to the acrylic backbone. The acrylic backbone can be a homopolymer, random copolymer, or block copolymer composed of repeating units of acrylic monomers. The acrylic monomers can be any monomeric (meth)acrylate, such as C1-C6 alkyl (meth)acrylates, as well as functionalized (meth)acrylates, such as (meth)acrylates with hydroxyl, carboxylic acid, and / or epoxy groups. Acrylic (meth)acrylate oligomers may be prepared using any procedure known in the art, such as by oligomerizing monomers, at least a portion of which are functionalized with hydroxyl, carboxylic acid and / or epoxy groups (e.g., hydroxyalkyl (meth)acrylates, (meth)acrylic acid, glycidyl (meth)acrylate) to obtain a functionalized oligomeric intermediate, which is then reacted with one or more (meth)acrylate-containing reactants to introduce the desired (meth)acrylate functionality.

[0158] Suitable polydiene (meth)acrylate oligomers include oligomers that may be described as having an oligomeric polydiene backbone functionalized with one or more (meth)acrylate groups, which may be at the end of the oligomer and / or pendant to the polydiene backbone. The polydiene backbone may be a homopolymer, random copolymer, or block copolymer composed of repeating units of diene monomers. The diene monomer may be any monomeric conjugated diene, such as 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2,4-hexadiene, and mixtures. The polydiene (meth)acrylate oligomers can be prepared using any procedure known in the art, such as by reacting a hydroxylated and / or epoxidized polydiene resin with (meth)acrylic acid.

[0159] The total amount of (meth)acrylate functionalized oligomer in the polymerizable composition can be 0 to 99.5%, 1 to 99%, 2 to 90%, 5 to 80%, 10 to 70%, 15 to 60%, 20 to 50%, 25 to 45%, or 30 to 40% by weight based on the weight of the composition. In particular, the polymerizable composition can include 50 to 99%, 50 to 95%, 50 to 90%, 50 to 85%, 50 to 80%, or 50 to 75% by weight of (meth)acrylate functionalized oligomer based on the weight of the composition. Alternatively, the polymerizable composition can include 1 to 50%, 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 oligomer based on the weight of the composition.

[0160] The ethylenically unsaturated compound may comprise an amine-modified acrylate.The ethylenically unsaturated compound may comprise a mixture of amine-modified acrylates.

[0161] Reacting an acrylate-functionalized compound with an amine-containing compound (aza-Michael addition) provides an amine-modified acrylate that contains at least one remaining acrylate group (i.e., an acrylate group that did not react with the amine-containing compound during the aza-Michael addition) and / or at least one (meth)acrylate group (which may not be reactive toward primary or secondary amines).

[0162] The acrylate-functionalized compounds may be acrylate-functionalized monomers and / or acrylate-functionalized oligomers as defined above.

[0163] The amine-containing compound contains a primary or secondary amine group and optionally a tertiary amine group. The amine-containing compound may contain two or more primary and / or secondary amine groups. The amine-containing compound may be selected from monoethanolamine (2-aminoethanol), 2-ethylhexylamine, octylamine, cyclohexylamine, sec-butylamine, isopropylamine, diethylamine, diethanolamine, dipropylamine, dibutylamine, 2-(methylamino)ethano-1,2-methoxyethylamine, bis(2-hydroxypropyl)amine, diisopropylamine, dipentylamine, dihexylamine, bis(2-ethylhexyl)amine, 1,2,3,4-tetrahydroisoquinoline, N-benzylmethylamine, morpholine, piperidine, dioctylamine and di-cocoamine, dimethylaminopropylamine, dimethylaminopropylaminopropylamine, 1,4-bis(3-aminopropyl)piperazine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(3-aminopropyl)piperazine, aniline and optionally substituted benzocaine (ethyl-4-aminobenzenate).

[0164] Examples of commercially available amine modified acrylates include CN3705, CN3715, CN3755, CN381 and CN386, all available from Arkema. Polymeric or multi-amino types are also suitable.

[0165] The polymerizable composition may comprise from 0% to 25%, specifically from 2.5% to 20%, more specifically from 5 to 15%, by weight of the amine-modified acrylate, based on the total weight of the polymerizable composition.

[0166] Photoinitiators The polymerizable compositions of the present invention may include a photoinitiator.

[0167] The photoinitiator may be a radical photoinitiator, in particular a radical photoinitiator with Norrish Type I activity and / or Norrish Type II activity, more particularly a radical photoinitiator with Norrish Type I activity.

[0168] Non-limiting types of radical photoinitiators suitable for use in the polymerizable compositions of the present invention include, for example, benzoin, benzoin ethers, acetophenone, α-hydroxyacetophenone, benzil, benzil ketals, anthraquinones, phosphine oxides, acylphosphine oxides, α-hydroxyketones, phenylglyoxylates, α-aminoketones, benzophenones, thioxanthones, xanthones, acridine derivatives, phenazene derivatives, quinoxaline derivatives, triazine compounds, benzoyl formates, aromatic oximes, metallocenes, acylsilyl or acylgermanyl compounds, camphorquinone, polymeric derivatives thereof, and mixtures thereof.

[0169] Examples of suitable radical photoinitiators include 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-benzylanthraquinone, 2-t-butylanthraquinone, 1,2-benzo-9,10 anthraquinone, benzil, benzoin, benzoin ether, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-phenylbenzoin, Michler's ketone, acetophenone, e.g., 2,2-dialkoxybenzophenone, and 1-hydroxyphenyl. ketone, benzophenone, 4,4'-bis-(diethylamino)benzophenone, acetophenone, 2,2-diethyloxyacetophenone, diethyloxyacetophenone, 2-isopropylthioxanthone, thioxanthone, diethylthioxanthone, 1,5-acetonaphthylene, benzyl ketone, α-hydroxyketo, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzyl dimethyl ketal, 2,2-dimethoxy-1,2-diphenylethanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4- (Methylthio)phenyl]-2-morpholinopropanone-1,2-hydroxy-2-methyl-1-phenyl-propanone, oligomeric alpha-hydroxyketones, benzoylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphinic acid, anisoin, anthraquinone, anthraquinone-2-sulfonic acid, sodium salt monohydrate, (benzene)tricarbonylchromium, benzyl, benzoin isobutyl ether, benzophenone / 1-hydroxycyclo Hexyl Phenyl Ketone, 50 / 50 Blend, 3,3',4,4'-Benzophenonetetracarboxylic Dianhydride, 4-Benzoylbiphenyl, 2-Benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 4,4'-Bis(diethylamino)benzophenone, 4,4'-Bis(dimethylamino)benzophenone, Camphorquinone, 2-Chlorothioxanthen-9-one, Dibenzosuberenone, 4,4'-Dihydroxybenzophenone, 2,2-Dimethoxy-2-phenylacetophenone, 4-(Dimethylamino)benzophenone, 4,4'-Dimethylbenzyl, 2,5-Dimethylbenzophenone, 3,4-Dimethylbenzophenone, Diphenyl(2,4,6)-trimethylbenzoyl)phosphine oxide / 2-hydroxy-2-methylpropiophenone, 50 / 50 blend, 4'-Ethoxyacetophenone, 2,4,6-Trimethylbenzoyldiphenylphosphine oxide, Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, Ferrocene, 3'-Hydroxyacetophenone, 4'-Hydroxyacetophenone, 3-Hydroxybenzophenone, 4-Hydroxybenzophenone, 1-Hydroxy These include, but are not limited to, cyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-methylbenzophenone, 3-methylbenzophenone, methylbenzoyl formate, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, phenanthrenequinone, 4'-phenoxyacetophenone, (cumene)cyclopentadienyliron(II) hexafluorophosphate, 9,10-diethoxy and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, thioxanthen-9-one, and combinations thereof.

[0170] In particular, the photoinitiator may be a benzophenone (such as Speedcure® BP, Speedcure® 7005, Speedcure® 7006), a thioxanthone (such as Speedcure® 7010, Speedcure® ITX), an α-hydroxyacetophenone, an acylphosphine oxide (such as Speedcure® BPO, Speedcure® TPO, Speedcure® TPO-L). Preferably, the photoinitiator is Speedcure® BPO.

[0171] The amount of photoinitiator in the polymerizable composition can vary as may be appropriate depending on, among other factors, the photoinitiator selected, the amount and type of polymerizable species intended to be photopolymerized, the radiation source and radiation conditions used, etc. Typically, however, the amount of photoinitiator in the polymerizable composition can be from 0 to 15%, 0.05 to 10%, 0.1 to 5%, or 0.5 to 5% by weight based on the weight of the polymerizable composition.

[0172] Amine Synergists The polymerizable composition of the present invention may include an amine synergist. The polymerizable composition may include a mixture of amine synergists.

[0173] Amine synergists can be introduced into the polymerizable compositions of the present invention to act synergistically with Norrish type II photoinitiators and / or to reduce oxygen inhibition. Amine synergists are typically tertiary amines. When used in combination with Norrish type II photoinitiators, tertiary amines provide active hydrogen donor sites for the excited triplet state of the photoinitiator, thus generating reactive alkyl-amino radicals that can then initiate polymerization. Tertiary amines can also convert non-reactive peroxy species formed by the reaction of oxygen with free radicals into reactive alkyl-amino radicals, thus reducing the effect of oxygen on curing.

[0174] When the polymerizable composition comprises an amine-modified acrylate monomer or oligomer as defined above, it may not be necessary to add an amine synergist to the composition.

[0175] Examples of suitable amine synergists include low molecular weight tertiary amines (i.e., having a molecular weight of less than 200 g / mol), such as triethanolamine, N-methyldiethanolamine, etc. Other types of amine synergists are aminobenzoates, polymeric aminobenzoates, polymeric aminobenzoates, and mixtures thereof. Examples of aminobenzoates include ethyl 4-(dimethylamino)benzoate (EDB), pentyl 4-(dimethylamino)benzoate, 2-ethylhexyl 4-(dimethylamino)benzoate, and 2-butoxyethyl 4-(dimethylamino)benzoate (BEDB).

[0176] The concentration of the amine synergist in the polymerizable composition will vary depending on the type of compound used, but typically the polymerizable composition is formulated to contain from 0% to 25%, particularly from 0.5% to 20%, and more particularly from 1 to 15%, by weight of amine synergist, based on the total weight of the polymerizable composition.

[0177] Other flame retardants The polymerizable composition of the present invention may comprise a flame retardant other than component a).The polymerizable composition may comprise a mixture of flame retardants other than component a).

[0178] Other flame retardants may be aromatic amines. Examples of suitable aromatic amines include melamine, melamine condensates (i.e., melam, melem, or melon), melamine derivatives (e.g., melamine cyanurate, melamine borate), and reaction products of melamine or melamine condensates with phosphoric acid or condensed phosphoric acids (e.g., dimelamine phosphate, dimelamine pyrophosphate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melon polyphosphate, and melem polyphosphate, and mixed polysalts).

[0179] Other flame retardants are of the formula (NH4) r’ H 3-r’ PO4 or (NH4PO3) s’where r' is from 1 to 3 and s' is from 1 to 10,000. Examples are ammonium hydrogen phosphate, ammonium dihydrogen phosphate or ammonium polyphosphate.

[0180] Other flame retardants may be metal or metalloid compounds. Metal or metalloid compounds may include M-containing oxides, M-containing halides, M-containing alkoxides, M-containing hydroxides, M-containing nitrates, M-containing sulfates, M-containing sulfides, M-containing carboxylates, M-containing carbonates, M-containing borates, M-containing phosphates, M-containing stannates and combinations thereof, where M is a metal or metalloid selected from the group consisting of Li, Na, K, Ce, Mg, Ca, Sr, Ba, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Cu, Zn, Cd, Hg, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, and Bi, particularly Si, Mg, Zn, Al. Examples of such compounds include antimony oxide, salts and esters of orthosilicic acid and its condensates, silica, silicates, zeolites, glass powders, glass ceramic powders, ceramic powders, magnesium hydroxide, hydrotalcite, magnesium carbonate, magnesium calcium carbonate, aluminum hydroxide, aluminum phosphate, boehmite, zinc oxide, zinc stannate, zinc hydroxystannate, zinc phosphate, zinc borate, zinc sulfide, bismuth oxide, molybdenum oxide, zinc borate, barium metaborate, calcium borate.

[0181] Other flame retardants may be selected from halogenated compounds. Examples of halogenated compounds are halogenated phosphates such as tris(2-chloropropyl)phosphate, tris(2,3-dibromopropyl)phosphate and tris(1,3-dichloropropyl)phosphate. Other examples of halogenated compounds are bromine- or chlorine-containing acid components or bromine- or chlorine-containing alcohol components such as hexachloroendomethylenetetrahydrophthalic acid, tetrabromophthalic acid, tetrabromophthalic anhydride and dibromoneopentyl glycol. Other examples of halogenated compounds are bromine- or chlorine-containing aromatic and aliphatic compounds such as brominated polystyrene, polybromobenzyl acrylate, tetrabromobisphenol A and derivatives, polybrominated diphenyl ether, ethylenebistetrabromophthalimide, brominated epoxy oligomers, polybrominated diphenyl ethane, hexabromocyclododecane, chloroparaffin and dodecachloropentacyclooctadecadiene.

[0182] Another flame retardant may be graphite. Suitable graphites are known in the art and may include natural and synthetic graphite. Non-limiting examples of suitable graphites may include expanded graphite and / or exfoliated graphite. In certain embodiments, expanded graphite in solid or powder form is intercalated with an acid, such as, but not limited to, organic acids (e.g., acetic acid) and inorganic acids (e.g., H2SO4 and HNO3).

[0183] The other flame retardant may be a phosphinate or diphosphinate and / or a polymer thereof. Examples include the phosphinate of formula (XXXVI) and the diphosphinate of formula (XXXVII): TIFF2024519049000021.tif58170 R 35 and R' 35 is independently selected from alkyl and aryl; R 36 is a bivalent linker as defined above for R; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitro base; s'', t'' and u' are independently 1 to 4.

[0184] The other flame retardant may be a phosphate ester or an oligomeric phosphate ester. The phosphate ester may be according to formula (XXXVIII) and the oligomeric phosphate ester may be according to formula (XXXIX): TIFF2024519049000022.tif53170 expression R 37 , R' 37 and R'' 37 is independently selected from alkyl, aryl, and alkoxyalkyl; Or, R 37 and R' 37 may form, together with the oxygen atom to which they are attached, an optionally substituted ring having at least five ring atoms; R 38 and R' 38 is independently selected from alkyl, aryl, and alkoxyalkyl; or if v' is 1, R 38 and R' 38 may form, together with the oxygen atom to which they are attached, an optionally substituted ring having at least five ring atoms; R 39 is R 32 is a bivalent linker as defined above for v' is between 1 and 50.

[0185] Examples of monomeric phosphate esters are triphenyl phosphate, naphthyl diphenyl phosphate, dinaphthyl phenyl phosphate, tricresyl phosphate, tributoxyethyl phosphate, and diphenyl-2-ethylhexyl phosphate. Examples of oligomeric phosphate esters are resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), resorcinol bis(bis(2,6-dimethylphenyl)phosphate), hydroquinone bis(bis(2,6-dimethylphenyl)phosphate), and biphenol bis(bis(2,6-dimethylphenyl)phosphate).

[0186] The other flame retardant may be a phosphonate or a polymeric phosphonate.

[0187] The phosphate ester may be according to formula (XXXX) and the oligomeric phosphate ester may be according to formula (XXXXI), TIFF2024519049000023.tif54170 expression R 40 and R 43 is independently selected from alkyl and aryl; R 41 and R' 41 is independently selected from alkyl, aryl, and alkoxyalkyl; Or, R 41 and R' 41 can form, together with the oxygen atom to which they are attached, an optionally substituted ring having at least five ring atoms; R 42 and R' 42 is independently selected from alkyl, aryl, and alkoxyalkyl; or if w' is 1, R 42 and R' 42 may form together with the oxygen atom to which they are attached an optionally substituted ring having at least five ring atoms; R 44 is R 32is a bivalent linker as defined above for w' is from 1 to 50.

[0188] Examples of such phosphonates include monomeric phosphonates such as dimethyl methyl phosphonate, diethyl ethyl phosphonate, and the like, as well as oligomeric phosphonates such as ethylene bis(diethoxyphosphonate), ethylene bis(dimethoxyphosphonate), methylene bis(diethoxyphosphonate), methylene bis(dimethoxyphosphonate), and the like.

[0189] The amount of other flame retardants can vary widely. In certain embodiments, the polymerizable composition comprises up to 35% (by weight) based on the weight of the composition.

[0190] In a preferred embodiment, the polymerizable composition is substantially free of halogenated flame retardants and / or metallic or semi-metallic flame retardants.

[0191] Additives The polymerizable composition of the present invention may comprise an additive. The polymerizable composition may comprise a mixture of additives.

[0192] In particular, the additives may be selected from stabilizers (antioxidants, light blockers / absorbers, polymerization inhibitors), foam inhibitors, flow or leveling agents, colorants, dispersants, slip additives, fillers, chain transfer agents, thixotropic agents, matting agents, impact modifiers, waxes, mixtures thereof, and any other additive conventionally used in coating, sealant, adhesive, molding, 3D printing or ink technology.

[0193] The polymerizable composition may include a stabilizer.

[0194] Stabilizers may be introduced into the polymerizable composition of the present invention to provide sufficient storage stability and shelf life. In addition, stabilizers may be used during the preparation of the polymerizable composition to protect the ethylenically unsaturated components of the polymerizable composition from undesired reactions during processing. The stabilizer may be a compound or material that retards or prevents the reaction or curing of the chemically polymerizable functional groups present in the composition in the absence of actinic radiation. However, it may be advantageous to select the amount and type of stabilizer such that the composition remains curable when exposed to actinic radiation (i.e., the stabilizer does not interfere with radiation curing of the composition). The stabilizer may in particular be a free radical stabilizer (i.e., a stabilizer that functions by inhibiting free radical reactions).

[0195] Any of the stabilizers known in the art related to (meth)acrylate functionalized compounds can be utilized in the present invention. Quinones represent a particularly preferred class of stabilizers that can be used in the context of the present invention. As used herein, the term "quinone" includes both quinone and hydroquinone, as well as their ethers, such as the monoalkyl, monoaryl, monoaralkyl, and bis(hydroxyalkyl) ethers of hydroquinone. Hydroquinone monomethyl ether is an example of a suitable stabilizer that can be utilized. Other stabilizers known in the art include hydroquinone (HQ), 4-tert-butylcatechol (TBC), 3,5-di-tertiobutyl-4-hydroxytoluene (BHT), phenothiazine (PTZ), pyrogallol, phosphorous compounds, triphenylantimony, and tin (II) salts.

[0196] The concentration of the stabilizer in the polymerizable composition varies depending on the particular stabilizer or combination of stabilizers selected for use, as well as the degree of stabilization desired and the susceptibility of the components of the polymerizable composition to degradation in the absence of the stabilizer. Typically, however, the polymerizable composition is formulated to contain 5 to 5000 ppm of stabilizer. According to certain embodiments of the present invention, the reaction mixture at each stage of the process used to produce the polymerizable composition contains at least some stabilizer, for example at least 10 ppm of stabilizer.

[0197] The polymerizable composition may include a colorant. The colorant may be a dye, a pigment, and a mixture thereof. The term "dye" as used herein means a colorant having a solubility of 10 mg / L or more in the medium in which it is introduced at 25°C. The term "pigment" is defined in DIN 55943 as a colorant that is substantially insoluble in the application medium under the relevant ambient conditions and thus has a solubility of less than 10 mg / L at 25°C. The term "CI" is used as an abbreviation for Colour Index.

[0198] The polymerizable composition of the present invention may include a dispersant, which may be used to disperse insoluble materials, such as pigments or fillers, in the polymerizable composition.

[0199] The dispersant may be a polymeric dispersant, a surfactant, and mixtures thereof.

[0200] solvent The polymerizable compositions of the present invention may be solvent-based or water-based. As used herein, the term "solvent" refers to a non-reactive organic solvent, i.e., a solvent containing carbon and hydrogen atoms that does not react when exposed to actinic radiation used to cure the polymerizable compositions described herein.

[0201] The polymerizable composition of the present invention may be formulated to be solvent-free. For example, the polymerizable composition of the present invention may contain little or no solvent, for example, less than 10%, or less than 5%, or less than 1%, or even 0%, based on the total weight of the polymerizable composition.

[0202] formulation The polymerizable compositions of the present invention can be formulated as one-component or one-part systems, i.e., the polymerizable compositions can be cured directly, i.e., not combined with another component or second part prior to curing.

[0203] In a first embodiment, the polymerizable composition of the present invention comprises: a) a polymerizable flame retardant according to the present invention, b) ethylenically unsaturated compounds, c) optionally a photoinitiator; d) optionally additives; e) optionally a solvent may include.

[0204] The polymerizable composition of the first embodiment is a) 0.5 to 25%, in particular 1 to 20%, more particularly 2 to 10%, of a polymerizable flame retardant; b) from 40 to 99.5%, in particular from 50 to 95%, more particularly from 60 to 90%, of ethylenically unsaturated compounds; c) 0 to 10%, in particular 0.5 to 6%, more particularly 1 to 3%, of a photoinitiator; d) 0 to 30% additive; e) 0 to 30% solvent; The percentages are weight percent based on the weight of the composition, and can comprise, consist essentially of, or consist of.

[0205] Preferably, the polymerizable composition of the present invention does not contain any component other than components a) to e), and therefore the total weight of components a), b), c), d) and e) may represent 100% of the weight of the composition.

[0206] In preferred embodiments of the invention, the polymerizable composition is liquid at 25° C. In various embodiments of the invention, the polymerizable composition described herein is formulated to have a viscosity of less than 10,000 mPa.s, or less than 5,000 mPa.s, or less than 1,000 mPa.s, or less than 500 mPa.s, or less than 250 mPa.s, or even less than 100 mPa.s, measured at 25° C. using a Brookfield Viscometer, Model DV-II, using a 27 spindle (spindle speeds typically vary between 20 and 200 rpm depending on viscosity). In advantageous embodiments of the invention, the viscosity of the polymerizable composition is 10 to 10,000 mPa.s, or 10 to 5,000 mPa.s, or 10 to 1,000 mPa.s, or 10 to 500 mPa.s, or 10 to 250 mPa.s, or 10 to 100 mPa.s at 25° C.

[0207] The polymerizable composition described herein may be a composition that is subjected to curing by free radical polymerization. In certain embodiments, the polymerizable composition may be photocured (i.e., cured by exposure to actinic radiation, such as light, particularly visible light, near UV light or UV light).

[0208] The polymerizable composition of the present invention can be a coating composition, an adhesive composition, a sealant composition, a 3D printing composition, a composite composition or a molding composition.

[0209] End uses of the polymerizable compositions include, but are not limited to, inks, paints, lacquers, varnishes, adhesives, sealants, additive manufacturing resins (such as 3D printing resins), molding resins, composite materials, electronic materials, or packaging materials.

[0210] The polymerizable composition according to the present invention can be used to obtain a cured product or a 3D printed article as described below.

[0211] Method / Usage The method for preparing a cured product according to the present invention comprises curing the polymerizable composition of the present invention. In particular, the polymerizable composition can be cured by exposing the composition to radiation. More particularly, the polymerizable composition can be cured by exposing the composition to UV, near UV and / or visible radiation.

[0212] Curing can be accelerated or promoted by providing energy to the polymerizable composition, for example by heating the polymerizable composition. Thus, the cured product can be considered a reaction product of the polymerizable composition formed by curing. The polymerizable composition may be partially cured by exposure to actinic radiation, and further curing is achieved by heating the partially cured article. For example, the product formed from the polymerizable composition can be heated at a temperature of 40° C. to 120° C. for a period of 5 minutes to 12 hours.

[0213] The polymerizable composition may be applied to at least a portion of a substrate prior to curing. The composition may be applied by any known conventional method, such as by spraying, jetting, knife coating, roller coating, casting, drum coating, dipping, and the like, and combinations thereof. Indirect application using a transfer process may also be used.

[0214] The substrate on which the polymerizable composition is applied and cured can be of any type. Suitable substrates are detailed below. When used as an adhesive, the polymerizable composition is placed between two substrates and then cured, whereby the cured composition can bond the substrates together to provide an adhesive article. The polymerizable composition according to the present invention can be formed or cured in a bulk manner (e.g., the polymerizable composition can be cast into a suitable mold and then cured).

[0215] The present invention further relates to a method of coating a substrate comprising applying to at least a portion of the substrate the polymerizable composition described above.

[0216] The polymerizable composition of the present invention can be applied to a wide variety of substrates. Non-limiting examples of suitable substrates may include, but are not limited to, cellulosic materials (such as paper, cardboard, wood, straw, etc., or materials containing plant fibers such as bamboo, cotton, flax, hemp, jute, lyocell, modal, rayon, raffia, ramie, or sisal), wool, fur, silk, leather, metals, natural and / or synthetic stone, ceramics, glass, brick, concrete, drywall (also called gypsum board, wall board, slate rock, cement board, or gypsum board), roofing board, asphalt, fiberglass, mineral wool, thermoplastic materials, thermosetting materials, polymer composites, and combinations thereof. Metals may include, but are not limited to, aluminum, cold-rolled steel, electrogalvanized steel, hot-dip galvanized steel, titanium, and alloys. Thermoplastic materials refer to any material that can be softened or fused when heated and can be solidified (hardened) again when cooled. Non-limiting examples of suitable thermoplastic materials may include polyolefins, polyurethanes, polyesters, polyamides, polyureas, acrylics, and mixtures thereof. Thermosetting materials refer to any material that becomes permanently rigid after heating and / or curing. Non-limiting examples may include polyurethane polymers, polyester polymers, polyamide polymers, polyurea polymers, polycarbonate polymers, acrylic polymers, resins, copolymers thereof, and mixtures thereof. There is no limit to the shape of the substrate. It may be a sheet, a film, a non-woven or woven fiber mat, or a three-dimensional object.

[0217] In a non-limiting example, the coating composition of the present invention can be applied to at least a portion of an article of manufacture, such as an architectural structure or vehicle. "Vehicle" includes, but is not limited to, civilian, commercial, and military land, water, and air vehicles, such as automobiles, trucks, boats, ships, submarines, airplanes, helicopters, and tanks. The article of manufacture can be an architectural structure. "Architectural structure" includes, but is not limited to, residential, commercial, and military structures, such as at least a portion of a structure including a roof, floor, support beams, walls, etc.

[0218] The polymerizable flame retardants of the present invention are particularly useful in radiation curable compositions, especially UV or LED curable compositions.

[0219] The polymerizable flame retardant of the present invention can be used in a polymerizable composition selected from a coating composition, an adhesive composition, a sealant composition, a 3D printing composition, a composite composition or a molding composition.

[0220] In particular they can be used in intumescent paints and lacquers, coatings applied to wood, textiles and other cellulose-containing products, adhesives for electronic applications or fiber-reinforced composites.

[0221] The polymerizable flame retardants of the present invention may be used to obtain cured products that have flame retardant and / or heat resistance and / or reduced amounts of extractables.

[0222] In particular, the cured product may be selected from an ink, a paint, a lacquer, a varnish, an adhesive, a sealant, a 3D printed article, a moulded article, a composite material, an electronic material or a packaging material.

[0223] Improved flame and / or heat resistance refers to an assessment of the degree to which flame and / or heat resistance is improved as compared to a cured product that does not include the flame retardant material. Flame retardancy can be determined using the test methods described herein.

[0224] The reduction in the amount of extractables can be evaluated in comparison to a cured product obtained using a conventional flame retardant (i.e., a non-polymerizable phosphorus-based flame retardant). Extractables may be any component that migrates from the cured product. In particular, extractables may be the flame retardant or its residues.

[0225] Terms The present invention may be as defined in the following clauses.

[0226] Clause 1. Polymerizable flame retardants, - 1 or 2 (meth)acrylate-containing moieties, - one phosphorus-containing moiety containing two or more phosphorus atoms, and optionally one or more urethane or ester bonds A polymerizable flame retardant comprising:

[0227] Clause 2. The polymerizable flame retardant of clause 1, wherein each (meth)acrylate-containing moiety independently has 1 to 6 (meth)acrylate groups, particularly 1 to 3 (meth)acrylate groups, and more particularly 1 (meth)acrylate group.

[0228] Clause 3. Each (meth)acrylate-containing moiety independently comprises the formula (Ia): TIFF2024519049000024.tif32170 expression R1 is H or methyl; R2 is an (a+1)-valent linker; a is 1 to 6, in particular 1 or 2, more particularly 1; Including the portion corresponding to 3. A polymerizable flame retardant according to clause 1 or 2.

[0229] Clause 4. Each (meth)acrylate-containing moiety independently comprises the formula (Ib): TIFF2024519049000025.tif32170, wherein R1, R2, and a are as defined in clause 3; Including the portion corresponding to 4. A polymerizable flame retardant according to any one of clauses 1 to 3.

[0230] Clause 5. The polymerizable flame retardant according to clause 3 or 4, wherein R2 is an (a+1)-valent linker selected from an aliphatic or aromatic hydrocarbon linker, a polyether linker, a polyester linker, a polycarbonate linker, a polyurethane linker, a polyorganosiloxane linker, a polycaprolactone linker, a polybutadiene linker, an isocyanurate linker, and combinations thereof, in particular, R2 is selected from an aliphatic or aromatic hydrocarbon linker, a polyether linker, a polyester linker, and combinations thereof, more particularly, R2 is selected from an alkylene, an alkoxylated linker, and a polyester linker.

[0231] Clause 6. R2 is selected from a trivalent linker corresponding to formula (II) or (III), a tetravalent linker corresponding to formula (IV) or (V), and a hexavalent linker corresponding to formula (VI); TIFF2024519049000026.tif33170 expression R4, R'4, R5, R'5, R6 and R'6 are independently H or methyl; R7 is selected from H, alkyl and alkoxy, in particular R7 is alkyl; c, c' and c'' are independently 0 to 2, with the proviso that at least two of c, c' and c'' are not 0, and in particular, c, c' and c'' are all 1 or c is 0 and c' and c'' are 1; d, d' and d'' are independently 2 to 4, in particular 2; e, e' and e'' are independently 0 to 10, in particular 1 to 6; TIFF2024519049000027.tif40170 expression R 11 , R 12 , R 13 , R 14 , R 15 and R 16 is independently H or methyl, in particular H; l, m and n are independently 1 to 6, in particular 2; TIFF2024519049000028.tif45170 expression R8, R'8, R9, R'9, R 10 , R' 10 , R 11 and R' 11 are independently H or methyl; f, f', f'', and f''' are independently 0 to 2, with the proviso that at least three of f, f', f'', and f''' are not 0, and in particular f, f', f'', and f''' are all 1; g, g', g'' and g''' are independently 2 to 4, in particular 2; h, h', h'' and h'''' are independently 0 to 10, in particular 1 to 6; TIFF2024519049000029.tif34170 expression R 12 , R' 12 , R 13 , R' 13 , R 14 , R' 14 , R 15 and R' 15 are independently H or methyl; i, i', i'' and i'''' are independently 2 to 4, in particular 2; j, j', j'' and j'''' are independently 0 to 10, in particular 1 to 6; TIFF2024519049000030.tif42170 expression R 16 , R' 16 , R 17 , R' 17 , R 18 , R' 18 , R 19 , R' 19 , R 20 , R' 20 , R 21 and R' 21 are independently H or methyl; k, k', k'', k''', k* and k** are independently 2 to 4, in particular 2; 6. The polymerizable photoinitiator according to any one of clauses 3 to 5, wherein l, l', l'', l''', l* and l** are independently from 0 to 10, in particular from 1 to 6.

[0232] Clause 7.R2 is a compound represented by the formula (VII) to (XI): -(CR 22 R' 22 ) m -(VII) -[(CR 23 R' 23 ) n -O] o -(CR 23 R' 23 ) n -(VIII) -[(CR 24 R' 24 ) p -O] q -(CR 25 R' 25 ) r -[O-(CR 26 R' 26 ) p’ ] q’ -(IX) -[(CR 27 R' 27 ) s -C(=O)O] t -(CR 28 R' 28 ) u -*(X) -[(CR 29 R' 29 ) v -OC(=O)-(CR 30 R' 30 ) w -C(=O)-O] x -(CR 29 R' 29 ) v -(XI) During the ceremony R 22 , R' 22 , R 25 , R' 25 , R 29 , R' 29 , R 30 and R' 30are independently H or alkyl; R 23 , R' 23 , R 24 , R' 24 , R 26 , R' 26 , R 27 , R' 27 , R 28 and R' 28 are independently H or methyl; m is from 2 to 20; n, p and p' are independently 2 to 4; o is from 1 to 20; q and q' are independently 0 to 20, with the proviso that at least one of q and q' is not 0; r is between 2 and 20; s is between 3 and 12, t is from 1 to 20, u is from 2 to 8, v is from 2 to 20, w is from 2 to 30; x is 1 to 20, the symbol * indicates the point of attachment to the (meth)acrylate group; In particular, R2 is an alkylene, such as 1,2-ethanediyl, 1,2- or 1,3-propanediyl, 1,2-, 1,3- or 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,8-octanediyl, 1,9-nonanediyl, 1,10-decanediyl, 1,12-decanediyl, 2-methyl-1,3-propanediyl, 2,2-diethyl-1,3-propanediyl, 3-methyl-1,5-pentanediyl, 3,3-dimethyl-1,5-pentanediyl, 2,2-dimethyl-1,3-propanediyl, 2,4-diethyl-1,5-pentanediyl; 6. The polymerizable photoinitiator according to any one of clauses 3 to 5, wherein the divalent linker is selected from: alkoxylated derivatives; esterified derivatives of the aforementioned alkylenes; residues of di-, tri-, tetra- or polyoxyalkylenes having no OH groups, such as di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol, di-, tri- or tetrabutylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, poly(ethylene glycol-co-propylene glycol); and residues of polyester polyols not containing OH groups.

[0233] Clause 8. The phosphorus-containing moiety comprises two or more phosphorus-containing units, each unit comprising a phosphorus atom, in particular, each phosphorus-containing unit independently comprises a phosphate moiety, a phosphonate moiety, or a phosphinate moiety, and more particularly, each phosphorus-containing unit comprises a group represented by the following formula (XII): TIFF2024519049000031.tif22170, R 31 is independently OH, alkyl, alkoxy, aryl, aryloxy, alkylaryl or alkylaryloxy, in particular C1-C4 alkyl or C1-C4 alkoxy.

[0234] Clause 9. The phosphorus-containing moiety comprises a moiety represented by formula (XIII) or (XIX), TIFF2024519049000032.tif60170 expression Each R 31 is independently OH, alkyl, alkoxy, aryl, aryloxy, alkylaryl or alkylaryloxy, in particular C1-C4 alkyl or C1-C4 alkoxy; Each R 32 are independently alkylene optionally substituted with one or more phenyl groups, alkyleneoxyalkylene optionally substituted with one or more phenyl groups, poly(alkyleneoxyalkylene) optionally substituted with one or more phenyl groups, arylene or alkylarylene, in particular alkylene, alkyleneoxyalkylene or poly(alkyleneoxyalkylene), Each R 33 and R' 33 are independently alkylene, particularly C2-C4 alkylene; y is from 1 to 50, in particular from 1 to 10; 9. The polymerizable flame retardant according to any one of the preceding clauses, wherein z and z' are independently 0 to 20, with the proviso that at least one of z and z' is not 0, in particular z and z' are independently 1 to 20.

[0235] Article 10.R 32 Formula (XIV) to (XVIII): -(CR 33 R' 33 ) m’ -(XVI) -[(CR 34 R' 34 ) n’ -O] o’ -(CR 34 R' 34 ) n’ -(XV) -Ph-(XVI) -(CR 35 R' 35 ) p’’ -Ph-(CR 36 R' 36 ) q’’ -(XVII) -Ph-(CR 37 R'37 ) r’’ -Ph-(XVIII) During the ceremony Each R 33 , R' 33 , R 34 and R' 34 is independently selected from H, alkyl and phenyl; Each R 35 , R' 35 , R 36 , R' 36 , R 37 and R' 37 is independently selected from H and alkyl; Ph is optionally substituted phenylene; m' is 1 to 10; n' is 2 to 4; o' is from 1 to 50, p'' and q'' are independently 0 to 10, with the proviso that at least one of p'' and q'' is not 0; 10. The polymerizable flame retardant according to claim 8 or 9, wherein r″ is selected from one of the following:

[0236] Clause 11. The polymerizable flame retardant according to any one of clauses 1 to 10, comprising at least one linker L connecting the (meth)acrylate-containing moiety and the phosphorus-containing moiety, in particular comprising two linkers L, each linker L connecting the (meth)acrylate-containing moiety to one end of the phosphorus-containing moiety.

[0237] Clause 12. The linker L is represented by the following formula (XX) or (XXI): TIFF2024519049000033.tif37170, During the ceremony L1 is selected from an aliphatic linker, an alicyclic linker, an aromatic linker, and an araliphatic linker; L2 is selected from an aliphatic linker, a cycloaliphatic linker, an aromatic linker, and an araliphatic linker; In particular, the linker L corresponds to the formula (XX): 12. A polymerizable flame retardant as defined in clause 11.

[0238] Clause 13. The linker L1 is the residue of a diisocyanate of formula OCN-L1-NCO or a derivative thereof that does not have an NCO group; in particular, the diisocyanate of formula OCN-L1-NCO is an aliphatic diisocyanate, a cycloaliphatic diisocyanate, an aromatic diisocyanate and an araliphatic diisocyanate or a derivative thereof; more particularly, the diisocyanate of formula OCN-L1-NCO is 2,4- and 2,6-toluene diisocyanate (TDI), isophorone diisocyanate (corresponding to IPDI-3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate), tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate, 13. Polymerizable flame retardants according to clause 12, which are diisocyanates (TMDI), 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), 2,2'-, 2,4'- and 4,4'-dicyclohexylmethane diisocyanate (H12MDI), 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 1,4-benzene diisocyanate, 1,5-naphthalene diisocyanate (NDI), 1,3- and 1,4-cyclohexane diisocyanate, 1-methyl-2,4-diisocyanatocyclohexane, 1-methyl-2,6-diisocyanatocyclohexane, dodecane diisocyanate, m-tetramethylene xylylene diisocyanate, 4,6-xylylene diisocyanate and derivatives thereof.

[0239] Item 14. The linker L2 is COOR 38 having no group, formula R 38 OOC-L2-COOR 38 where R is the residue of a diacid or diester of 38 is H or alkyl, or the linker L2 corresponds to a cyclic anhydride moiety that forms a ring with the -C(=O)-OC(=O)- group; in particular, the formula R 38 OOC-L2-COOR 38The diacids or diesters of formula R are aliphatic diacids or diesters, cycloaliphatic diacids or diesters, aromatic diacids or diesters, araliphatic diacids or diesters, and aliphatic diacids or diesters; more particularly, diacids or diesters of formula R 38 OOC-L2-COOR 38 13. The polymerizable flame retardant according to claim 12, wherein the diacid or diester is an aliphatic diacid or diester, and even more particularly a saturated or unsaturated aliphatic diacid or diester.

[0240] Clause 15. One of the structures of formulae (XXII) to (XXV), Y-PHOS-ACR(XXII) ACR-PHOS-ACR(XXIII) Y-PHOS-L-ACR(XXIV) ACR-L-PHOS-L-ACR(XXV) During the ceremony ACR is a (meth)acrylate-containing moiety as defined in any one of clauses 2 to 7; PHOS is a phosphorus-containing moiety as defined in any one of clauses 8 to 10; L is a linker as defined in any one of clauses 11 to 14, Y is a terminal group 15. The polymerizable flame retardant according to any one of claims 1 to 14,

[0241] Clause 16. The polymerizable flame retardant according to clause 15, wherein Y is selected from H, alkyl and aryl, in particular Y is H or alkyl.

[0242] Clause 17. Structures of formulae (XXVI) to (XXVII) TIFF2024519049000034.tif23170(XXIV) TIFF2024519049000035.tif23170(XXV) TIFF2024519049000036.tif24170(XXVI) TIFF2024519049000037.tif24170(XXVII) During the ceremony R1 and a are as defined in Clause 3; R2 is as defined in any one of clauses 3 to 7; R 31 , R 33 , R' 33 , y, z and z' are as defined in Clause 9; R 32 is as defined in clause 9 or 10, L is as defined in any one of clauses 11 to 14; Y is as defined in clause 15 or 16 17. The polymerizable flame retardant according to any one of the preceding claims, which corresponds to one of the following:

[0243] Clause 18. A method for preparing a polymerizable flame retardant as defined in any one of clauses 1 to 17, wherein the polymerizable flame retardant is a reaction product of at least one phosphorus-containing compound, at least one (meth)acrylate-containing compound and, optionally, at least one OH-reactive compound.

[0244] Clause 19. The phosphorus-containing compound corresponds to formula (XXX), the (meth)acrylate-containing compound corresponds to formula (XXXI) or (XXXII), and the OH-reactive compound is selected from a diisocyanate or a derivative thereof corresponding to formula (XXXIII), a diacid or diester corresponding to formula (XXXIV), and a cyclic anhydride corresponding to formula (XXXV); TIFF2024519049000038.tif94170OCN-L1-NCO(XXXIII) R 34 OOC-L2-COOR 34 (XXXIV) TIFF2024519049000039.tif24170 expression R1 and a are as defined in Clause 3; R2 is as defined in any one of clauses 3 to 7; R 31 , R 33 , R' 33, y, z and z' are as defined in Clause 9; R 32 is as defined in clause 9 or 10, L1 is as defined in clause 12 or 13; L2 is as defined in clause 12 or 14; R 34 and R' 34 are independently H or alkyl; The method of claim 18, wherein Y and Y' are independently selected from H, alkyl and aryl, with the proviso that at least one of Y and Y' is H.

[0245] Clause 20. The method according to clause 18 or 19, wherein the polymerizable flame retardant is a reaction product of at least one phosphorus-containing alcohol, at least one (meth)acrylate-containing alcohol, and at least one OH-reactive compound selected from diisocyanates, diisocyanate derivatives, diacids, diesters and cyclic anhydrides, in particular the polymerizable flame retardant is obtained by a method comprising the following successive steps: reacting at least one OH-reactive compound with at least one (meth)acrylate-containing alcohol, and then adding at least one phosphorus-containing alcohol to the product obtained.

[0246] Clause 21.a) A polymerizable flame retardant according to any one of clauses 1 to 17 or prepared according to the method according to any one of clauses 18 to 20, b) Ethylenically unsaturated compounds other than a) 1. A polymerizable composition comprising:

[0247] Clause 22. The polymerizable composition of clause 21, wherein the ethylenically unsaturated compound is selected from (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, amine-modified acrylates, and mixtures thereof, in particular, the ethylenically unsaturated compound comprises a (meth)acrylate-functionalized monomer.

[0248] Clause 23. The polymerizable composition, - 10 to 95%, 20 to 90%, 30 to 85%, 40 to 80%, 50 to 75%, or 60 to 70% of component a), - 5 to 90%, 10 to 80%, 15 to 70%, 20 to 60%, 25 to 50%, or 30 to 40% of component b), % is weight percent based on the total weight of components a) and b); 23. The polymerizable composition of claim 21 or 22, comprising:

[0249] Clause 24. The polymerizable composition according to any one of clauses 21 to 23, further comprising one or more compounds selected from photoinitiators, amine synergists, flame retardants other than component a), additives, and solvents.

[0250] Clause 25. The polymerizable composition of any one of clauses 21 to 24, wherein the polymerizable composition is a coating composition, an adhesive composition, a sealant composition, a 3D printing composition, a composite composition, or a molding composition.

[0251] Clause 26. A method for preparing a cured product comprising curing a polymerizable composition according to any one of clauses 21 to 25, in particular by exposing the polymerizable composition to radiation, such as UV, near UV and / or visible radiation.

[0252] Clause 27. Use of a polymerizable flame retardant according to any one of clauses 1 to 17 or prepared according to the method according to any one of clauses 18 to 20 in a radiation curable composition, in particular a UV or LED curable composition.

[0253] Clause 28. Use of a polymerizable flame retardant according to any one of clauses 1 to 17 or prepared according to the method according to any one of clauses 18 to 20 to obtain a cured product having improved flame retardancy and / or improved heat resistance and / or reduced amount of extractables.

[0254] Clause 29. A substrate to which the polymerizable composition according to any one of clauses 21 to 25 has been applied, in particular the substrate is a cellulosic material, wool, fur, silk, leather, metal, natural and / or synthetic stone, ceramic, glass, brick, concrete, drywall, roofing shingles, asphalt, fiberglass, mineral wool, thermoplastic materials, thermosetting materials, polymer composites and combinations thereof.

[0255] Although the embodiments have been described herein in a manner that enables a clear and concise specification to be written, it is intended and will be understood that the embodiments can be combined or separated in various ways without departing from the invention, For example, it will be understood that all preferred features described herein are applicable to all aspects of the invention described herein.

[0256] Although the invention has been illustrated and described herein with reference to specific embodiments, it is not intended that the invention be limited to the details shown, but rather various modifications may be made thereto within the scope and range of equivalents of the claims without departing from the invention. EXAMPLES

[0257] material The following materials were used in the examples: TIFF2024519049000040.tif114170

[0258] Example 1: Preparation of polymerizable flame retardant PRO 32351 33.3 parts of IPDI were added to the reaction vessel under stirring at 200 rpm and protected with dry air. 17.3 parts of HEA were added slowly to the reaction vessel to react with IPDI starting at room temperature, then exothermed to 60° C. and maintained at 60° C. for 30 minutes. 49.4 parts of Exolit® OP 550 were added slowly to the reaction vessel at 60° C., exothermed to 80° C. and maintained at 80° C. for 1 hour. Aliquots were taken to check the NCO content every hour until the NCO content was less than 0.1%. The reaction vessel was then cooled to 60° C. and the resin was transferred from the reaction vessel to a storage vessel.

[0259] Example 2: Preparation of polymerizable flame retardant PRO 32403 37 parts of HMDI were added to the reactor under stirring at 200 rpm and protected with dry air. 16.4 parts of HEA were added slowly to the reactor to react with HMDI starting at room temperature, then allowed to exotherm to 60° C. and held at 60° C. for 30 minutes. 46.6 parts of Exolit® OP 550 were added slowly to the reactor at 60° C., allowed to exotherm to 80° C. and held at 80° C. for 1 hour. Aliquots were taken to check the NCO content every hour until the NCO content was less than 0.1%. The reactor was then cooled to 60° C. and the resin was transferred from the reactor to a storage vessel.

[0260] Example 3: Preparation of polymerizable flame retardant PRO 32362 52.7 parts of HT100 were added to the reactor under stirring at 200 rpm and protected with dry air. 23.3 parts of HEA were added slowly to the reactor to react with HT100 starting at room temperature, then allowed to exotherm to 60°C and held at 60°C for 30 minutes. 24 parts of Exolit® OP 550 were added slowly to the reactor at 60°C, allowed to exotherm to 80°C and held at 80°C for 1 hour. Aliquots were taken to check the NCO content every hour until the NCO content was less than 0.1%. The reactor was then cooled to 60°C and the resin was transferred from the reactor to a storage vessel.

[0261] Example 4: Preparation of polymerizable flame retardant PRO 21500 41.8 parts of TDI were added to the reactor under stirring at 200 rpm and protected with dry air. 27.9 parts of HEA were added slowly to the reactor and reacted with TDI starting at room temperature, then exothermed to 70° C. and maintained at 70° C. for 6 hours. 149.9 parts of Exolit® OP 560 were added slowly to the reactor at 70° C., exothermed to 90° C. and maintained at 90° C. for 2 hours. Aliquots were taken to check the NCO content every hour until the NCO content was less than 0.1%. The reactor was then cooled to 60° C. and the resin was transferred from the reactor to a storage vessel.

[0262] Example 5: Preparation of polymeric flame retardant PRO 21501 27.0 parts of TDI were added to the reactor under stirring at 200 rpm and protected with dry air. 53.3 parts of SR495B were added slowly to the reactor and reacted with TDI starting at room temperature, then exothermed to 60° C. and maintained at 60° C. for 4 hours. 88.6 parts of Exolit® OP 560 were added slowly to the reactor at 60° C. and exothermed to 1100° C. and maintained at 110° C. for 4 hours. Aliquots were taken to check the NCO content every hour until the NCO content was less than 0.1%. The reactor was then cooled to 60° C. and the resin was transferred from the reactor to a storage vessel.

[0263] Example 6: Preparation of polymeric flame retardant PRO 21502 57.2 parts MAA, 2 parts TPPte, 1 part EMHQ, 2 parts BHT, 0.025 parts TEMPOL and 41.6 parts Exolit® OP 560 were added to the reaction vessel under stirring at 200 rpm and protected with dry air. The reaction vessel was brought to 90° C. and maintained at 90° C. for 6 hours. The reaction vessel was then heated at 110° C. for 23 hours. The organic phase was washed three times with 60 g water (stirring time 5 min, decanting time 1 h). The organic phases were combined and the solvent was removed by distillation under reduced pressure (80° C., 80 mBar for 4 hours).

[0264] The product obtained had the following characteristics: Appearance:Transparent Viscosity at 25°C: 36.5 Pa.s Acid value: 199.3mgKOH / g

[0265] Example 7: Flame Retardancy Testing and Results A polymerizable composition was obtained by mixing the following ingredients (amounts are in parts by weight): TIFF2024519049000041.tif30170

[0266] A cured film was obtained in the following manner. TIFF2024519049000042.tif40170

[0267] The flame retardant properties of the cured files were evaluated using the following test methods. TIFF2024519049000043.tif27170

[0268] Flame retardancy grades G0, G1, G2, G3, G4 and G5 were visually evaluated. Photographs corresponding to each grade G1 to G5 are shown in Figure 1.

[0269] The flame retardancy results of the cured films are shown in the table below. TIFF2024519049000044.tif94170

[0270] As shown in Figure 2, the films obtained with the polymerizable flame retardant PRO 32403 (Figure 2a), PRO 32351 (Figure 2b) or PRO 32362 (Figure 2c) as the only ethylenically unsaturated compound had good flame retardancy. They did not ignite easily, had no flame drips and produced only a small amount of white smoke. The films obtained with conventional acrylates (CN991 or DPHA) as the only ethylenically unsaturated compound ignite much more easily and produce a lot of black smoke. The introduction of 30% to 70% (by weight) of the polymerizable flame retardant into the composition based on CN991 or DPHA improves the flame retardancy of the resulting film. PRO32351 performs better than PRO32403 and PRO32362. The best combination is obtained with DPHA as the other ethylenically unsaturated compound.

Claims

1. A polymerizable flame retardant, - 1 or 2 (meth)acrylate-containing moieties, - one phosphorus-containing moiety containing two or more phosphorus atoms, and optionally one or more urethane or ester bonds A polymerizable flame retardant comprising:

2. 2. The polymerizable flame retardant of claim 1, comprising two (meth)acrylate-containing moieties, in particular two terminal (meth)acrylate-containing moieties.

3. Each (meth)acrylate-containing moiety independently has the formula (Ia): During the ceremony R １ is H or methyl, R ２ is an (a+1)-valent linker, a is 1 to 6, in particular 1 or 2, more particularly 1; Including the portion corresponding to The polymerizable flame retardant according to claim 1.

4. The phosphorus-containing moiety comprises two or more phosphorus-containing units, each unit comprising a phosphorus atom, in particular each phosphorus-containing unit independently comprises a phosphate moiety, a phosphonate moiety, or a phosphinate moiety, and more particularly each phosphorus-containing unit comprises a group represented by the following formula (XII): In the formula, R ３１ is OH, alkyl, alkoxy, aryl, aryloxy, alkylaryl or alkylaryloxy, in particular C1-C4 alkyl or C1-C4 alkoxy, 2. The polymerizable flame retardant of claim 1, comprising independently a phosphate or phosphonate moiety corresponding to:

5. the phosphorus-containing moiety comprises a moiety represented by formula (XIII) or (XIX): During the ceremony Each R ３１ is independently OH, alkyl, alkoxy, aryl, aryloxy, alkylaryl or alkylaryloxy, in particular C1-C4 alkyl or C1-C4 alkoxy; Each R ３２ are independently alkylene optionally substituted with one or more phenyl groups, alkyleneoxyalkylene optionally substituted with one or more phenyl groups, poly(alkyleneoxyalkylene) optionally substituted with one or more phenyl groups, arylene or alkylarylene, in particular alkylene, alkyleneoxyalkylene or poly(alkyleneoxyalkylene), Each R ３３ and R' ３３ is independently alkylene, particularly C2-C4 alkylene; y is from 1 to 50, in particular from 1 to 10; 2. The polymerizable flame retardant of claim 1, wherein z and z' are independently from 0 to 20, with the proviso that at least one of z and z' is not 0, in particular z and z' are independently from 1 to 20.

6. 2. The polymerizable flame retardant according to claim 1, comprising at least one linker L connecting a (meth)acrylate-containing moiety and a phosphorus-containing moiety, in particular comprising two linkers L, each linker L connecting a (meth)acrylate-containing moiety to one end of a phosphorus-containing moiety.

7. The linker L has the following formula (XX) or (XXI): is a bond or linker corresponding to one of During the ceremony L １ is selected from an aliphatic linker, a cycloaliphatic linker, an aromatic linker, and an araliphatic linker; L ２ is selected from an aliphatic linker, a cycloaliphatic linker, an aromatic linker, and an araliphatic linker; In particular, the linker L corresponds to formula (XX): The polymerizable flame retardant according to claim 6.

8. One of the structures of formulae (XXII) to (XXV): Y-PHOS-ACR(XXII) ACR-PHOS-ACR(XXIII) Y-PHOS-L-ACR(XXIV) ACR-L-PHOS-L-ACR(XXV) During the ceremony ACR is a (meth)acrylate-containing moiety as defined in claim 3; PHOS is a phosphorus-containing moiety as defined in claim 4 or 5, L is a linker as defined in claim 6 or 7, Y is a terminal group, in particular Y is selected from H, alkyl and aryl, more particularly Y is H or alkyl.

2. The polymerizable flame retardant of claim 1, which corresponds to

9. Structures of formulae (XXVI) to (XXVII) (XXIV) (XXV) (XXVI) (XXVII) During the ceremony R １ and a are as defined in claim 3, R ２ is as defined in claim 3, R ３１ , R ３２ , R ３３ , R' ３３ , y, z and z′ are as defined in claim 5; L is as defined in claim 6 or 7, Y is a terminal group, in particular Y is selected from H, alkyl and aryl, more particularly Y is H or alkyl.

2. The polymerizable flame retardant according to claim 1, which corresponds to one of the following:

10. 2. A method for preparing the polymerizable flame retardant as defined in claim 1, wherein the polymerizable flame retardant is a reaction product of at least one phosphorus-containing compound, at least one (meth)acrylate-containing compound and, optionally, at least one OH-reactive compound.

11. the phosphorus-containing compound corresponds to formula (XXX), the (meth)acrylate-containing compound corresponds to formula (XXXI) or (XXXII), the OH-reactive compound is selected from a diisocyanate or derivative thereof corresponding to formula (XXXIII), a diacid or diester corresponding to formula (XXXIV), and a cyclic anhydride corresponding to formula (XXXV); OCN-L １ -NCO (XXXXXXIII) R ３４ O-L ２ -COORA ３４ (XXXIV) During the ceremony R １ and a are as defined in claim 3, R ２ is as defined in claim 3, R ３１ , R ３２ , R ３３ , R' ３３ , y, z and z′ are as defined in claim 5; L １ is as defined in claim 7, L ２ is as defined in claim 7, R ３４ and R' ３４ is independently H or alkyl; 11. The method of claim 10, wherein Y and Y' are independently selected from H, alkyl and aryl, with the proviso that at least one of Y and Y' is H.

12. a) a polymerizable flame retardant according to claim 1 or prepared according to the method of claim 10; b) Ethylenically unsaturated compounds other than a) 1. A polymerizable composition comprising:

13. 13. A method for preparing a cured product comprising curing the polymerizable composition of claim 12, in particular by exposing the polymerizable composition to radiation, such as UV, near UV and / or visible radiation.

14. 11. Use of the polymerizable flame retardant according to claim 1 or prepared according to the method of claim 10 to obtain a cured product having improved flame retardancy and / or improved heat resistance and / or reduced amount of extractables.

15. 13. A substrate having applied thereto the polymerizable composition of claim 12, in particular a substrate selected from the group consisting of cellulosic materials, wool, fur, silk, leather, metal, natural and / or synthetic stone, ceramic, glass, brick, concrete, drywall, roofing shingles, asphalt, fiberglass, mineral wool, thermoplastic materials, thermoset materials, polymer composites and combinations thereof.

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