Ethylenically unsaturated compounds, methods for their preparation, and the use thereof in coating compositions

Abstract

Compounds that contain an ethylenically unsaturated group, an active-hydrogen group, and an aspartate group and / or hydantoin group are described. Also disclosed are methods for producing and using such compounds, such as their use in coating compositions, such as coating compositions suitable for application to optical glass fiber substrates.

Description

ETHYLENICALLY UNSATURATED COMPOUNDS, METHODS FOR THEIR PREPARATION, AND THE USE THEREOF IN COATING COMPOSITIONSFIELD

[0001] This specification relates to compounds that contain an ethylenically unsaturated group and an active -hydrogen group. This specification also relates to methods for producing such compounds, as well as to the use of such compounds in, for example, coating compositions, such as coating compositions suitable for application to optical glass fiber substrates.BACKGROUND

[0002] Radiation-curable, such as ultraviolet ("UV") radiation-curable, coating compositions are used in many applications due to, for example, their ability to cure especially rapidly to produce cured coatings exhibiting many desirable properties. "Radiation-curable" coating compositions, as used herein, refers to coating compositions that require radiation to initiate crosslinking to transfonn a liquid (uncured) composition to a solid (cured) coating. One specific use of radiation-curable coating compositions is in the production of coated optical fibers.

[0003] Optical fibers are composed of glass fibers obtained by hot melt spinning of glass, in which one or more coating layers is disposed over the glass fibers for protective reinforcement.Typically, radiation curable optical fiber coatings are the cured product of a composition containing a mixture of one or more components possessing one or more ethylenically unsaturated bonds which, under the influence of irradiation, undergo crosslinking by free-radical polymerization.

[0004] In many cases, optical fibers are coated with a multi-layer coating system that includes an inner "primary coating" that directly contacts the optical fiber and a "secondary coating" that overlays the primary coating. Tire inner primary coatings are typically formulated to possess a significantly lower modulus, i.e., lower hardness, than secondary coatings.

[0005] The relatively soft inner primary coating provides resistance to microbending, which can be induced by thermal stresses and / or mechanical lateral forces. Microbends are microscopic curvatures in the optical fiber involving local axial displacements of a few micrometers and spatial wavelengths of a few millimeters. They result in added attenuation of the signal transmission (i.e. signal loss) of the coated optical fiber and are tiierefore undesirable. Primary coatings that exhibit good microbending performance are typically characterized by exhibiting a low Young's modulus.

[0006] In addition to a low Young's modulus, several other properties are important for the primary coating. First, the primary coating should have a high peel strength, which is a measure of the coating's adhesion to the optical fiber. Second, because optical fibers are subject to various mechanicalstresses during fiber production, cabling, installation, handling, and operation, the primary coating should exhibit other good mechanical properties, such as high toughness, high tensile strength and high elongation at break. Third, the composition used to produce the primary coating should exhibit a relatively low viscosity, to aid in material handling and processing.

[0007] It is very challenging to improve all desired optical fiber primary coating properties simultaneously since improvement in some desired properties often has a detrimental effect on other properties. For example, it is difficult to achieve a desirably low modulus while still achieving a desirably high toughness in same primary coating. Balancing adhesion and viscosity with other properties is also difficult. One of the biggest challenges in the development of primary coatings is to find the most desired balance of overall coating perfonnance.

[0008] In view of the foregoing, it would be highly desirable to provide ethylenically unsaturated compounds suitable for use in compositions used to produce coatings for optical fibers, in which the coatings can exhibit significantly reduced Young's modulus without significantly sacrificing toughness, and while simultaneously exhibited significantly increased peel strength. It would also be desirable if such compounds were of relatively low viscosity.SUMMARY

[0009] In some respects, this specification relates to ethylenically unsaturated compounds. The ethylenically unsaturated compounds comprise: (a) a moiety of the structure (1):• - N - n - G1— Zp— G'H° (1):(bl) a moiety of the structure (2):O(b2) a moiety of the structure (3):(3); or (b3) a combination of a moiety of the structure (2) and a moiety of the structure (3); and, optionally, (c) a moiety of the structure (3a):• -HN - n - G 1 - Z Pp- G i - n - N11- • *O OL Jn (3£in which (i) each R1. which may be the same or different, represents an organic group that is inert to isocyanate groups at temperatures of 100°C or less; (ii) each R2. which may be the same or different, represents hydrogen or an organic group that is inert to isocyanate groups at temperatures of 100°C or less; (iii) each " - • " represents a linkage to another portion of the ethylenically unsaturated compound; (iv) each G1is 0 or S, (v) m has a value of 1 to 5, such as 1 to 3, or 1, (vi) n has a value of 1 to 5, 1 to 3, or 1, and (vii) Zprepresents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Ci s alkylene group or a Cs-Ce cycloalkylene group.

[0010] This specification also relates to methods for producing such ethylenically unsaturated compounds, compositions, such as a coating composition, that include such ethylenically unsaturated compounds, and substrates, such as glass substrates, including optical fibers, which are at least partially coated with a coating, such as a primary coating, deposited from such coating compositions.DETAILED DESCRIPTION

[0011] Various implementations are described and illustrated in this specification to provide an overall understanding of the structure, function, properties, and use of the disclosed inventions. It is understood that the various implementations described and illustrated in this specification arc nonlimiting and non-exhaustive. Thus, the invention is not limited by the description of the various nonlimiting and non-exhaustive implementations disclosed in this specification. The features and characteristics described in connection with various implementations may be combined with the featuresand characteristics of other implementations. Such modifications and variations are intended to be included within the scope of this specification. As such, the claims may be amended to recite any features or characteristics expressly or inherently described in, or otherwise expressly or inherently supported by, this specification. Further, Applicant(s) reserve the right to amend the claims to affinnatively disclaim features or characteristics that may be present in the prior art. Therefore, any such amendments comply with the requirements of 35 U.S.C. § 112 and 35 U.S.C. § 132(a). The various implementations disclosed and described in this specification can comprise, consist of, or consist essentially of the features and characteristics as variously described herein.

[0012] Any patent, publication, or other disclosure material identified herein is incorporated by reference into this specification in its entirety unless otherwise indicated, but only to the extent that the incorporated material does not conflict with existing definitions, statements, or other disclosure material expressly set forth in this specification. As such, and to the extent necessary, the express disclosure as set forth in this specification supersedes any conflicting material incorporated by reference herein. Any material, or portion thereof, that is said to be incorporated by reference into this specification, but which conflicts with existing definitions, statements, or other disclosure material set forth herein, is only incorporated to the extent that no conflict arises between that incorporated material and the existing disclosure material. Applicant(s) reserves the right to amend this specification to expressly recite any subject matter, or portion thereof, incorporated by reference herein.

[0013] In this specification, other than where otherwise indicated, all numerical parameters are to be understood as being prefaced and modified in all instances by the term "about", in which the numerical parameters possess the inherent variability characteristic of the underlying measurement techniques used to determine the numerical value of the parameter. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter described in the present description should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0014] Also, any numerical range recited in this specification is intended to include all subranges of the same numerical precision subsumed within the recited range. For example, a range of " 1.0 to 10.0" is intended to include all sub-ranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0. such as, for example. 2.4 to 7.6. Any maximum numerical limitation recited in this specification is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein. Accordingly, Applicant(s) reserves the right to amend this specification, including the claims, to expressly recite any sub-range subsumed within tire rangesexpressly recited herein. All such ranges are intended to be inherently described in this specification such that amending to expressly recite any such sub-ranges would comply with the requirements of 35 U.S.C. § 112 and 35 U.S.C. § 132(a).

[0015] Hie grammatical articles "one", "a", "an", and "the", as used in this specification, are intended to include "at least one" or "one or more", unless otherwise expressly indicated. Tirus, the articles are used in this specification to refer to one or more than one (i.e.. to "at least one") of the grammatical objects of the article.

[0016] Throughout this specification "Si" refers to silicon, "H" refers to hydrogen, "C" refers to carbon, "N" refers to nitrogen, "0" refers to oxygen, and "S" refers to sulfur.

[0017] As indicated, certain implementations of the present specification relate to ethylenically unsaturated compounds, such compounds may be a monomer or an oligomer. In some implementations, the ethylenically unsaturated monomers of this specification have a molecular weight, calculated from the molecular formula of the ethylenically unsaturated compound, of 400 to less than 2000 g / mol, such as 400 to 1000 g / mol. In some implementations, the ethylenically unsaturated oligomers of this specification have a number average molecular w eight (Mn) of at least 800 g / mol. More specifically, in some cases, these oligomers have a Mn of 800 to 35,000 g / mol, 1000 g / mol to 35,000 g / mol, 2000 g / mol to 30,000 g / mol. 2000 g / mol to 25,000 g / mol, 2000 g / mol to 20.000 g / mol, 2,200 to 10,000 g / mol, or 2,200 to 5,500 g / mol. The molecular weight (including Mn. Mw, and Mz) values of oligomers and polymers referenced herein (unless otherwise indicated) are as measured by size exclusion chromatography (SEC) using a Waters GPC (Gel Permeation Chromatography) system with refractive index (RI) detector, a photodiode array detector, in which: (a) for chromatographic separation, chromatographic Size Exclusion columns: 3 x 7.8 mm x 300 mm TSK-GEL MULTIPORE HXL-M, 5 m, TosoHaas or equivalent, are used; (b) detectors and columns are operated at 40° C; (c) polystyrene molecular weight standards are used to establish a calibration curve: (d) prior to conducting SEC. each respective oligomer and polystyrene molecular weight standard is dissolved at a concentration ranging from 0.5 to 10 mg / ml in high purity grade tetrahydrofuran (THF) containing BHT stabilizer, in which this THF solution is also used as an eluent in SEC analysis at a flow rate of 1.0 ml / min; (e) after completion of the dissolution, the relative molar mass and molar mass distribution are then determined with the above-referenced detection method using the refractive index and absorbance: (f) a calibration curve is generated with a series of polystyrene standards assigning each data slice a molecular weight and from which the relative molar mass and distribution can be obtained; and (g) the calibration curve, molecular mass averages, and the molar mass distributions are determined by integration of the whole refractive index chromatogram. As will be appreciated, polydispersity index (PDI) values reported herein refer to Mw / Mn.

[0018] As used herein, the term "oligomer" means a molecule of intermediate relative molecular mass, the structure of which comprises a plurality of units derived, actually or conceptually, from molecules of lower relative molecular mass. As used herein, the term "ethylenically unsaturated compound" means a compound that comprises a polymerizable carbon-carbon double bond, i.e., a carboncarbon double bond that can react with another carbon-carbon double bond in a polymerization reaction. As will be appreciated, a polymerizable carbon-carbon double bond is generally comprised in an acryloyl (-C(=O)-CH=CH2), methacryloyl (-C(=O)-C(CH3)=CH2) or vinyl (-CH=CH2) group. In some implementations, the ethylenically unsaturated compound comprises at least one acrylate group, methacrylate group, acrylamide group, methacrylamide group, vinyloxy group, N-vinyl amide group, or any combination thereof. In some embodiments, the ethylenically unsaturated compound comprises only one of the aforementioned ethylenically unsaturated groups. In some implementations, the ethylenically unsaturated compound comprises 1 to 4. such as 1 to 2, or, in some cases, 1 ethylenically unsaturated group. Thus, as will be appreciated, in some implementations, the ethylenically unsaturated compounds of this specification comprise an end group of structure (1) and an end group of the structure (la):E (la)in which E represents a group that includes any of the aforementioned groups that comprise a polymerizable carbon-carbon double bond, such as an acryloyl, methacryloyl, or vinyl group and - • represents a linkage to another portion of the ethylenically unsaturated compound. For example, in some implementations, the end group of structure (la) has the structure (lb):(lb)in which R3is H or CHs and • represents a linkage to another portion of the ethylenically unsaturated oligomer. In some cases, the first end group and the second end group are arranged at opposite ends of the ethylenically unsaturated oligomer.

[0019] More specifically, the ethylenically unsaturated compounds of this specification comprise: (a) a moiety of the structure (1):H• - N G1— Zp— G'H(i);(bl) a moiety of the structure (2):(2); or (b2) a moiety of the structure (3):O(b3) a combination of a moiety of the structure (2) and a moiety of the structure (3): and, optionally, (c) a H H> N G1- Zp- G1NiJO mo ety of the structure(3a): m -1n (3a) in which (i) each R1, which may be the same or different, each represent an organic group that is inert to isocyanate groups at temperatures of 100°C or less; (ii) each R2, which may be the same or different, each represent hydrogen or an organic group that is inert to isocyanate groups at temperatures of 100°C or less: (iii) each " - • " represents a linkage to another portion of the ethylenically unsaturated compound; (iv) each G1is 0 or S, (v) m has a value of 1 to 5, such as 1 to 3, or 1, (vi) n has a value of 1 to 5, 1 to 3, or 1, and (vii) Zprepresents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanatc-incrt oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a Cs-Ce cycloalkylene group. As used herein, the phrase that a group is "inert towards isocyanate groups at temperatures of 100°C or less" means that the group is inert towards isocyanate groups at such temperatures when, as is depicted in the various structures illustrated herein, the group iscovalently attached to another atom in the structure being discussed. As will be appreciated, Zerevitinov-active hydrogens are not inert towards isocyanate groups at such temperatures and, as such, any organic group described in this specification as being inert towards isocyanate groups at such temperatures does not include a Zerevitinov-active hydrogen (Zerevitinov-active hydrogen is defined in Rompp's Chemical Dictionary (Rommp Chemie Lexikon), 10thed., Georg Thieme Verlag Stuttgart. 1996). Generally, groups with Zerevitinov-active hydrogen are understood in the art to mean hydroxyl (OH), amino (NHX), and thiol (SH) groups.

[0020] In some implementations, (i) each R1in structures (2) and (3), which may be the same or different, represents an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where each R1in structures (2) and (3), which may be the same or different, represents a methyl group, an ethyl group, a propyl group or a butyl group; (ii) each R2in structures (2) and (3), which may be the same or different, represents a hydrogen or an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where each R2in structures (2) and (3), which may be the same or different, represents a hydrogen, methyl group, an ethyl group, a propyl group or a butyl group.

[0021] In some embodiments, the ethylenically unsaturated compounds of this specifically are not moisture curable. As a result, in some of these such embodiments, the ethylenically unsaturated compounds of this specification are free of silane groups. As used herein, when it is stated that an ethylenically unsaturated compounds is free of silane groups, it means that the ethylenically unsaturated compound being discussed does not include any moiety of the structure:• - Y1— Si(X)3in which (i) Y1represents a linear or branched linking group comprising 1 or more carbon atoms, (ii) each X. which may be the same or different, represents an alkoxy group or an organic group that is inert towards isocyanate groups at temperatures of 100°C or less, with the proviso that at least one X represents an alkoxy group, and (iii) - • represents a linkage to another portion of the ethylenically unsaturated compound.

[0022] In some cases, an end group of structure (1) and an end group of structure (la) are arranged at opposite ends of the ethylenically unsaturated compound. Moreover, as will be appreciated, the moiety of structure (2) and / or the moiety of structure (3) is arranged between the end group of structure (1) and the end group of structure (la).

[0023] In some specific implementations, the ethylenically unsaturated compounds of this specification are represented by the structure (4):in which (i) each Y, which may be the same or different, represents a group comprising a branched or straight chain alkylene radical, such as where the branched or straight chain alkylene radical has at least 2, 2 to 8, or 2 to 4 carbon atoms; (ii) each G1, which may be the same or different, represents 0 or S; (iii) each G, which may be the same or different, represents 0, S, NH, or NR' in which R' is an alkyl radical, such as an alkyl radical having 1 to 6 carbon atoms, (iv) Zprepresents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a Cs-Ce cycloalkylene group; (v) each R3, which may be the same or different, represents H or CH3, (vi) m has a value of 1 to 5, such as 1 to 3, or 1, (vii) n has a value of 1 to 5, 1 to 3, or 1, (viii) q has a value of at least 1, such as 1 to 20, 1 to 5, or 1 to 3, (ix) r is 1, 2 or 3; (x) LNis represented by the structure:m n, in which Z1represents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a C -C, cycloalkylene group, m and n arc each as described above, and " - • " represents a linkage to another portion of the ethylenically unsaturated compound, and (xi) each L2, which may be tire same or different, is represented by the structure L1or LB, with the proviso that at least one occurrence of L2is represented by the structure LB, in which L1is represented by structure (4a):H H N G1- Zp- G1N>O O-J m -1n (4a)in which Zp, G1, m, n and " - • " are each as described above with respect to structure (4); and LBis represented by structure (4b):in which: (i) ZArepresents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a G-C,, cycloalkylcnc group; (ii) each R1in structure (4b), which may be the same or different, represents an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where each R1in structure (4b), which may be the same or different, represents a methyl group, an ethyl group, a propyl group or a butyl group; (iii) each R3in structure (4b), which may be the same or different, represents a hydrogen or an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where each R1and R2in structure (4b), which may be the same or different, represents a hydrogen, methyl group, an ethyl group, a propyl group or a butyl group; (iv) m and n arc each as described above with reference to structure (4): and (v) each " - • " represents a linkage to another portion of the ethylenically unsaturated compound.

[0024] As will be appreciated, in some implementations of the ethylenically unsaturated compound represented by structure (4), the value of m and / or n in LBor L1can be more than 1, in which case more than one bond linkage from LNto NH will be present and / or more than one bond linkage from L2to LNwill be present resulting in a further branched structure within the substructure encompassed within the "{

[0025] In some implementations of the ethylenically unsaturated compound represented by¬ structure (4), Y in structure (4) comprises a linear or branched alkylene radical having 1 to 8 carbon atoms, such as a linear alkylene radical having 2 to 4 or, in some cases 3, carbon atoms (such as a propylene radical), or a branched alkylene radical having 5 to 6 carbon atoms.

[0026] In some implementations of the ethylenically unsaturated compound represented by structure (4), at least one Y is:; or a combination of any two or more thereof, in which each -• " represents a linkage to another portion of the ethylenically unsaturated compound.

[0027] In some implementations of the ethylenically unsaturated compound represented by structure (4), Z1is:, in which x has a value of 3 to 19;R10, in which R10is C2H5 or H and each of XI, X2, X3 and X4, which may be the same or different, has a value of 1 to 10, provided that the structure has a molecular weight of 200 to 1500;•; orin which each " - • " represents a linkage to another portion of the ethylenically oligomer compound.

[0028] In addition, in some implementations of the ethylenically unsaturated compound represented by structure (4), each R1in structure (4b), which may be the same or different, represents an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where R1, which may be the same or different, represents a methyl group, an ethyl group, a propyl group or a butyl group and each R2in structure (4b) represents a hydrogen.

[0029] Further, as indicated, Zprepresents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a Ch-C, cycloalkylene group. In some implementations, Zpin any of the foregoing structures is a portion of the residue of a polyol, such as a diol, a triol, or a higher functionality' polyol, such as a polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, acry lic polyol, among others, including combinations of any two or more thereof.

[0030] In some implementations, Zpin any of the foregoing structures is a portion of a residue of a polyether polyol, such as, for example, a polyethylene glycol, a polypropylene glycol, a polypropylene glycol-ethylene glycol copolymer, a polytetramethylene glycol, a polyhexamethylene glycol, a polyheptamethylene glycol, a polydecamethylene glycol, and polyether diols obtained by ring-opening copolymerization of two or more ion-polymerizable cyclic compounds, such as cyclic ethers, including, for example, ethylene oxide, propylene oxide, isobutene oxide, tetrahydrofuran, 2 -methyltetrahydrofuran, 3 -methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate. Specific examples of combinations of two or more ion-polymerizable cyclic compounds include combinations for producing a binary copolymer such as tetrahydrofuran and 2 -methyltetrahydrofuran, tetrahydrofuran and 3 -methyltetrahydrofuran, and tetrahydrofuran and ethylene oxide; and combinations for producing a ternary copolymer such as a combination of tetrahydrofuran, 2 -methyltetrahydrofuran, and ethylene oxide, a combination of tetrahydrofuran, butene-l-oxide, and ethylene oxide, and the like. Hie ring-opening copolymers of these ion-polymerizable cyclic compounds may be either random copolymers or block copolymers.

[0031] In some implementations, Zpin any of the foregoing structures is a portion of a residue of a polyester polyol, such as may be obtained by reacting a polyhydric alcohol and a polybasic acid. Asexamples of the polyhydric alcohol, ethylene glycol, polyethylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, 3 -methyl- 1,5 -pentanediol, 1,9-nonanediol, 2-methyl-l,8-octanediol, and the like can be given. As examples of the polybasic acid, phthalic acid, dimer acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebasic acid, and the like can be given.

[0032] Zp, in some implementations of any of the foregoing structures, is a portion of a residue of a polycarbonate polyol, such as, for example, a polycarbonate of polytctrahydrofuran. a poly(hexanediol carbonate), a poly(nonanediol carbonate), and a poly(3 -methyl- 1,5 -pentamethylene carbonate).

[0033] Further, in some implementations, Zpin any of the foregoing structures is a portion of a residue of a polycaprolactone diol, such as may be obtained by reacting e-caprolactone and a diol to provide a polycaprolactone polyol having a melting point of 0°C or higher. Suitable diols for producing such polycaprolactone diols include, without limitation, ethylene glycol, polyethylene glycol, polypropylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 1,4-butanediol, among others, including combinations of any two or more thereof.

[0034] Still other suitable polyols from which Zpin any of the foregoing structures may be derived include, without limitation, ethylene glycol. 1.4-butanediol. 1.5 -pentanediol, 1,6-hexanediol, polyoxyethylene bisphenol A ether, polyoxypropylene bisphenol A ether, polyoxyethylene bisphenol F ether, and polyoxypropylene bisphenol F ether, including combinations thereof.

[0035] In some implementations, Zpin any of the foregoing structures is a portion of a residue of a polyol that has a number average molecular weight, derived from the hydroxyl number of the polyol, of 62 to 20,000 g / mol, such as 500 to 15.000 g / mol, 900 to 9,000 g / mol, or, in some cases, 1,800 to 6,000 g / mol or 2,500 to 5.000 g / mol.

[0036] In other implementations, the ethylenically unsaturated compound of this specification comprises the structure (5):in which Y, G, G1, R3. m, n, q. r, LNand Zpare each as described above with reference to structure (4) and each L3, which may be the same or different, is represented by the structure L1or Lc, with the proviso that at least one occurrence of L3is represented by the structure Lc, in which L1is represented by structure (4a) described above; and Lcis represented by structure (5b):in which: (i) ZA, R1, R2, m, and n are each as described above with reference to structure (4b), and (iii) each " - • " represents a linkage to another portion of the ethylenically unsaturated compound.

[0037] As will be appreciated, in some implementations of the ethylenically unsaturated compound represented by structure (5), the value of m and / or n in Lcand / or L1can be more than 1, in which case more than one bond linkage from LNto NH will be present and / or more than one bond linkage from L3to LNwill be present, resulting in a further branched structure within the substructure encompassed within the " { } " .

[0038] In yet other implementations, the ethylenically unsaturated compound of this specification comprises the structure (6):H(6) in which Y2represents a group comprising a branched or straight chain alkylene radical, such as where the branched or straight chain alkylene radical has at least 2. 2 to 8, or 2 to 4 carbon atoms, and R3, G1, Zp, L2. LN. m, n, q, and r are each as described above with reference to structure (4).

[0039] In some implementations. Y2in structure (6) comprises a linear or branched alkylene radical having 1 to 8 carbon atoms, such as a linear alkylene radical having 2 to 4 or, in some cases 3, carbon atoms (such as a propylene radical), or a branched alkylene radical having 5 to 6 carbon atoms.

[0040] In some implementations of the ethylenically unsaturated compound represented by¬ structure (6), at least one Y2is:a combination of any two or more thereof, in which each " - • " represents a linkage to another portion of the ethylenically unsaturated compound.

[0041] As will be appreciated, in some implementations of the ethylenically unsaturated compound represented by structure (6), the value of m and / or n in LBand / or L1can be more than 1, in which case more than one bond linkage from LNto NH will be present and / or more than one bond linkage from L2to LNwill be present, resulting in a further branched structure within the substructure encompassed within the " { } " .

[0042] In still other implementations, the ethylenically unsaturated compound of this specification comprises the structure (7):in which Y2represents a group comprising a branched or straight chain alkylene radical, such as where the branched or straight chain alkylene radical has at least 2, 2 to 8, or 2 to 4 carbon atoms, and R3, G1, Zp, L3, LN, m, n, q, and r are each as described above with reference to structure (5).

[0043] As will be appreciated, in some implementations of the ethylenically unsaturated compound represented by structure (7), the value of m and / or n in Lcand / or L1can be more than 1, in which case more than one bond linkage from LNto NH will be present and / or more than one bond linkage from L3to LNwill be present, resulting in a further branched structure within the substructure encompassed within the " { } " .

[0044] In further implementations, the ethylenically unsaturated compound of this specification comprises the structure (8):(8),in which Y, R3, G. G1. Zp. LN. m, n, q. and r are each as described above with reference to structure (4), and each L4, which may be the same or different, is represented by the structure L1or LD, with the proviso that at least one occurrence of L4is represented by the structure LD, in which L1is represented by structure (4a) described above and LDis represented by structure (8b) or the structure (8c):(8b)in which: (i) Z3represents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a Cs-C,, cycloalkylene group; (ii) G, R1, R2, m, and n are each as described above with reference to structure (4), and (iii) each " - • " represents a linkage to another portion of the ethylenically unsaturated compound.

[0045] As will be appreciated, in some implementations of the ethylenically unsaturated compound represented by structure (8), the value of m and / or n in LDand / or L1can be more than 1, in which case more than one bond linkage from LNto NH will be present and / or more than one bond linkage from L4to LNwill be present, resulting in a further branched structure within the substructure encompassed within the " { } " .

[0046] In other further implementations, the ethylenically unsaturated compound of this specification comprises the structure (9):(9),in which Y, R3, G, G1, Zp, LN, m, n, q, and r are each as described above with reference to structure (4), and each L5, which may be the same or different, is represented by the structure L1or LE, with the proviso that at least one occurrence of L' is represented by the structure LE, in which L1is represented by structure (4a) described above and LEis represented by structure (9b) or structure (9c):in which: (i) Z3represents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a G-C, cycloalkylene group; (ii) G, R1, R2, m, and n are each as described above with reference to structure (4), and (iii) each " - • " represents a linkage to another portion of the ethylenically unsaturated compound

[0047] As will be appreciated, in some implementations of the ethylenically unsaturated compound represented by structure (9), the value of m and / or n in LEand / or L1can be more than 1, in which case more than one bond linkage from LNto NH will be present and / or more than one bond linkage from L5to LNw ill be present, resulting in a further branched structure within the substructure encompassed within tire " { } " .

[0048] In still further implementations, the ethylenically unsaturated compound of this specification has the structure (10):in which R3, G1, Zp, LN, m, n, q, and r are each as described above with reference to structure (4), L4is as described above with reference to structure (8), and Y2is as described above with reference to structure (6).

[0049] As will be appreciated, in some implementations of the ethylenically unsaturated compound represented by structure (10), the value of m and / or n in L1and / or LDcan be more than 1, in which case more than one bond linkage from LNto NH will be present and / or more than one bond linkage from L4to LNwill be present, resulting in a further branched structure within the substructure encompassed within the " { } " .

[0050] In yet other further implementations, the ethylenically unsaturated compound of this specification comprises the structure (11):(H), in which Y, R3, G1, Zp, LN, m, n, q, and r are each as described above with reference to structure (4), L5is as described above with reference to structure (9), and Y2is as described above with reference to structure (6).

[0051] As will be appreciated, in some implementations of the ethylenically unsaturated compound represented by structure (11), the value of m and / or n in L1and / or LEcan be more than 1, in which case more than one bond linkage from LNto NH will be present and / or more than one bond linkage from L5to LNwill be present, resulting in a further branched structure within the substructure encompassed within tire " { } " .

[0052] In further implementations, the ethylenically unsaturated compound of this specification comprises the structure (12):(12) in which: (i) Y, R3, Zp, G, G1, LN, m, n, and r are each as described above with reference to structure (4); (ii) q has a value of 2 to 20, 2 to 5, or 2 or 3; and (ii) each L6, which may be the same or different, is represented by the structure L1, the structure LD. or the structure LB, with the proviso that at least one occurrence of Lbis represented by the structure LDand at least one occurrence of L6is represented by the structure LB, in which L1is represented by structure (4a) described above, LDis represented by structure (8b) and structure (8c) described above, and LBis represented by the structure (4b) described above.

[0053] As will be appreciated, in some implementations of the ethylenically unsaturated compound represented by structure (12), the value of m and / or n in L1, LBand / or LDcan be more than 1, in which case more than one bond linkage from LNto Lbwill be present and / or more than one bond linkage from L6to LNwill be present, resulting in a further branched structure within the substructure encompassed within the " { } " .

[0054] In still further implementations, the ethylenically unsaturated compound of this specification comprises the structure (13):m (13) in which: (i) Y, R3, Zp, G, G1, LN, m, n, and r are each as described above with reference to structure (4); (ii) q has a value of 2 to 20, 2 to 5, or 2 or 3; and (ii) each L7, which may be the same or different, is represented by the structure L1, the structure LE, or the structure Lc, with the proviso that at least one occurrence of L7is represented by the structure LEand at least one occurrence of L6is represented by the structure Lc, in which L1is represented by structure (4a) described above, LEis represented by structure (9b) and structure (9c) described above, and Lcis represented by the structure (5b) described above.

[0055] As will be appreciated, in some implementations of the ethylenically unsaturated compound represented by structure (13), the value of m and / or n in L1, Lcand / or LEcan be more than 1,in which case more than one bond linkage from LNto L7will be present and / or more than one bond linkage from L7to LNwill be present, resulting in a further branched structure within the substructure encompassed within tire " { } " .

[0056] In other further implementations, the ethylenically unsaturated compound of this specification has the structure (14):(14)in which: (i) R3, G, G1, LN, m, n, and r are each as described above with reference to structure (4); (ii) q has a value of 2 to 20, 2 to 5, or 2 or 3; and (iii) Y2is as described above with reference to structure (6); L6is as described above with reference to structure (12).

[0057] As will be appreciated, in some implementations of the ethylenically unsaturated compound represented by structure (14), the value of m and / or n in L1, LBand / or LDcan be more than 1, in which case more than one bond linkage from L6to LNwill be present and / or more than one bond linkage from LNto NH will be present, resulting in a further branched structure within the substructure encompassed within the " { } " .

[0058] In some other implementations, the ethylenically unsaturated compound of this specification comprises the structure (15):(15) in which: (i) R3, G, G1, LN, m, n, and r are each as described above with reference to structure (4); (ii) q has a value of 2 to 20, 2 to 5, or 2 or 3; and (iii) Y2is as described above with reference to structure (6); L7is as described above with reference to structure (13).

[0059] As will be appreciated, in some implementations of the ethylenically unsaturated compound represented by structure (15), the value of m and / or n in L1, Lcand / or LEcan be more than 1, in which case more than one bond linkage from LNto L3will be present and / or more than one bondlinkage from L3to Y2will be present, resulting in a further branched structure within the substructure encompassed within the " { } " .

[0060] Some implementations of the ethylenically unsaturated compounds of this specification, which include an end-group of structure (1), comprise a reaction product of reactants comprising or consisting of: (a) a polyisocyanate; (b) an active hydrogen-containing ethylenically unsaturated compound; (c) a compound comprising more than one active hydrogen atoms; and (d) polyaspartate amine.

[0061] Examples of suitable polyisocyanates (a) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, (hydrogenated) xylylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5 -naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3, 3'-dimethyl-4, d'diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3 '-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate. 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexylisocyanate), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4 trimethyl hexamethylene diisocyanate, hexamethylene diisocyanate, 2,4- and / or 4,4-methylenedicyclohexyl diisocyanate, methylene diphenyl diisocyanate, tetramethyl xylene diisocyanate, 1,5-pentane diisocyanate, bis(2-isocyanato-ethyl)fumarate, 6-isopropyl-l,3-phenyl diisocyanate, 4 -diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, lysine isocyanate, hexamethylene diisocyanate trimers (such as is commercially available as Desmodur® N3300A from Covestro), triphenylmethane-4,4',4"-triisocyanate (such as is commercially available as Desmodur® RE from Covestro), hexamethylene diisocyanate trimers (such as is commercially available as Desmodur® N3200 from Covestro), aromatic polyisocyanates based on toluene diisocyanate (such as is commercially available as Desmodur® IL BA from Covestro), polyisocyanurates of toluene diisocyanate (such as is commercially available as Desmodur® RC from Covestro). or a combination of any two or more thereof.

[0062] In some implementations, the polyisocyanate (a) has the structure:1OCN—JIniZ1— |1~ NCOJii , in which Z1, m and n are each as described above with reference to structure (4). In some cases, Z1is:, in which x has a value of 3 to 19;R10, in which each XI, X2, X3 and X4, which may be the same or different, has a value of 1 to 10, provided that the structure has a molecular weight of 200 to 1500, and R10is C2H5 or H;in which each " - • " represents a linkage to an NCO group.

[0063] In some of these implementations, the active hydrogen-containing ethylenically unsaturated compound (b) comprises an active hydrogen-containing (meth) acrylate of the structure:, in which R3, Y, G and r are each as described above with reference to structure (4).

[0064] In some cases, the compound comprising more than one active hydrogen atoms (c) HG1— ZpG'Hcomprises a compound of the structure:mn, in which G1, Zp, m and n are each as described above with reference to structure (4).

[0065] Suitable polyaspartate amines (d) for use in preparing such ethylenically unsaturated compounds include, without limitation, those of the structure:in which R1, R2, ZA, m, and n are each as described above with reference to structure (4b).

[0066] Such polyaspartate amines can be produced by reacting a primary polyamine corresponding to the formula: (NH2)mZ3(NH2)n , in which Z3represents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a Cs-Ce cycloalkylene group and m+n is an integer having a value of at least 2, such as 2 to 4, with a maleic or fumaric acid ester of the fonnula (with bothisomers as represented by wavy bonds):r24, in which each R23, which may be the same or different, represents an organic groups that is inert towards isocyanate groups at temperatures of 100°C or less and each R24. which may be the same or different, represents hydrogen or an organic groups that is inert towards isocyanate groups at temperatures of 100°C or less.

[0067] Specific examples of suitable primary polyamines include, without limitation, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3 -diaminobutane, 1,4-diaminobutanc, 1,5-diaminopcntanc, 1,6-diaminohcxanc, 1,7-diaminohcptanc, 1,8-diaminooctanc, 2,5-diamino-2,5-dimethylhexane, 2,2,4-and / or 2,4,4-trimethyl-l,6-diaminohexane, 1, 11 -diaminoundecane, 1,12-diaminododecane, bis-(3 -aminopropyl) ether, l,2-bis-(3-aminopropyloxy)ethane, l,3-bis-(3-aminopropyloxy)-2,2'-dimethylpropane, 1,2-bisaminocyclohexane, 1,3-bisaminocyclohexane, 1,4-bisaminocyclohexane, 1,3-bisaminomethylcyclohexane, 1 ,4-bisaminomethylcyclohexane, 1,3-bisaminoethylcyclohexane, 1,4-bisaminoethyl cyclohexane, 1,3-bisaminopropylcyclohexane, 1,4-bisaminopropylcyclohcxanc, hydrogenated 4,4'-diaminodiphcnylmcthanc, l-amino-3,3,5-trimcthyl-5-aminomethyl-cyclohexane, 2,4-and / or 2,6-hexahydrotoluylene diamine, 2,4'-and / or 4,4'-diamino-dicyclohexyl methane, 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methane, propane- 1, 2, 3-triamine, pentane-l,3,5-triamine, benzene-l,3,5-triamine, isophoronediamine, menthanediamine, 1,4-bisaminopropylpiperazine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, 2,4-toluenediamine, 2,4'-and / or 4,4'-diaminodiphenyl methane, m-aminobenzylamine, 4-chloro-o-phenylenediamine, tetrachloro-p-xylylenediamine, 4-methoxy-6-methyl-m-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, benzidine, 4,4'-bis(o-toluidine), dianisidine, 4,4'-diaminodiphenylmethane, 2,2-(4,4'-diaminodiphenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-thiodianiline, 4,4'-diaminodiphenylsulfone, 4,4'-diaminoditolylsulfone, methylenebis(o-chloroaniline), 3, 9-bis(3 -aminopropyl) 2,4,8, 10-tetraoxaspiro[5,5]undecane, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine. 1.4-bis(aminoethylpiperazine), l,4-bis(aminopropylpiperazine), 2,6-diaminopyridine, and bis(3,4-diaminophenyl)sulfone, relatively high molecular weight polyether polyamines containing aliphatically bound primary amino groups (such as the JEFF AMINE® products commercially available from Huntsman Corp.), and combinations of any two or more of any of the foregoing.

[0068] Specific examples of suitable maleic or fumaric acid esters include, without limitation, dimethyl, diethyl and di-n-butyl esters of maleic acid and fumaric acid and the corresponding maleic or fumaric acid esters substituted by methyl in the 2- and / or 3 -position.

[0069] Tire preparation of the polyaspartate amine from the above mentioned starting materials may be carried out, for example, at a temperature of -20°C to 100°C using the starting materials in proportions such that 0.8 to 1.2, such as 1, olefinic double bond is present for each primary amino group. The reaction may be carried out solvent-free or in the presence of suitable solvents such as methanol, ethanol, propanol, dioxane and mixtures of such solvents. The reaction may optionally be carried out in the presence of a catalyst such as an organic metal catalyst where the catalyst comprises a copper compound, such as copper naphthenate, a cobalt compound, such as cobalt naphthenate, a zinc compound, such as zinc naphthenate, a bismuth compound, such as bismuth neodecanoate, a tin compound, such as di-n-butyl tin dilaurate or a combination of any two or more of the foregoing.

[0070] The reaction of the poly isocyanate (a) with (b) the active hydrogen-containing ethylenically unsaturated compound, (c) the compound comprising more than one active hydrogen atoms, and (d) the polyaspartate amine to produce the ethylenically unsaturated compound of certain embodiments of this specification may, if desired, be carried out in the presence of a catalyst. Suitable catalysts include, without limitation, an organic metal cataly st, an amine catalyst, or a combination thereof, such as where the catalyst comprises a copper compound, such as copper naphthenate, a cobaltcompound, such as cobalt naphthenate, a zinc compound, such as zinc naphthenate, a bismuth compound, such as bismuth neodecanoate, a tin compound, such as di-n-butyl tin dilaurate, triethylamine, triethylenediamine, DABCO, DMEA, or a combination of any two or more of the foregoing. In some implementations, the reaction takes place at a temperature of 10 to 120°C or 25 to 100°C. In addition, in some implementations, the reactants are employed in relative amounts to provide a molar ratio of isocyanate-reactive groups to isocyanate groups of at least 1:1, such as more than 1 to less than 1.5. The resulting ethylenically unsaturated compound comprises aspartate groups from the polyaspartate amine, as is depicted, for example, by structure (4) described earlier.

[0071] In some implementations, tire resulting aspartate group-containing ethylenically unsaturated compound is subjected to further processing to convert the aspartate group to a hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, such as a Bronsted acids, a carboxylic acid, a sulfonic acid, a phenol, or a mixture of any two or more thereof, at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, or 80 to 100°C. The resulting ethylenically unsaturated compound comprises a hydantoin group, as is depicted, for example, by structure (5) described earlier.

[0072] As a result, this specification also relates to methods for making an ethylenically unsaturated compound which includes an end-group of structure (1). Hie method comprises reacting (a) a polyisocyanate with (b) an active hydrogen-containing ethylenically unsaturated compound, (c) a compound comprising more than one active hydrogen atoms, and (d) a polyaspartate amine, optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising an aspartate group. In some implementations, the method further comprises converting the aspartate group to a hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising a hydantoin group.

[0073] In other implementations, the ethylenically unsaturated compounds of this specification, which include an end-group of structure (1), comprise a reaction product of reactants comprising: (a) a polyisocyanate; (b) an isocyanate-containing ethylenically unsaturated compound; (c) a compound comprising more than one active hydrogen atoms; and (d) a polyaspartate amine. In these implementations, suitable polyisocyanates, compounds comprising more than one active hydrogen atoms, and aspartate silanes include any of those mentioned earlier. In addition, suitable isocyanate-containing ethylenically unsaturated compounds include those having the structure:in which herein R3, Y2and r are each as described above with reference to structure (6). Specific examples of suitable isocyanate-containing ethylenically unsaturated compounds include, without limitation, isocyantoethyl methacrylate, isocyanatopropyl methacrylate, isocyanatobutyl methacrylate, isocyanatoethyl acrylate, isocyanatopropyl acrylate, isocyanatobutyl acrylate, or a mixture of any two or more thereof.

[0074] Other suitable isocyanate-containing ethylenically unsaturated compounds, which may be used in lieu of or combination with any one or more of the isocyanate-containing ethylenically unsaturated compounds previously mentioned, are tire reaction products of reactants comprising: (i) a monohydroxy-substituted monofunctional or multifunctional (meth)acrylate, and (ii) a polyisocyanate. Specific examples of suitable monohydroxy -substituted monofunctional and / or multifunctional (meth)acrylates include, without limitation, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl 2-chloro acrylate, 2-hydroxyethyl 2-ethylacrylate, 2-hydroxyethyl 2-propylacrylate, 2-hydroxyethyl 2-butylacrylate, 3-hydroxypropyl methacrylate, 3 -hydroxypropyl -2-propylacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl 2-butylacrylate, 3-hydroxypropyl 2-bromo acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate. 3 -hydroxybutyl 2-ethylacrylate, 4-hydroxybutyl 2-butylacrylate, 2-hydroxybutyl 2-propylacrylate, 4- hydroxybutyl 2-chloro acrylate, bis(methacryloyloxy)propanol, bis(acryloyloxy)propanol, pentaerythritol tnacrylatc. or a combination of any two or more thereof. Specific examples of suitable polyisocyanates for use in reacting with the monohydroxy-substituted monofunctional and / or multifunctional (meth)acrylate to fomr the isocyanate-functional ethylenically unsaturated compound include, without limitation, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1.3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1.5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3.3'-dimethyl-4.4'-diphenylmethane diisocyanate.4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexylisocyanate), 2,2,4-trimcthylhcxamcthylcnc diisocyanatc, 2,4,4 trimcthylhcxamcthylcnc diisocyanatc, hcxamcthylcnc diisocyanate, bis(2-isocyanato-ethyl)fumarate, 6-isopropyl-l,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, lysine isocyanate, hexamethylene diisocyanate trimers (such as iscommercially available as Desmodur® N3300A from Covestro), triphenylmethane-4,4',4"-triisocyanate (such as is commercially available as Desmodur® RE from Covestro), hexamethylene diisocyanate trimers (such as is commercially available as Desmodur® N3200 from Covestro), aromatic polyisocyanates based on toluene diisocyanate (such as is commercially available as Desmodur® IL BA from Covestro), polyisocyanurates of toluene diisocyanate (such as is commercially available as Desmodur® RC from Covestro), or a combination of any two or more thereof.

[0075] The reaction of the polyisocyanate (a) and (b) the isocyanate-containing ethylenically unsaturated compound with (c) the compound comprising more than one active hydrogen atoms, and (d) the polyaspartate amine to produce the ethylenically unsaturated compound of certain embodiments of this specification may, if desired, be carried out in tire presence of a catalyst. Suitable catalysts include, without limitation, an organic metal catalyst, an amine catalyst, or a combination thereof, such as where the catalyst comprises a copper compound, such as copper naphthenate, a cobalt compound, such as cobalt naphthenate, a zinc compound, such as zinc naphthenate, a bismuth compound, such as bismuth neodecanoate, a tin compound, such as di-n-butyl tin dilaurate, triethylamine, triethylenediamine, DABCO, DMEA, or a combination of any two or more of the foregoing. In some implementations, the reaction takes place at a temperature of 10 to 120°C or 25 to 100°C. In addition, in some implementations, the reactants are employed in relative amounts to provide a molar ratio of isocyanatereactive groups to isocyanate groups of at least 1:1, such as more than 1 to less than 1.5. The resulting ethylenically unsaturated compound comprises aspartate groups from the polyaspartate amine, as is depicted, for example, by structure (6) described earlier.

[0076] In some implementations, tire resulting aspartate group-containing ethylenically unsaturated compound is subjected to further processing to convert the aspartate group to a hydantoin group, w herein such conversion is carried out optionally in the presence of a catalyst, such as a Bronsted acids, a carboxylic acid, a sulfonic acid, a phenol, or a mixture of any two or more thereof, at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, or 80 to 100°C. The resulting ethylenically unsaturated compound comprises a hydantoin group, as is depicted, for example, by structure (7) described earlier.

[0077] As a result, this specification also relates to methods for making an ethylenically unsaturated compound that includes an end-group of structure (1). The method comprises reacting (a) a polyisocyanate and (b) an isocyanate -containing ethylenically unsaturated compound with (c) a compound comprising more than one active hydrogen atoms, and (d) a polyaspartate amine, optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising aspartate groups. In some implementations, tire method further comprises converting one or more of the aspartate groups toa hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising a hydantoin group.

[0078] In still other implementations, the ethylenically unsaturated compounds of this specification, which include an end-group of structure (1) described earlier, comprise a reaction product of reactants comprising: (a) a polyisocyanate; (b) an active hydrogen-containing ethylenically unsaturated compound; (c) a compound comprising more than one active hydrogen atoms; and (d) an active hydrogen-containing aspartate. In these implementations, suitable polyisocyanates, active hydrogencontaining ethylenically unsaturated compounds, and compounds comprising more than one active hydrogen atoms include any of those mentioned earlier.

[0079] In these implementations, suitable active hydrogen-containing aspartates include, withoutlimitation, those of the structure:are each as described above with reference to structure (8b) and structure (8c).

[0080] Tire reaction of (a) the polyisocyanate with (b) the active hydrogen-containing ethylenically unsaturated compound, (c) the compound comprising more than one active hydrogen atoms, and (d) the active hydrogen-containing aspartate to produce the ethylenically unsaturated compound of certain embodiments of this specification may, if desired, be carried out in the presence of a catalyst. Suitable catalysts include, without limitation, an organic metal catalyst, an amine catalyst, or a combination thereof, such as where the catalyst comprises a copper compound, such as copper naphthenate, a cobalt compound, such as cobalt naphthenate, a zinc compound, such as zinc naphthenate, a bismuth compound, such as bismuth neodecanoate, a tin compound, such as di-n-butyl tin dilaurate, triethylamine, triethylenediamine. DABCO. DMEA, or a combination of any two or more of the foregoing. In some implementations, the reaction takes place at a temperature of 10 to 120°C or 25 to 100°C. In addition, in some implementations, the reactants are employed in relative amounts to provide a molar ratio of isocyanate-reactive groups to isocyanate groups of at least 1:1, such as more than 1 to less than 1.5. The resulting ethylenically unsaturated compound comprises an aspartate group, as is depicted, for example, by structure (8) described earlier.

[0081] In some implementations, the resulting aspartate group-containing ethylenically unsaturated compound is subjected to further processing to convert at least some of the aspartate groups to a hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, such as a Bronsted acids, a carboxylic acid, a sulfonic acid, a phenol, or a mixture of any two or more thereof, at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, 80 to 100°C, 90 to 120°C, or 100 to 120°C. The resulting ethylenically unsaturated compound comprises a hydantoin group, as is depicted, for example, by structure (9) described earlier.

[0082] As a result, this specification also relates to methods for making an ethylenically unsaturated compound that includes an end-group of structure (1). The methods comprise reacting (a) a polyisocyanate with (b) an active hydrogen-containing ethylenically unsaturated compound, (c) a compound comprising more than one active hydrogen atoms, and (d) an active hydrogen-containing aspartate, optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising an aspartate group. In some implementations, the method further comprises converting at least some aspartate groups to a hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising a hydantoin group.

[0083] In yet other implementations, the ethylenically unsaturated compounds of this specification, which include an end-group of structure (1) described earlier, comprise a reaction product of reactants comprising: (a) a polyisocyanate; (b) an isocyanate-containing ethylenically unsaturated compound; (c) a compound comprising more than one active hydrogen atoms; and (d) an active hydrogen-containing aspartate. In these implementations, suitable polyisocyanates, isocyanate-containing ethylenically unsaturated compounds, compounds comprising more than one active hydrogen atoms, and active hydrogen-containing aspartates include any of those described earlier.

[0084] The reaction of (a) the polyisocyanate and (b) the isocyanate-containing ethylenically unsaturated compound with (c) the compound comprising more than one active hydrogen atoms, and (d) the active hydrogen-containing aspartate to produce the ethylenically unsaturated compound of certain embodiments of this specification may, if desired, be carried out in the presence of a catalyst. Suitable catalysts include, without limitation, an organic metal catalyst, an amine catalyst, or a combination thereof, such as where the catalyst comprises a copper compound, such as copper naphthenate, a cobalt compound, such as cobalt naphthenate, a zinc compound, such as zinc naphthenate, a bismuth compound, such as bismuth neodecanoate, a tin compound, such as di-n-butyl tin dilaurate, triethylamine, triethylenediamine, DABCO, DMEA, or a combination of any two or more of the foregoing. In some implementations, the reaction takes place at a temperature of 10 to 120°C or 25 to 100°C. In addition, in some implementations, the reactants arc employed in relative amounts to provide a molar ratio of isocyanate-reactive groups to isocyanate groups of at least 1:1, such as more than 1 to less than 1.5. lireresulting ethylenically unsaturated compound comprises an aspartate group, as is depicted, for example, by structure (10) described earlier.

[0085] In some implementations, tire resulting aspartate group-containing ethylenically unsaturated compound is subjected to further processing to convert at least some of the aspartate groups to a hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, such as a Bronsted acids, a carboxylic acid, a sulfonic acid, a phenol, or a mixture of any two or more thereof, at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, 80 to 100°C, 90 to 120°C, or 100 to 120°C. The resulting ethylenically unsaturated compound comprises a hydantoin group, as is depicted, for example, by structure (11) described earlier.

[0086] As a result, this specification also relates to methods for making an ethylenically unsaturated compound that includes an end-group of structure (1). The methods comprise reacting (a) a polyisocyanate and (b) an isocyanate -containing ethylenically unsaturated compound with (c) a compound comprising more than one active hydrogen atoms, and (d) an active hydrogen-containing aspartate, optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising an aspartate group. In some implementations, the method further comprises converting at least some aspartate groups to a hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising a hydantoin group.

[0087] In some other implementations, the ethylenically unsaturated compounds of this specification, which include an end-group of structure (1) described earlier, comprise a reaction product of reactants comprising: (a) a polyisocyanate; (b) an active -hydrogen-containing ethylenically unsaturated compound; (c) a compound comprising more than one active hydrogen atoms; (d) an active hydrogencontaining aspartate; and (e) a polyaspartate amine. In these implementations, suitable polyisocyanates, active hydrogen-containing ethylenically unsaturated compounds, compounds comprising more than one active hydrogen atoms, active hydrogen-containing aspartates, and polyaspartate amines include any of those described earlier.

[0088] Tire reaction of (a) the polyisocyanate with (b) the active -hydrogen-containing ethylenically unsaturated compound, (c) the compound comprising more than one active hydrogen atoms, (d) the active hydrogen-containing aspartate, and (e) the polyaspartate amine to produce the ethylenically unsaturated compound of certain embodiments of this specification may, if desired, be carried out in the presence of a catalyst. Suitable catalysts include, without limitation, an organic metal catalyst, an amine catalyst, or a combination thereof, such as where the catalyst comprises a copper compound, such as copper naphthenate, a cobalt compound, such as cobalt naphthenate, a zinc compound, such as zinc naphthenate, a bismuth compound, such as bismuth ncodccanoatc, a tin compound, such as di-n-butyl tin dilaurate, triethylamine, triethylenediamine, DABCO, DMEA, or a combination of any two or more of theforegoing. In some implementations, the reaction takes place at a temperature of 10 to 120°C or 25 to 100°C. In addition, in some implementations, the reactants are employed in relative amounts to provide a molar ratio of isocyanate-reactive groups to isocyanate groups of at least 1:1, such as more than 1 to less than 1.5. Tire resulting ethylenically unsaturated compound comprises an aspartate group, as is depicted, for example, by structure (12) described earlier.

[0089] In some implementations, the resulting aspartate group-containing ethylenically unsaturated compound is subjected to further processing to convert at least some of the aspartate groups to a hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, such as a Bronsted acids, a carboxylic acid, a sulfonic acid, a phenol, or a mixture of any two or more thereof, at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, 80 to 100°C, 90 to 120°C, or 100 to 120°C. The resulting ethylenically unsaturated compound comprises a hydantoin group, as is depicted, for example, by structure (13) described earlier.

[0090] As a result, this specification also relates to methods for making an ethylenically unsaturated compound that includes an end-group of structure (1). The methods comprise reacting (a) a polyisocyanate with (b) an active -hydrogen-containing ethylenically unsaturated compound, (c) a compound comprising more than one active hydrogen atoms, (d) an active hydrogen-containing aspartate, and (e) a polyaspartate amine, optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising an aspartate group. In some implementations, the method further comprises converting at least some aspartate groups to a hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising a hydantoin group.

[0091] In yet other implementations, the ethy lenically unsaturated compounds of this specification, which include an end-group of structure (1) described earlier, comprise a reaction product of reactants comprising: (a) a polyisocyanate; (b) an isocyanate-containing ethylenically unsaturated compound; (c) a compound comprising more than one active hydrogen atoms; (d) an active hydrogencontaining aspartate; and (e) a polyaspartate amine. In these implementations, suitable polyisocyanates, isocyanate-containing ethylenically unsaturated compounds, compounds comprising more than one active hydrogen atoms, active hydrogen-containing aspartates, and polyaspartate amines include any of those described earlier.

[0092] The reaction of (a) the polyisocyanate and (b) the isocyanate-containing ethylenically unsaturated compound with (c) the compound comprising more than one active hydrogen atoms, (d) the active hydrogen-containing aspartate, and (e) the polyaspartate amine to produce the ethylenically unsaturated compound of certain embodiments of this specification may, if desired, be carried out in the presence of a catalyst. Suitable catalysts include, without limitation, an organic metal catalyst, an aminecatalyst, or a combination thereof, such as where the catalyst comprises a copper compound, such as copper naphthenate, a cobalt compound, such as cobalt naphthenate, a zinc compound, such as zinc naphthenate, a bismuth compound, such as bismuth neodecanoate, a tin compound, such as di-n-butyl tin dilaurate, tri ethylamine, triethylenediamine, DABCO, DMEA, or a combination of any two or more of the foregoing. In some implementations, the reaction takes place at a temperature of 10 to 120°C or 25 to 100°C. In addition, in some implementations, the reactants are employed in relative amounts to provide a molar ratio of isocyanate-reactive groups to isocyanate groups of at least 1:1, such as more than 1 to less than 1.5. The resulting ethylenically unsaturated compound comprises an aspartate group, as is depicted, for example, by structure (14) described earlier.

[0093] In some implementations, tire resulting aspartate group-containing ethylenically unsaturated compound is subjected to further processing to convert at least some of the aspartate groups to a hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, such as a Bronsted acids, a carboxylic acid, a sulfonic acid, a phenol, or a mixture of any two or more thereof, at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, 80 to 100°C, 90 to 120°C, or 100 to 120°C. Tire resulting ethylenically unsaturated compound comprises a hydantoin group, as is depicted, for example, by structure (15) described earlier.

[0094] As a result, this specification also relates to methods for making an ethylenically unsaturated compound that includes an end-group of structure (1). The methods comprise reacting (a) a polyisocyanate and (b) an isocyanate -containing ethylenically unsaturated compound with (c) a compound comprising more than one active hydrogen atoms, (d) an active hydrogen-containing aspartate, and (e) a polyaspartate amine, optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising an aspartate group. In some implementations, the method further comprises converting at least some aspartate groups to a hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising a hydantoin group.

[0095] To produce the various ethylenically unsaturated compound described above, the various compounds that include isocyanate groups react with the various compounds that include active hydrogen groups. As will be appreciated, the reaction results in a reaction product mixture that has a statistical distribution of structures and molecular weights that depends on order of material addition, weight percentage content of materials and process conditions, such as reaction temperature. The resulting reaction product mixture will include at least some content an ethylenically unsaturated compound of the type described in this specification. The control of the sequence of reaction between isocyanate group-containing compounds and active hydrogen group-containing compounds can be accomplished by in a variety of ways, such as by varying order of material addition. As will also beappreciated, different processes can have significant impact on reaction product mixture composition and performance.

[0096] This specification also relates to use of the various ethylenically unsaturated compounds described above. More particular, in some respects, this specification relates to the use of such compounds in, for example, coating compositions, such as radiation curable coating compositions, including such composition that are suitable for application to optical glass fiber substrates. In fact, it has been surprisingly observed that at least some embodiments of such ethylenically unsaturated compounds, while being of relatively low viscosity and readily and efficiently synthesized, can provide cured coatings exhibiting surprisingly reduced Young's modulus without significantly sacrificing toughness, and while simultaneously exhibited significantly increased peel strength.

[0097] Some aspects of this specification, therefore, relate to radiation curable coating compositions that comprise (a) the ethylenically unsaturated compounds as described above. In some implementations, an ethylenically unsaturated compound of the type described above is present in the radiation curable composition as part of a mixture of two or more different ethylenically unsaturated compounds, in which, for example, such a mixture of two or more different ethylenically unsaturated compounds is present is an amount of in an amount of 1 to 99% by weight, 10 to 90% by weight, 20 to 50 by weight. 40 to 70% by weight, 60 to 80% by weight, 65 to 99% by weight, 80 to 99% by weight, or, in some cases, 1 to 30 % by weight, based on tire total weight of solids in the radiation curable coating composition. Moreover, in some implementations, the ethylenically unsaturated compound described above is present in an amount of 1 to 99% by weight, 1 to 90% by weight, such as 10 to 90% by weight, 20 to 80% by weight, 30 to 70% by w eight, or 40 to 60% by weight, based on the total weight of the ethylenically unsaturated compounds present in the coating composition.

[0098] Thus, in these implementations, the radiation curable coating composition may include other compounds having radiation-curable groups, such other radiation-curable composition may be used in amounts of up to, for example, 90% by weight, 75% by weight, or 70% by weight, based on the total weight of solids in the radiation curable coating composition. Examples of such other radiation-curable compounds are oligomers and polymers including, without limitation, polyether (meth)acrylates, polyester (meth)aciy dates, urethane (meth)acn dates, epoxy (meth)acrylates, and the known reactive diluents from radiation curing (cf. Rompp Lexikon Chemie, p. 491, 10thEd. 1998. Georg-Idiieme-Verlag. Stuttgart).

[0099] In some implementations, the radiation curable coating composition comprises a mixture of two or more different ethylenically unsaturated compounds, in which such a mixture comprises an ethylenically unsaturated compound (b) that is different from ethylenically unsaturated compound (a) described above, such as where ethylenically unsaturated compound (b) does not contain an aspartategroup or a hydantoin group. In some implementations, the ethylenically unsaturated compound (b) comprises an oligomer that has a number average molecular weight (Mn) of at least 400 g / mol, 1000 g / mol to 35,000 g / mol, 1000 g / mol to 30,000 g / mol, 1000 g / mol to 25,000 g / mol, 1000 g / mol to 20,000 g / mol, 2,200 to 10,000 g / mol, or 2,200 to 5,500 g / mol, measured as described earlier in this specification. These ethylenically unsaturated compounds comprise at least one ethylenically unsaturated group, in some case, 2 or more ethylenically unsaturated groups, per molecule.

[0100] In some implementations, the ethylenically unsaturated compound (b) comprises a urethane (meth)acrylatc oligomer, comprising a (meth)acrylate group, urethane groups and a backbone, such as where the backbone is derived from a polyol which has been reacted with an isocyanate, such as a polyisocyanate, and a hydroxyl group-containing (meth)acrylate. As used in this specification "(meth)acrylate" encompasses acrylates and methacrylates.

[0101] Examples of suitable polyols for use in preparing the ethylenically unsaturated compound (b) are, without limitation, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, acrylic polyols, and mixtures of any two or more thereof.

[0102] Suitable polyether polyols include, without limitation, polyethylene glycol, polypropylene glycol, polypropylene glycol-ethylene glycol copolymer, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, and polyether diols obtained by ring-opening copolymerization of two or more ion-polymerizable cyclic compounds, such as cyclic ethers, including, without limitation, ethylene oxide, isobutene oxide, tetrahydrofuran, 2-methyltetrahydrofiiran, 3 -methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, isoprene monoxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate. Specific examples of combinations of two or more ion-polymerizable cyclic compounds include, without limitation, combinations for producing a binary- copolymer, such as tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3 -methyltetrahydrofuran, and tetrahydrofuran and ethylene oxide; and combinations for producing a ternary copolymer such as a combination of tetrahydrofuran, 2-methyltetrahydrofuran, and ethylene oxide, a combination of tetrahydrofuran, butene-l-oxide, and ethylene oxide, and the like. The ring-opening copolymers of these ion-polymerizable cyclic compounds may be either random copolymers or block copolymers.

[0103] Suitable polyester diols include, without limitation, those obtained by reacting a polyhydric alcohol and a polybasic acid. Suitable polyhydric alcohols include, without limitation, ethylene glycol, polyethylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, 3-mcthyl- 1,5 -pentanediol, 1,9-nonancdiol, 2-mcthyl-l,8-octancdiol, and mixtures of any two or more thereof. Suitable polybasic acids include, without limitation, phthalic acid, dimer acid, isophthalic acid.terephthalic acid, maleic acid, fumaric acid, adipic acid, sebasic acid, and mixtures of any two or more thereof.

[0104] Suitable polycarbonate polyols include, without limitation, polycarbonates of polytetrahydrofuran. poly(hexanediol carbonate), poly(nonanediol carbonate), poly(3 -methyl- 1,5-pentamethylene carbonate), and mixtures of any two or more thereof.

[0105] Suitable polycaprolactone diols include, without limitation, those having a melting point of 0°C or higher that are obtained by reacting e-caprolactone and a diol compound. Suitable diol compounds include, without limitation, ethylene glycol, polyethylene glycol, polypropylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-butanediol, and mixtures of any two or more thereof.

[0106] Other suitable polyols include, without limitation, ethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1 ,6-hexanediol, polyoxyethylene bisphenol A ether, polyoxypropylene bisphenol A ether, polyoxyethylene bisphenol F ether, polyoxypropylene bisphenol F ether, and mixtures of any two or more thereof. In some embodiments, these other polyols have an alkylene oxide structure in the molecule, such as polyols containing polytetramethylene glycol and copolymer glycols of butylene oxide and ethylene oxide.

[0107] In some implementations, the number average molecular weight derived from the hydroxyl number of the polyol is 50 to 15,000 g / mol, such as 1,000 to 8,000 g / mol.

[0108] Suitable polyisocyanates for preparing the urethane (meth)acrylate oligomer include, without limitation, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5 -naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3.3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate. 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexylisocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis(2-isocyanato-ethyl)fumarate, 6-isopropyl-l,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, lysine isocyanate, hexamethylene diisocyanate trimers (such as is commercially available as Desmodur® N3300A from Covestro). triphenylmethane-4,4',4"-triisocyanate (such as is commercially available as Desmodur® RE from Covestro), hexamethylene diisocyanate trimers (such as is commercially available as Desmodur® N3200 from Covestro), aromatic polyisocyanates based on toluene diisocyanate (such as is commercially available as Desmodur® IL BA from Covestro), polyisocyanuratcs of toluene diisocyanatc (such as is commercially available as Desmodur® RC from Covestro). as well as combinations of any two or more thereof.

[0109] Suitable hydroxyl group-containing (meth)acrylates for use in preparing the urethane (meth)acrylate oligomer include, without limitation, (meth)acrylates derived from (meth)acrylic acid and epoxy and (meth)acrylates comprising alkylene oxides, such as, in particular, 2-hydroxy ethyl(meth )acry late. 2-hydroxypropylacrylate and 2-hydroxy-3-o\yphcnyl(mcth)acr latc.

[0110] To prepare the urethane (meth)acrylate oligomer, the ratio of polyol, polyisocyanate, and hydroxyl group-containing (meth)acrylate is, in some implementations, determined so that 0.1 to 0.9 equivalents of a hydroxyl group included in the hydroxyl group-containing (meth)acrylate and 1.0 to 1.5 equivalents of total hydroxyl groups present from the polyol and the hydroxyl group-containing (meth)acrylate are used for one equivalent of isocyanate group included in the polyisocyanate.[OHl] In some embodiments, a urethanization catalyst is present during the reaction of the foregoing three components. Suitable such catalysts included, without limitation, copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyl tin dilaurate, bismuth neodecanoate, triethylamine. triethylenediamine-2 -methyltriethyleneamine, as well as mixtures of any two or more thereof. In some implementations, the urethanization catalyst is used in an amount of 0.01 to 1% by weight, based on the total weight of the reactants. In some cases, the reaction is carried out at a temperature of 10 to 90°C, such as 30 to 80°C.

[0112] When the radiation curable coating composition includes both (a) an ethylenically unsaturated compound of the type described in this specification, which includes at least one aspartate group or hydantoin group, and ethylenically unsaturated compound (b), which may be an aspartate-free and hydantoin-free urethane (meth)acrylate oligomer, the composition can be produced by separately preparing (a) an ethylenically unsaturated compound of the type described in this specification and (b) a urethane (meth)acrylate oligomer that may be an aspartate-free and hydantoin-free urethane (mcth)acr late oligomer, and then mixing them together. Alternatively, an ethylenically unsaturated compound of the type described in this specification (a) and the ethylenically unsaturated compound (b) can also be synthesized together in one pot.

[0113] In such a one-pot synthesis, the various compounds that include isocyanate groups react with the various compounds that include active hydrogen containing groups. In some embodiments, the various components are combined in amounts such that the ratio of active hydrogen groups present to isocyanate groups present is from 1 to 1.5. As will be appreciated, the reaction results in a reaction product mixture that has a statistical distribution of structures and molecular weights depends on the order of material addition, weight percentage content of materials and process conditions, such as reaction temperature. When multiple oligomers are synthesized in one pot synthesis, the resulting reaction product mixture will include at least some content an ethylenically unsaturated compound of the type described in this specification. The control of the sequence of reaction between isocyanate group-containingcompounds and active hydrogen group -containing compounds can be accomplished by in a variety of ways, such as by varying order of material addition. As will also be appreciated, different processes can have significant impact on reaction product mixture composition and performance..

[0114] In addition to, or in lieu of, the previously described urethane (meth)acrylate (b)s, other ethylenically unsaturated compounds (b), which may be aspartate-free and hydantoin-free, can be used in embodiments of the radiation curable compositions of this specification, such as polyester (meth)acrylates, epoxy (mcth)acrylatcs. polyamide (meth)acrylates, siloxane polymers having a (meth)acryloyloxy group, reactive polymers obtained by reacting (meth)acrylic acid and a copolymer of glycidyl methacrylate and other polymerizable compounds, as well as mixtures of any two or more thereof. In some implementations, such an oligomer comprises a bisphenol A based acrylate oligomer, such as alkoxylated bisphenol-A-diacrylates and diglycidyl-bisphenol-A-diacrylates.

[0115] In some implementations, the ethylenically-unsaturated compound (b) may comprise an unsaturated urethane-free oligomer, such as an unsaturated urethane-free polyester acrylate oligomer and / or an unsaturated urethane-free alkyd acrylate oligomer. Examples of such oligomeric unsaturated compounds are acrylated epoxy resins, acrylated polyethers, and acrylated polyesters. Further examples of unsaturated oligomers are unsaturated polyester resins, such as those prepared from maleic acid, phthalic acid and one or more diols and which have molecular weights of greater than about 500.Unsaturated oligomers of this type are also known as prepolymers. Typical examples of unsaturated compounds are esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers containing ethylenically unsaturated groups in the chain or in side groups, including unsaturated polyesters, polyamides and copolymers thereof, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers containing (meth)acrylic groups in side-chains, as well as mixtures of one or more than one such polymer. Illustrative examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, unsaturated fatty acids such as linolenic acid or oleic acid. Suitable polyols are aromatic, aliphatic and cycloaliphatic polyols. Aromatic polyols are typically hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane, as well as novolacs and cresols. Polyepoxides include those based on the cited polyols, for instance on the aromatic polyols and epichlorohydrin.

[0116] One or more of the aforementioned ethylenically unsaturated compounds (b) can be employed in compositions according to the present invention in any suitable amount and may be chosen singly or in combination of one or more of the types enumerated herein. In some implementations, the ethylenically unsaturated compound (b) is present in an amount of 5 to 95 % by weight, 10 to 90% by weight, 10 to 80 % by weight or 30 to 90% by weight, or 50 to 80% by weight, based on the total weight of solids in the radiation curable composition.

[0117] In addition, in some implementations, the radiation curable coating composition comprises a reactive diluent compound (c) comprising one or more ethylenically unsaturated groups. Examples of such compounds include those containing one double bond, such as alkyl or hydroxyalkyl (meth)acrylates, suitable examples of which include, without limitation, methyl, ethyl, butyl, 2-ethylhexyl and 2 -hydroxyethyl acrylate, isobomyl acrylate, methyl and ethyl methacrylate, lauryl-acrylate, ethoxylated nonyl-phenol acrylate, phenoxyethyl (meth)acrylate, diethylene-glycol-ethyl-hexyl acylate (DEGEHA), acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamides, vinyl esters, such as vinyl acetate, styrene, alkyl styrenes, halostyrenes, N-vinylpyrrolidone, N-vinyl caprolactam, vinyl chloride, vinylidene chloride, and mixtures of any two or more thereof. Examples of such reactive diluent compounds that contain more than one double bond are ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylatc. bisphenol A diacrylate, 4,4'-bis(2-acryloyloxyethoxy)diphenylpropane, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate and tetraacrylate, vinyl acrylate, divinyl benzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, tris(2-acryloylethyl)isocyanurate, and mixtures of any two or more thereof.

[0118] In some embodiments, reactive diluent compound (c) is present in an amount of 5 to 90% by weight. 10 to 90% by weight, 10 to 80% by weight, 10 to 60% by weight, 10 to 40% by weight, or 10 to 30% by weight, based on the total weight of solids in the radiation curable composition.

[0119] In some implementations, the radiation curable compositions of this specification include a free-radical photoinitiator (d). More specifically, in some cases, the free-radical photoinitiator comprises an acylphosphine oxide, such as a bisacylphosphine oxide (BAPO) and / or monoacylphosphine oxide (MAPO), an a-hydroxy ketone, or a mixture of any two or more thereof.

[0120] In some embodiments, the photoinitiator (d) comprises a bisacylphosphine oxide having the structure:in which wherein R5o is C1-C12 alkyl, cyclohexyl or phenyl, which is unsubstituted or is substituted by 1 to 4 halogen atoms, or Ci-Cs alkyl; R51 and R52 arc each independently of the other Ci-Cs alkyl or Ci-Csalkoxy; R53 is hydrogen or Ci-Cs alkyl; and R is hydrogen or methyl. For example, in some implementations, R50 is C2-C10 alkyl, cyclohexyl or phenyl which is unsubstituted or is substituted by 1 to 4 C1-C4 alkyl, Cl or Br. In another embodiment, R50 is Cs-Cs alkyl, cyclohexyl or phenyl which is unsubstituted or is substituted in the 2-, 3-, 4- or 2,5 -positions by C1-C4 alkyl. In some cases, R50 is C4-C12 alkyl or cyclohexyl, R51 and R52 are each independently of the other Ci-Cs alkyl or Ci-Cs alkoxy and R53 is hydrogen or Ci-Cs alkyl. In some embodiments. R51 and R52 are C1-C4 alkyl or C1-C4 alkoxy and R53 is hydrogen or C1-C4 alkyl. Another embodiment is where Rsi and R52 are methyl or methoxy and R53 is hydrogen or methyl, such as where R51, R52 and R53 are methyl. Still another embodiment is where R51, R52 and R53 are methyl and R5 is hydrogen. In yet other embodiments, R50 is Cs-Cs alkyl, such as where R51 and R52 are methoxy, R53 and R54 are hydrogen and R50 is isooctyl. In some cases, R50 is isobutyl or phenyl. Specific examples of suitable bisacylphosphine oxides include, without limitation, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-(2,4-bis-pentyloxyphenyl)phosphine oxide, or a mixture thereof.

[0121] Specific examples of suitable photoinitiator blends include, without limitation, those disclosed in U.S. Pat. Nos. 6,020,528 and 7,169,826. In some implementations, the photoinitiator blends comprises mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (CAS #162881-26-7) and 2,4,6,-trimethylbenzoylethoxyphenylphosphine oxide (CAS #84434-11-7) in a ratio by weight of, for example, 1: 11 to 1:7. In other implementations, the photoinitiator blend comprises a mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6, -trimethylbenzoylethoxyphenylphosphine oxide and 2-hydroxy-2-methyl-l -phenyl- 1 -propanone (CAS #7473-98-5) in a weight ratios of, for example, 3:1:15 to 4: 1 : 16. In another embodiments, the photoinitiator blend comprises a mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2 -hydroxy -2 -methyl- 1 -phenyl- 1 -propanone in a weight ratio of, for example, 1:3 to 1:5.

[0122] Other suitable photoinitiators include, without limitation, other mono- or bisacylphosphinoxides, such as diphenyl-2,4,6-trimethylbenzoylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphineoxide; a-hydroxyketones, such as 1-hydroxycyclohexylphenylketone and 2-hydroxy-l-[4-(2-hydroxyethoxy)phenyl]-2-methyl-l-propanone; a-aminoketones, such as 2-niethyl-l-[4-(methylthio)phenyl]-2-(4-morpholinyl)-l-propanone, 2-benzyl-2-(dimethylamino)-l-[4-(4-morpholinyl)phenyl]-l-butanone, 2-(4-methylbenzyl-2-(dimethylamino)-l-[4-(4-morpholinyl)phenyl] - 1 -butanone and 2-benzyl-2-(dim ethylamino)- 1 -[3, 4-dim ethoxyphenyl] - 1 -butanone; benzophenones, such as benzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 2-methylbenzophenone, 2 -methoxy carbonylbenzophenone, 4,4'-bis(chloromethyl)-benzophenone, 4-chlorobcnzophcnonc, 4-phcnylbcnzophcnonc, 4,4'-bis(dimcthylamino)-bcnzophcnonc, 4,4'-bis(diethylaniino)benzophenone, methyl2-benzoylbenzoate, 3,3'-dimethyl-4-methoxybenzophenone, 4-(4-methylphenylthio)benzophenone, 2,4,6-trimethyl-4'-phenyl-benzophenone and 3-methyl-4'-phenyl-benzophenone; ketal compounds, such as 2.2 -dimethoxy- 1,2-diphenyl -ethanone; and compoundic or dimeric phenylglyoxylic acid esters, such as methylphenylglyoxylic acid ester, 5,5 '-oxo-di(ethyleneoxydicarbonylphenyl) and l,2-(benzoylcarboxy)ethane, as well as mixtures of any tw o or more thereof.

[0123] Still other suitable photoinitiators include, without limitation, oxime esters as disclosed in U.S. Pat. No. 6,596,445. Also suitable are phenyl glyoxalates, such as are disclosed in U.S. Pat. No. 6,048,660 and germanium-based photoinitiators as disclosed in Dalton Trans. 2021, 50, 12392-12398.

[0124] In some implementations, tire free-radical photoinitiator (d) is present in an amount of 0.1 to 10 % by weight, such as 0.1 to 5 % by weight, or, in some cases, 1 to 5 % by weight, based on the total weight of the radiation curable composition.

[0125] Photoinitiators suitable for use in the radiation curable compositions of this specification are also described in United States Patent Application Publication No. US 2021 / 0088720 Al at

[0080] -

[0128] , the cited portion of which being incorporated herein by reference.

[0126] As will be appreciated, the radiation curable compositions of this specification may include any of a variety of further components, including any of a variety of various additives that may enable the composition to achieve certain desirable characteristics such as improved shelf life, improved coating oxidative and hydrolytic stability, improved cure speed, additional coating functional performance, and the like. For example, in some implementations, the radiation curable compositions of this specification may include one or more of a photosensitizer, a radiation cure amine synergist, a UV absorber, an antioxidant, a UV stabilizer, a light stabilizer, a filler material, a chain transfer thiol compound, a surface active compound, a viscosity modifier, an additional addition promoter, a water scavenger such as tetraethyl orthosilicate (TEOS) and orthoformate, oxygen quencher or a functional material including pigments, dyes, photochromic dyes, laser dyes, liquid crystals, light emitting materials, nano materials, quantum dots, fluorescent materials, dichroic dyes, antistatic materials, refractive index modifier and bioactive materials, among others. Some suitable additives are described in United States Patent Application Publication No. US 2021 / 0088720 Al at

[0122] -

[0134] , the cited portion of which being incorporated herein by reference.

[0127] In some implementations, the radiation curable compositions of this specification comprise an adhesion promoter (e). Suitable adhesion promoters (e) include silane coupling agents, such as hydrolysable silane compounds which contain a mercapto group and / or a plurality of alkoxy groups, such as those described in United States Patent Application Publication No. US 2002 / 0013383 Al, the relevant portions of which being incorporated herein by reference. Specific examples of such adhesionpromoters are gamma-mercaptopropyltrimethoxysilane, trimethoxysiliylpropyl acrylate, 3-trimetoxysilylpropane-1 -thiol, and mixtures of any two or more thereof.

[0128] In some implementations, tire adhesion promoter (e) may comprise an ethylenically unsaturated silane monomer comprising: (a) a moiety of the structure (1):Y - Si(X)3(1); and (b)(1) a moiety of the structure (2):(2); or (b)(2) a moiety of the structure (3):(3); or(b)(3) a combination of a moiety of the structure (2) and a moiety of the structure (3), in which (i) Y represents a linear or branched linking group comprising 1 or more carbon atoms, (ii) each X, which may be the same or different, represents an alkoxy group or an organic group that is inert towards isocyanate groups at temperatures of 100°C or less, with the proviso that at least one X represents an alkoxy group, (iii) R1and R2, which may be the same or different, each represent an organic group that is inert to isocyanate groups at temperatures of 100°C or less; (iv) R3and R4, which may be the same or different, each represent hydrogen or an organic group that is inert to isocyanate groups at temperatures of 100°C or less; and (v) each " - • " represents a linkage to another portion of the ethylenically unsaturated silane. Such ethylenically unsaturated silanes, as well the preparation thereof, are described in U.S. Provisional Patent Application Serial No. 63 / 616,890, entitled ETHYLENICALLY UNSATURATED COMPOUNDS, METHODS FOR THEIR PREPARATION, AND THE USE THEREOF IN COATING COMPOSITIONS, which is incorporated herein by reference.

[0129] In some implementations, the adhesion promoter (e) may include a poly-silane, such as a poly-silane monomer comprising: (a) at least two, in some cases two, moieties of the structure (1):Y7— Si(X9) (1); and(bl) a moiety of the structure (2):O(2);(b2) a moiety of the structure (3):O(3); or (b3) a combination of a moiety of the structure (2) and a moiety of the structure (3).in which (i) Y7represents a linear or branched linking group comprising 1 or more carbon atoms, (ii) each X9represents an alkoxy group or an organic group that is inert towards isocyanate groups at temperatures of 100°C or less, with the proviso that at least one X9represents an alkoxy group, (iii) R26and R27, which may be the same or different, each represent an organic group that is inert to isocyanate groups at temperatures of 100°C or less: (iv) R28and R29, which may be the same or different, each represent hydrogen or an organic group that is inert to isocyanate groups at temperatures of 100°C or less; and (v) each " - • " represents a linkage to another portion of the poly-silane. Such poly-silanes, as well the preparation thereof, are described in U.S. Provisional Patent Application Serial No. 63 / 616,868 entitled POLYSILANES, METHODS FOR THEIR PREPARATION, AND THE USE THEREOF IN COATING COMPOSITIONS, which is incorporated herein by reference.

[0130] In some cases, the adhesion promoter (e) may include an ethylenically unsaturated oligomer comprising: (a) a moiety of the structure (1):• - Y1— Si(X)3(i);(bl) a moiety of the structure (2):(2); or(b2) a moiety of the structure (3):O(3); or (b3) a combination of a moiety of the structure (2) and a moiety of the structure (3): and(c) a moiety of the structure (3a):in which (i) Y1represents a linear or branched linking group comprising 1 or more carbon atoms, (ii) each X, which may be tire same or different, represents an alkoxy group or an organic group that is inert towards isocyanate groups at temperatures of 100°C or less, with the proviso that at least one X represents an alkoxy group, (iii) each R1. which may be the same or different, represents an organic group that is inert to isocyanate groups at temperatures of 100°C or less; (iv) each R2, which may be the same ordifferent, represents hydrogen or an organic group that is inert to isocyanate groups at temperatures of 100°C or less; (v) each " - • " represents a linkage to another portion of the ethylenically unsaturated oligomer; (vi) each G1is 0 or S, (vii) m has a value of 1 to 5, such as 1 to 3, or 1, (viii) n has a value of 1 to 5, 1 to 3, or 1, and (ix) Zprepresents an organic group that is inert towards isocyanate groups at temperatures of 100°C or less. Such ethylenically unsaturated oligomers, as well the preparation thereof, are described in U.S. Patent Application Serial No. 18 / 596,114 entitled ETHYLENICALLY UNSATURATED OLIGOMERS, METHODS FOR THEIR PREPARATION, AND THE USE THEREOF IN COATING COMPOSITIONS, which is incorporated herein by reference.

[0131] In some embodiments, the radiation curable compositions of this specification have a total silane content (detennined as described in the Examples section of this specification) of up to 10 mmol, such as 1 to 10 mmol, 1 to 8 mmol, or, in some cases 2 to 6 mmol, per 100 gram of the radiation curable composition. Also, in some implementations, the radiation curable compositions of this specification have a total content of urea+urethane (determined as described in the Examples section of this specification) of 20 to 200 mmol, such as 30 to 150 mmol, or, in some cases 40 to 100 mmol, per 100 gram of the radiation curable composition.

[0132] Further, in some embodiments, a cured coating deposited from a coating composition of this specification exhibits a peel strength of at least 40 gram-force / inch ("gf / in"), at least 55 gf / in, at least 70 gf / in. at least, at least 80 gf / in, at least 100 gf / in, at least 150 gf / in, or at least 200 gf / in. when measured as described in the Examples section of this specification. In some of these embodiments, the peel strength is up to 300 gf / in. In addition, in some embodiments, a cured coating deposited from a coating composition of this specification exhibits an elongation at break of at least 35 %, at least 50%, at least 80%, or at least 100%, when measured as described in the Examples section of this specification. In some of these embodiments, the elongation at break is up to 200%, up to 150%, or up to 120%. Further, in some cases, a cured coating deposited from a coating composition of this specification exhibits a tensile modulus of less than 5 MPa, less than 2 MPa, less than 1.5 MPa, or less than 1.0 MPa. Methods for describing in-situ modulus are well-known in the art and are described in, inter alia, US 7,171,103 and US 6,961,508, which are incorporated herein by reference.

[0133] In addition, in some embodiments, the coating compositions of this specification are configured to possess a viscosity of at least >0.1 Pascal seconds (Pa s), at least 0.2, at least 0.5, at least 1 Pa s, and / or less than 15 Pa s. less than 12 Pa-s. or less than 10 Pa s, or 1 to 15 Pa s. 2 to 12 Pa s. or 3 to 10 Pa s, wherein viscosity is measured at 25 °C and a shear rate of 50 s’1.

[0134] As should be appreciated, in some respects, this specification relates to a method for coating an optical fiber. Such methods comprise providing a glass optical fiber, such as by drawing a glass optical fiber through a draw tower; applying a primary coating composition onto the surface of theglass optical fiber; optionally, imparting a dose of UV light sufficient to at least partially cure said primary coating composition; applying a secondary coating composition to the primary coating composition; exposing the secondary coating composition to at least one radiation source capable of emitting ultraviolet radiation to affect curing of said secondary’ coating composition and, optionally said primary coating composition, to form a cured primary coating on the surface of the optical fiber, and a cured secondary coating on the surface of the cured primary coating. In these methods, the primary coating composition and / or the secondary coating composition is a composition of the type described in this specification.

[0135] As should also be appreciated, this specification also relates to coated optical fibers, the coated optical fiber comprising a glass core and a cladding layer in contact with and surrounding said glass core: and a coating portion, said coating portion further including a primary coating layer in contact with said cladding layer; and a secondary coating layer in contact with and surrounding said primary coating layer. According to this aspect, the primary coating layer and / or the secondary coating layer is a cured product of a coating composition of the type described in this specification. In some cases, the optical fiber comprises a core, a cladding, a primary coating contacting and surrounding the outer annular cladding region, and a secondary coating. According to some of these embodiments, the core comprises pure silica glass ( S i O2) or silica glass with one or more dopants that increase the index of refraction of tire glass core relative to pure, undoped silica glass. Suitable such dopants include, without limitation, GeO2. AI2O3, P2O5, TiCh, ZrCf. Nb20s, Ta20s, and / or combinations thereof. The cladding layer may comprise pure silica glass ( Si O2). silica glass with one or more dopants which increase the index of refraction (e.g., GeCf, AI2O3, P2O5, TiC>2, ZrC>2, Nb20.5 and / or Ta20s), such as when the cladding is “up-doped,” or silica glass with a dopant which decreases the index of refraction, such as fluorine, such as when the inner cladding is “down-doped”, so long as the maximum relative refractive index [A1MAX] of the core is greater than the maximum relative refractive index [A4MAXJ of the cladding. According to one embodiment, the cladding is pure silica glass. According to some of these embodiments, the primary coating has an in-situ (or on-fiber) modulus of less than 5 MPa, less than 2 MPa, less than 1.5 MPa, or less than 1.0 MPa. Methods for describing in-situ modulus are well-known in the art and are described in, inter alia, US 7,171,103 and US 6.961,508, which are incorporated herein by reference. In some embodiments, the primary coating has a glass transition temperature of less than -10°C, less than -35°C, less than -40°C. less than -45°C, and in other embodiments not less than -100 °C. Methods for describing glass transition temperature are also described in, inter alia, US 7,171,103 and US 6,961,508. A primary coating with a low in-situ modulus reduces the microbending which is the coupling mechanism between the modes propagating in the fiber. A low glass transition temperature ensures that the in-situ modulus of the primary coating will remain low even when the fiber is deployed in very cold environments.

[0136] The primary coating typically has a thickness in the range of 20 to 50 pm (e.g., about 25 or 32.5 pm), thinner thickness in the range of 15 to 25 pm for 200 pm fibers. In other embodiments, the primary coating has a thickness that is no more than 40 pm, such as 20 to about 40 pm, or, in some cases, 20 to 30 pm.

[0137] The secondary coating is in contact with and surrounds the primary coating. The secondary coating is, for example, the polymerization product of a coating composition whose molecules become highly crosslinked when polymerized. The secondary coating, according to an embodiment, may possess an in-situ modulus of greater than 800 MPa, greater than 1110 MPa, greater than 1300 MPa, greater than 1400 MPa, or, in some cases, greater than 1500 MPa. In some embodiments, the secondary coating has a high in-situ modulus (e.g., greater than about 800 MPa at 25°C) and a high Tg (e.g., greater than about 50°C). In some cases, the in-situ secondary modulus is from 1000 MPa to 8000 MPa, such as 1200 MPa to 5000 MPa or 1500 MPa to 3000 MPa. The in-situ Tg of the secondary coating is, in some embodiments, from 50°C to 120°C or, in some cases, 50°C to 100°C. Moreover, in some embodiments, the secondary coating has a thickness of no more than 40 pm, such as 20 to 40 pm, or, in some cases, 20 to 30 pm.

[0138] Suitable outer (or secondary) coating materials, as well as considerations related to selection of these materials, are also described in, for example, U.S. Patent Nos. 4,962,992 and 5,104,433, each of which being incorporated herein by reference. As an alternative to these, high modulus coatings have also been obtained using low oligomer content coating systems, as described in U.S. Patent No. 6,775,451 and U.S. Patent No. 6,689,463, each of which being incorporated herein by reference. Also suitable are high modulus coating produced using non-reactive oligomer components, as described in U.S. Patent Application Publication. No. US 2007 / 0100039 Al, which is incorporated herein by reference. The secondary coating may also include an ink, as is well known in the art and, in such cases, may be referred to as a "colored secondary coating."

[0139] The coated optical fiber may, if desired, comprise one or more additional layers disposed on the secondary layer, such as a standalone "ink" layer which is applied and cured separately from the secondary coating.

[0140] It is known in the art how to fonnulate typical optical fiber coating for primary and secondary coatings for fiber as described above, as well as for ink and matrix materials for curing using broadband UV lamps. A good discussion of this technology and associated chemistry and test methods can be found in sections 4.6 to the end of chapter 4 in the textbook, "Specialty Optical Fibers Handbook" by A. Mendez and T.F. Morse, (c) Elsevier Inc. 2007, published by Elsevier.

[0141] Any optical fiber type may be used in embodiments of inventions described herein. In some implementations, however, the coated optical fiber possesses a mode-field diameter from 8 to 10pm at a wavelength of 1310 nnr a mode-field diameter from 9 to 13 m at a wavelength of 1550 nm, and / or an effective area of 20 to 200 pm2. Such fibers may be single mode and / or large -effective area fibers, given the expected demand for coating processes for these fibers that utilize higher line or processing speeds. However, other fiber types, such as multimode fibers, may be used as well.

[0142] As should also be appreciated, this specification also relates to an optical fiber cable, wherein the optical fiber comprises at least one optical fiber as described herein, and / or wherein the optical fiber is the cured product of a coating composition as described herein.

[0143] Various aspects of the subject matter described herein are set out in the following numbered clauses:

[0144] Clause 1. An ethylenically unsaturated compound comprising: (a) a moiety of the structure (1):H N G1— Zp— O'! !(i);(bl) a moiety of the structure (2):(2); or(b2) a moiety of the structure (3):O(3); or(b3) a combination of a moiety of the structure (2) and a moiety of the structure (3); and, optionally, (c) a moiety of the structure (3a):(3a) in which (i) each R1. which may be the same or different, represents an organic group that is inert to isocyanate groups at temperatures of 100°C or less; (ii) each R2. which may be the same or different, represents hydrogen or an organic group that is inert to isocyanate groups at temperatures of 100°C or less; (iii) each " - • " represents a linkage to another portion of the ethylenically unsaturated compound; (iv) each G1is 0 or S; (v) m has a value of 1 to 5, such as 1 to 3, or 1; (vi) n has a value of 1 to 5, 1 to 3, or 1; and (vii) Zprepresents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Ci s alkylene group or a Cs-Ce cycloalkylene group.

[0145] Clause 2. The ethylenically unsaturated compound of clause 1, wherein the ethylenically unsaturated compound is a monomer, such as a monomer having a molecular weight, calculated from the molecular formula of the ethylenically unsaturated compound, of 400 to less than 2000 g / mol or 400 to 1000 g / mol.

[0146] Clause 3. The ethylenically unsaturated compound of clause 1, wherein the ethylenically unsaturated compound is an oligomer, such as an oligomer having a number average molecular weight (Mn) of at least 800 g / mol, 800 to 35,000 g / mol, 1000 g / mol to 35,000 g / mol, 2000 g / mol to 30,000 g / mol, 2000 g / mol to 25,000 g / mol, 2000 g / mol to 20,000 g / mol, 2,200 to 10,000 g / mol, or 2,200 to 5,500 g / mol, in which Mn is determined by size exclusion chromatography as described in the specification.

[0147] Clause 4. Hie ethylenically unsaturated compound of one of clause 1 to clause 3. wherein the ethylenically unsaturated compound comprises 1 to 4. 1 to 2, or 1 ethylenically unsaturated group.

[0148] Clause 5. The ethylenically unsaturated compound of one of clause 1 to clause 4, wherein the ethylenically unsaturated compound comprises and end group of structure (1) and an end group of tire structure (la):E - • (la)in which E represents a group that comprises a polymerizable carbon-carbon double bond, such as an acryloyl, methacryloyl, or vinyl group and • represents a linkage to another portion of the ethylenically unsaturated compound, such as where the end group of structure (la) has the structure (lb):(lb)in which R3is H or CH, and • represents a linkage to another portion of the ethylenically unsaturated oligomer.

[0149] Clause 6. The ethylenically unsaturated compound of one of clause 1 to clause 5, wherein an end group of structure (1) and an end group of structure (la) are arranged at opposite ends of the ethylenically unsaturated compound.

[0150] Clause 7. The ethylenically unsaturated compound of one of clause 1 to clause 6, wherein (i) each R1in structures (2) and (3), which may be the same or different, represents an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where each R1in structures (2) and (3), which may be the same or different, represents a methyl group, an ethyl group, a propyl group or a butyl group, and (ii) each R2in structures (2) and (3), which may be the same or different, represents a hydrogen or an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where each R2in structures (2) and (3), which may be the same or different, represents a hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group.

[0151] Clause 8. The ethylenically unsaturated compound of one of clause 1 to clause 7, wherein Zpis a portion of the residue of a polyol, such as a diol, a triol, or a higher functionality polyol, such as a polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, acrylic polyol, or a combination of any two or more thereof, such as where the polyol has a number average molecular weight, derived from the hydroxyl number of the polyol, of 62 to 20,000 g / mol, 500 to 15,000 g / mol. 900 to 9,000 g / mol, 1,800 to 6.000 g / mol or 2,500 to 5.000 g / mol.

[0152] Clause 9. The ethylenically unsaturated compound of one of clause 1 to clause 8, wherein the ethylenically unsaturated compound is not moisture curable, such as where the ethylenically unsaturated compound is free of silane groups.

[0153] Clause 10. Tire ethylenically unsaturated compound of one of clause 1 to clause 9, wherein the ethylenically unsaturated compound is represented by the structure (4):in which (i) each Y, which may be the same or different, represents a group comprising a branched or straight chain alkylene radical, such as where the branched or straight chain alkylene radical has at least 2, 2 to 8, or 2 to 4 carbon atoms; (ii) each G1, which may be the same or different, represents 0 or S; (iii) each G, which may be the same or different, represents 0, S, NH, or NR' in which R' is an alkyl radical, such as an alkyl radical having 1 to 6 carbon atoms; (iv) Zprepresents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a Cs-Ce cycloalkylene group; (v) each R3, which may be the same or different, represents H or CH3, (vi) m has a value of 1 to 5, such as 1 to 3, or 1; (vii) n has a value of 1 to 5, 1 to 3, or 1; (viii) q has a value of at least 1, such as 1 to 20, 1 to 5, or 1 to 3; (ix) r is 1, 2 or 3; (x) LNis represented by the structure:m n, in which Z1represents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a C -C, cycloalkylene group, m and n arc each as described above, and - • represents a linkage to another portion of the ethylenically unsaturated compound; and (xi) each L2. which may be the same or different, is represented by the structure L1or LB, with the proviso that at least one occurrence of L2is represented by the structure LB, in which L1is represented by structure (4a):H H N G1- Zp- G1N>O O-J m -1n (4a)in which Zp, G1, m, n and - • are each as described above with respect to structure (4); and LBis represented by structure (4b):in which: (i) ZArepresents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a Ci-C, cycloalkylcnc group; (ii) each R1, which may be the same or different, represents an organic group that is inert to isocyanate groups at temperatures of 100°C or less, such as where each R1in structure (4b), which may be the same or different, represents an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where each R1in structure (4b), which may be the same or different, represents a methyl group, an ethyl group, a propyl group or a butyl group; (iii) each R2, which may be the same or different, each represent an organic group that is inert to isocyanate groups at temperatures of 100°C or less, such as where each R2in structure (4b), which may be the same or different, represents a hydrogen, an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where each R2in structure (4b), which may be the same or different, represents a hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group; (iv) m and n are each as described above with reference to structure (4); and (v) each - • represents a linkage to another portion of the ethylenically unsaturated compound.

[0154] Clause 11. Tire ethylenically unsaturated compound of clause 10, w herein Y in structure (4) comprises a linear or branched alkylene radical having 1 to 8 carbon atoms, such as a linear alkylene radical having 2 to 4 or, in some cases 3, carbon atoms (such as a propylene radical), or a branched alkylene radical having 5 to 6 carbon atoms.

[0155] Clause 12. The ethylenically unsaturated compound of clause 10 or clause 11, wherein at least one Y in structure (4) is:. — C2H4— •, in which n has a value of 0 to 100, 0 to 50, or, in, in which n has a value of 0 to 100, 0 to 50, or 0 to 10;a combination of any two or more thereof, in which each • represents a linkage to another portion of the ethylenically unsaturated compound.

[0156] Clause 13. The ethylenically unsaturated compound of one of clause 10 to clause 12, wherein Z1in structure (4) is:, in w x has a of 3 to 19;R10, in which R10is C2H5 or H and each of XI, X2, X3 and X4, which may be the same or different, has a value of 1 to 10, provided that the structure has a molecular weight of 200 to 1500;in which each - • represents a linkage to another portion of the ethylenically oligomer compound.

[0157] Clause 14. The ethylenically unsaturated compound of one of clause 10 to clause 13, wherein each R1in structure (4b), which may be the same or different, represents an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where R1, which may be the same or different, represents a methy l group, an ethyl group, a propyl group or a butyl group and each R2in structure (4b) represents a hydrogen.

[0158] Clause 15. The ethylenically unsaturated compound of one of clause 10 to clause 14. wherein Zpin structure (4a) is a portion of the residue of a polyol, such as a diol, a triol, or a higher functionality polyol, such as a polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, acrylic polyol, among others, including combinations of any two or more thereof.

[0159] Clause 16. Tire ethylenically unsaturated compound of one of clause 10 to clause 15, wherein Zpin structure (4a) is a portion of a residue of a polyol that has a number average molecular weight, derived from the hydroxyl number of the polyol, of 62 to 20,000 g / mol, such as 500 to 15,000 g / mol, 900 to 9,000 g / mol, or, in some cases, 1,800 to 6,000 g / mol or 2,500 to 5,000 g / mol.

[0160] Clause 17. Tire ethylenically unsaturated compound of one of clause 1 to clause 9, wherein the ethylenically unsaturated compound is represented by the structure (5):(5) in which Y, G, G1, R3, m, n, q, r, LNand Zpare each as described above in clause 8 to clause 14 and each L3, which may be the same or different, is represented by the structure L1or Lc, with the proviso that at least one occurrence of L3is represented by the structure Lc, in which L1is represented by structure (4a) described above; and Lcis represented by structure (5b):in which: (i) ZA, R1, R2, m, and n are each as described above in clause 9 to clause 15, and (iii) each - • represents a linkage to another portion of the ethylenically unsaturated compound.

[0161] Clause 18. Tire ethylenically unsaturated compound of one of clause 1 to clause 9, wherein the ethylenically unsaturated compound is represented by the structure (6):in which Y2represents a group comprising a branched or straight chain alkylene radical, such as where the branched or straight chain alkylene radical has at least 2, 2 to 8, or 2 to 4 carbon atoms, and R3, G1, Zp, L2, LN, m, n, q, and r are each as described above in clause 10 to clause 16.

[0162] Clause 19. Tire ethylenically unsaturated compound of clause 18, wherein Y2in structure (6) comprises a linear or branched alkylene radical having 1 to 8 carbon atoms, such as a linear alkylene radical having 2 to 4 or, in some cases 3, carbon atoms (such as a propylene radical), or a branched alkylene radical having 5 to 6 carbon atoms.

[0163] Clause 20. Tire ethylenically unsaturated compound of clause 18 or clause 19, wherein at least one Y2is:, in which n has a value of 0 to 100, 0 to 50, or. in, in which n has a value of 0 to 100, 0 to 50, or 0 to 10;a combination of any two or more thereof, in which each - • represents a linkage to another portion of the ethylenically unsaturated compound.

[0164] Clause 21. Tire ethylenically unsaturated compound of one of clause 1 to clause 9, wherein the ethylenically unsaturated compound is represented by the structure (7):in which Y2represents a group comprising a branched or straight chain alkylene radical, such as where the branched or straight chain alkylene radical has at least 2, 2 to 8, or 2 to 4 carbon atoms, and R3, G1, Zp, L3, LN, m, n, q, and r are each as described above in clause 17.

[0165] Clause 22. The ethylenically unsaturated compound of one of clause 1 to clause 9, wherein the ethylenically unsaturated compound is represented by the structure (8):in which Y, R3, G. G1. Zp. LN. m, n, q. and r are each as described above in clause 10 to clause 16. and each L4, which may be the same or different, is represented by the structure L1or LD, with the proviso that at least one occurrence of L4is represented by the structure LD, in which L1is represented by structure (4a) as described in clause 10 to clause 16 and LDis represented by structure (8b):(8b),in which: (i) Z3represents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a Cs-C,, cycloalkylene group; (ii) G, R1, R2, m, and n are each as described above in clause 10 to clause 16, and (iii) each - • represents a linkage to another portion of the ethylenically unsaturated compound.

[0166] Clause 23. The ethylenically unsaturated compound of one of clause 1 to clause 9, wherein the ethylenically unsaturated compound is represented by the structure (9):in which Y, R3, G, G1, Zp, LN, m, n, q, and r are each as described above in clause 10 to clause 16, and each L5, which may be the same or different, is represented by the structure L1or LE, with the proviso that at least one occurrence of L5is represented by the structure LE, in which L1is represented by structure (4a) described in clause 10 to clause 16 and LEis represented by structure (9b):(9b), or the structure (9c):(9c) in which: (i) Z3represents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a CS-CA cycloalkylene group; (ii) G, R1, R2, m, and n are each as described above in clause 10 to clause 16, and (iii) each - • represents a linkage to another portion of the ethylenically unsaturated compound.

[0167] Clause 24. Tire ethylenically unsaturated compound of one of clause 1 to clause 9, wherein the ethylenically unsaturated compound is represented by the structure (10):(10), in which R3, G1, Zp, LN, m, n, q, and r are each as described above in clause 10 to clause 16, L4is as described above in clause 22, and Y2is as described above in clause 18 to clause 20.

[0168] Clause 25. Tire ethylenically unsaturated compound of one of clause 1 to clause 9, wherein the ethylenically unsaturated compound is represented by the structure (11):(ID,in which Y, R3, G1, Zp, LN, m, n, q, and r are each as described above in clause 10 to clause 16, L5is as described above in clause 23, and Y2is as described above in clause 18 to clause 20.

[0169] Clause 26. The ethylenically unsaturated compound of one of clause 1 to clause 9, wherein the ethylenically unsaturated compound is represented by the structure (12):(12) in which: (i) Y, R3, Zp, G, G1, LN, m, n, and r are each as described above in clause 10 to clause 16; (ii) q has a value of 2 to 20, 2 to 5, or 2 or 3; and (ii) each Lb, which may be the same or different, is represented by the structure L1, the structure LD, or the structure LB, with the proviso that at least one occurrence of L6is represented by the structure LDand at least one occurrence of L6is represented by the structure LB. in which L1is represented by structure (4a) described in clause 10 to clause 16, LDis represented by structure (8b) or structure (8c) described in clause 22, and LBis represented by the structure (4b) described in clause 10 to clause 16.

[0170] Clause 27. The ethylenically unsaturated compound of one of clause 1 to clause 9, wherein the ethylenically unsaturated compound is represented by the structure (13):(13) in which: (i) Y, R3, Zp, G, G1, LN, m, n, and r are each as described above in clause 10 to clause 16; (ii) q has a value of 2 to 20, 2 to 5, or 2 or 3; and (ii) each L7, which may be the same or different, is represented by the structure L1, the structure LE, or the structure Lc, with the proviso that at least one occurrence of L7is represented by the structure LEand at least one occurrence of L6is represented by the structure Lc, in which L1is represented by structure (4a) described in clause 10 to clause 16, LEis represented by structure (9b) or structure (9c) described above in clause 23, and Lcis represented by the structure (5b) described in clause 17.

[0171] Clause 28. The ethylenically unsaturated compound of one of clause 1 to clause 9, wherein the ethylenically unsaturated compound is represented by the structure (14):in which: (i) R3. G, G1, LN, m. n, and r are each as described above in clause 10 to clause 16; (ii) q has a value of 2 to 20, 2 to 5, or 2 or 3; (iii) Y2is as described above in clause 18 to clause 20; and L6is as described above in clause 26.

[0172] Clause 29. Tire ethylenically unsaturated compound of one of clause 1 to clause 9, wherein the ethylenically unsaturated compound is represented by the structure (15):in which: (i) R3, G, G1, LN, m, n, and r are each as described above in clause 10 to clause 16; (ii) q has a value of 2 to 20, 2 to 5, or 2 or 3; and (iii) Y2is as described above in clause 18 to clause 20; L7is as described above in clause 27.

[0173] Clause 30. The ethylenically unsaturated compound of one of clause 1 to clause 29, wherein the ethylenically unsaturated compound comprises a reaction product of reactants comprising or consisting of: (a) a polyisocyanate; (b) an active hydrogen-containing ethylenically unsaturated compound; (c) a compound comprising more than one active hydrogen atoms; and (d) polyaspartate amine.

[0174] Clause 31. Tire ethylenically unsaturated compound of clause 30, wherein the polyisocyanate (a) comprises include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, (hydrogenated) xylylene diisocyanate. 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3 '-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexylisocyanate),2,2,4-trimethylhexamethylene diisocyanate, 2,4,4 trimethyl hexamethylene diisocyanate, hexamethylene diisocyanate, 2,4- and / or 4,4'-methylenedicyclohexyl diisocyanate, methylene diphenyl diisocyanate, tetramethyl xylene diisocyanate, 1,5-pentane diisocyanate, bis(2-isocyanato-ethyl)fumarate, 6-isopropyl-1,3 -phenyl diisocyanate. 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, lysine isocyanate, a hexamethylene diisocyanate trimer, triphcii\imcthanc-4.4'.4"-trhsocyanatc. a hexamethylene diisocyanate trimcr. an aromatic polyisocyanate based on toluene diisocyanate, a polyisocyanurate of toluene diisocyanate, or a combination of any two or more thereof.

[0175] Clause 32. Tire ethylenically unsaturated compound of clause 30 or clause 31, wherein OCN — Z1— I— N( ()the polyisocyanate (a) has the structure:1l m 1 Jn, in which Z1. m and n are each as described above in clause 10 to clause 16.

[0176] Clause 33. Tire ethylenically unsaturated compound of one of clause 30 to clause 32, wherein the active hydrogen-containing ethylenically unsaturated compound (b) comprises an activehydrogen-containing (meth)acrylate of the structure:G and r are each as described above in clause 10 to clause 16.

[0177] Clause 34. The ethylenically unsaturated compound of one of clause 30 to clause 33, wherein the compound comprising more than one active hydrogen atoms (c) comprises a compound of f HG1— ] — zp— I— (i f l]the structure:1 Jm 1 J". in which G , Z , m and n are each as described above in clause 10 to clause 16.

[0178] Clause 35. The ethylenically unsaturated compound of one of clause 30 to clause 34, wherein the polyaspartate amine (d) is represented by the structure:ZA.— n in which R1, R2, ZA, m, and n are each as described above in clause 10 to clause 16.

[0179] Clause 36. Tire ethylenically unsaturated compound of clause 35, wherein the polyaspartate amine is a reaction product of a primary polyamine corresponding to the formula:(NH2)mZ3(NH2)n , in which Z3represents an organic group, in some cases a divalent organic group, that is inert tow ards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Ci g alkylene group or a Cs-Ce cycloalkylene group and m+n is an integer having a value of at least 2, such as 2 to 4, with a maleic or fumaric acid ester of the formula (with both isomers as represented bywavy bonds):, in w hich each R23, which may be the same or different, represents an organic groups that is inert towards isocyanate groups at temperatures of 100°C or less and each R24, which may be the same or different, represents hydrogen or an organic groups that is inert towards isocyanate groups at temperatures of 100°C or less.

[0180] Clause 37. Tire ethylenically unsaturated compound of clause 36, wherein the primary polyaminc comprises cthylcncdiaminc, 1,2-diaminopropanc, 1,3-diaminopropanc, 1,2-diaminobutanc, 1.3 -diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 2,5-diamino-2,5-dimethylhexane, 2.2,4-and / or 2,4,4-trimethyl-l,6-diaminohexane, 1,11 -diaminoundecane, 1,12-diaminododecane, bis-(3 -aminopropyl) ether, l,2-bis-(3-aminopropyloxy)ethane, l,3-bis-(3-aminopropyloxy)-2,2'-dimethylpropane, 1,2-bisaminocyclohexane, 1.3 -bisaminocyclohexane, 1,4-bisaminocyclohexane, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomcthylcyclohcxanc, 1,3-bisaminocthylcyclohcxanc, 1,4-bisaminocthylcyclohcxanc, 1,3-bisaminopropylcyclohexane, 1,4-bisaminopropylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, 1 -amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane, 2,4-and / or 2,6-hexahydrotoluylene diamine, 2,4'-and / or 4,4'-diamino-dicyclohexyl methane, 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methane, propane-1, 2, 3-triamine, pentane-l,3,5-triamine, benzene-l,3,5-triamine, isophoronediamine, menthanediamine, 1,4-bisaminopropylpiperazine. o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine. 2,6-tolylenediamine, 2.4-toluenediamine.2,4'-and / or 4,4'-diaminodiphenyl methane, m-aminobenzylamine, 4-chloro-o-phenylenediamine, tetrachloro-p-xylylenediamine, 4-methoxy-6-methyl-m -phenylenediamine, m-xylylenediamine, p-xylylenediamine, 1,5 -naphthalenediamine, 2,6-naphthalenediamine, benzidine, 4,4'-bis(o-toluidine), dianisidine, 4,4'-diaminodiphenylmethane, 2,2-(4,4'-diaminodiphenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-thiodianiline, 4.4'-diaminodiphenylsulfone. 4,4'-diaminoditolylsulfone. methylenebis(o-chloroaniline), 3,9-bis(3-aminopropyl) 2,4,8, 10-tetraoxaspiro[5.5]undecane. diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, l,4-bis(aminoethylpiperazine), 1,4-bis(aminopropylpiperazine), 2,6-diaminopyridine, and bis(3,4-diaminophenyl)sulfone, a polyether polyamine containing aliphatically bound primary amino groups, or a combinations of any two or more thereof.

[0181] Clause 38. The ethylenically unsaturated compound of clause 36 or clause 37, wherein the maleic or fumaric acid ester comprises a dimethyl, diethyl and / or di-n-butyl ester of maleic acid and / or fumaric acid, which are optionally substituted by methyl in the 2- and / or 3-position.

[0182] Clause 39. A method for making the ethylenically unsaturated compound of one of clause 1 to clause 38, comprising reacting (a) a polyisocyanate with (b) an active hydrogen-containing ethylenically unsaturated compound, (c) a compound comprising more than one active hydrogen atoms, and (d) a polyaspartate amine, optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising an aspartate group.

[0183] Clause 40. Tire method of clause 39, further comprising converting the aspartate group to a hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising a hydantoin group.

[0184] Clause 41. The method of clause 39 or clause 40. wherein the reacting is carried out in the presence of a catalyst comprising an organic metal catalyst, an amine catalyst, or a combination thereof, such as where the catalyst comprises a copper compound, such as copper naphthenate, a cobalt compound, such as cobalt naphthenate, a zinc compound, such as zinc naphthenate, a bismuth compound, such as bismuth ncodccanoatc, a tin compound, such as di-n-butyl tin dilauratc, tricthylaminc, triethylenediamine, DABCO, DMEA, or a combination of any two or more of the foregoing.

[0185] Clause 42. The method of one of clause 39 to clause 41, wherein the reacting takes place at atemperature of 10 to 120°C or 25 to 100°C.

[0186] Clause 43. Tire method of one of clause 39 to clause 42, wherein the reactants are employed in relative amounts to provide a molar ratio of isocyanate-reactive groups to isocyanate groups of at least 1:1, such as more than 1 to less than 1.5.

[0187] Clause 44. The method of clause 40, wherein the converting is carried out in the presence of a catalyst, such as a Bronsted acid, a carboxylic acid, a sulfonic acid, a phenol, or a mixture of any two or more thereof, at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, or 80 to 100°C.

[0188] Clause 45. Tire ethylenically unsaturated compound of one of clause 1 to clause 38, wherein the ethylenically unsaturated compound comprise a reaction product of reactants comprising or consisting of: (a) a polyisocyanate; (b) an isocyanate-containing ethylenically unsaturated compound: (c) a compound comprising more than one active hydrogen atoms: and (d) a polyaspartate amine.

[0189] Clause 46. Tire ethylenically unsaturated compound of clause 45, wherein the polyisocyanate (a) comprises any of the polyisocyanates identified in clause 31 or clause 32, the compound comprising more than one active hydrogen atoms (c) is as described in clause 34 and / or the polyaspartate amine (d) is as described in clause 35 to clause 38.

[0190] Clause 47. The ethylenically unsaturated compound of clause 45 or clause 46, wherein the isocyanate -containing ethylenically unsaturated compound is represented by the structure:in which R3, Y2and r are each as described above in clause 18 to clause 20.

[0191] Clause 48. The ethylenically unsaturated compound of one of clause 45 to clause 47. wherein the isocyanate-containing ethylenically unsaturated compound comprises isocyantoethyl methacrylate, isocyanatopropyl methacrylate, isocyanatobutyl methacrylate, isocyanatoethyl acrylate, isocyanatopropyl acr late, isocyanatobutyl acrylate, or a mixture of any two or more thereof.

[0192] Clause 49. Tire ethylenically unsaturated compound of one of clause 46 to clause 48, wherein the isocyanate-containing ethylenically unsaturated compound comprises a reaction product of reactants comprising: (i) a monohydroxy-substituted monofunctional or multifunctional (meth)acrylate, and (ii) a polyisocyanate, such as where the monohydroxy-substituted monofunctional and / ormultifunctional (meth)acrylates comprises 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl 2-chloro acrylate, 2-hydroxyethyl 2-ethylacrylate, 2-hydroxyethyl 2-propylacrylate, 2-hydroxyethyl 2 -butylacrylate, 3-hydroxypropyl methacrylate, 3 -hydroxypropyl -2-propylacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl 2-butylacrylate, 3-hydroxypropyl 2-bromo acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 3 -hydroxybutyl 2-ethylacrylate, 4-hydroxybutyl 2-butylacrylate, 2-hydroxybutyl 2-propylacrylate, 4- hydroxybutyl 2-chloro aery late, bis(methacryloyloxy)propanol, bis(acryloyloxy)propanol, pentaerythritol tnacry latc. or a combination of any two or more thereof, and the polyisocyanate comprises any of the polyisocyanates identified in clause 31.

[0193] Clause 50. A method for making the ethylenically unsaturated compound of one of clause 1 to clause 38 or clause 45 to clause 49, comprising reacting (a) a polyisocyanate and (b) an isocyanate-containing ethylenically unsaturated compound with (c) a compound comprising more than one active hydrogen atoms, and (d) a polyaspartate amine, optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising aspartate groups. In some implementations, the method further comprises converting one or more of the aspartate groups to a hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising a hydantoin group.

[0194] Clause 51. The method of clause 50, further comprising converting the aspartate group to a hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising a hydantoin group.

[0195] Clause 52. Tire method of clause 50 or clause 51, wherein the reacting is carried out in the presence of a catalyst comprising an organic metal catalyst, an amine catalyst, or a combination thereof, such as where the catalyst comprises a copper compound, such as copper naphthenate, a cobalt compound, such as cobalt naphthenate, a zinc compound, such as zinc naphthenate, a bismuth compound, such as bismuth neodecanoate, a tin compound, such as di-n-butyl tin dilaurate, triethylamine, triethylenediamine, DABCO, DMEA, or a combination of any two or more of the foregoing.

[0196] Clause 53. Tire method of one of clause 50 to clause 52, wherein the reacting takes place at a temperature of 10 to 120°C or 25 to 100°C.

[0197] Clause 54. The method of one of clause 50 to clause 53, wherein the reactants are employed in relative amounts to provide a molar ratio of isocyanate-reactive groups to isocyanate groups of at least 1:1, such as more than 1 to less than 1.5.

[0198] Clause 55. Tire method of clause 51, wherein the converting is carried out in the presence of a catalyst, such as a Bronstcd acid, a carboxy lic acid, a sulfonic acid, a phenol, or a mixture ofany two or more thereof, at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, or 80 to 100°C.

[0199] Clause 56. Tire ethylenically unsaturated compound of one of clause 1 to clause 38, wherein the ethy lenically unsaturated compound comprises a reaction product of reactants comprising or consisting of: (a) a polyisocyanate; (b) an active hydrogen-containing ethylenically unsaturated compound; (c) a compound comprising more than one active hydrogen atoms; and (d) an active hydrogen-containing aspartate.

[0200] Clause 57. Tire ethylenically unsaturated compound of clause 56, wherein the polyisocyanate (a) comprises any of the polyisocyanates identified in clause 31 or clause 32, the active hydrogen-containing ethylenically unsaturated compound (b) comprises an active hydrogen-containing ethylenically unsaturated compound as described in clause 33, and / or the compound comprising more than one active hydrogen atoms (c) comprises a compound comprising more than one active hydrogen atoms as described in clause 34.

[0201] Clause 58. Tire ethylenically unsaturated compound of clause 56 or clause 57, wherein the active hydrogen-containing aspartate is represented by the structure:n, in which G, Z3, R1, R2, m and n are each as described above in clause 22.

[0202] Clause 59. A method for making the ethylenically unsaturated compound of one of clause 1 to clause 38 or clause 56 to clause 58 comprising reacting (a) a polyisocyanate with (b) an active hydrogen-containing ethylenically unsaturated compound, (c) a compound comprising more than one active hydrogen atoms, and (d) an active hydrogen-containing aspartate, optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising an aspartate group.

[0203] Clause 60. Tire method of clause 59, further comprising converting at least some aspartate groups to a hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising a hydantoin group.

[0204] Clause 61. The method of clause 59 or clause 60. wherein the reacting is carried out in the presence of a catalyst comprising an organic metal catalyst, an amine catalyst, or a combinationthereof, such as where the catalyst comprises a copper compound, such as copper naphthenate, a cobalt compound, such as cobalt naphthenate, a zinc compound, such as zinc naphthenate, a bismuth compound, such as bismuth neodecanoate, a tin compound, such as di-n-butyl tin dilaurate, triethylamine, triethylenediamine, DABCO, DMEA, or a combination of any two or more of the foregoing.

[0205] Clause 62. The method of one of clause 59 to clause 61, wherein the reacting takes place at a temperature of 10 to 120°C or 25 to 100°C.

[0206] Clause 63. The method of one of clause 59 to clause 62, wherein the reactants are employed in relative amounts to provide a molar ratio of isocyanate-reactive groups to isocyanate groups of at least 1:1, such as more than 1 to less than 1.5.

[0207] Clause 64. Tire method of clause 60, wherein the converting is carried out in the presence of a catalyst, such as a Bronsted acid, a carboxylic acid, a sulfonic acid, a phenol, or a mixture of any two or more thereof, at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C. or 80 to 100°C.

[0208] Clause 65. Tire ethylenically unsaturated compound of one of clause 1 to clause 38, wherein the ethylenically unsaturated compound comprises a reaction product of reactants comprising or consisting of: (a) a polyisocyanate; (b) an isocyanate-containing ethylenically unsaturated compound; (c) a compound comprising more than one active hydrogen atoms; and (d) an active hydrogen-containing aspartate.

[0209] Clause 66. The ethylenically unsaturated compound of clause 65, wherein the polyisocyanate (a) comprises any of the polyisocyanates identified in clause 31 or clause 32, the isocyanate-containing ethylenically unsaturated compound (b) comprises any of the isocyanate-containing ethylenically unsaturated compounds described in clause 47 to clause 49, the compound comprising more than one active hydrogen atoms (c) comprises a compound comprising more than one active hydrogen atoms as described in clause 34. and / or the active hydrogen-containing aspartate (d) is as described in clause 58.

[0210] Clause 67. A method for making the ethylenically unsaturated compound of one of clause 1 to clause 38, clause 65 or clause 66 comprising reacting (a) a polyisocyanate and (b) an isocyanate-containing ethylenically unsaturated compound with (c) a compound comprising more than one active hydrogen atoms, and (d) an active hydrogen-containing aspartate, optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising an aspartate group.

[0211] Clause 68. The method of clause 67, further comprising converting at least some aspartate groups to a hydantoin group, wherein such conversion is carried out optionally in the presence of a cataly st, to produce an ethylenically unsaturated compound comprising a hydantoin group.

[0212] Clause 69. The method of clause 67 or clause 68, wherein the reacting is carried out in the presence of a catalyst comprising an organic metal catalyst, an amine catalyst, or a combination thereof, such as where the catalyst comprises a copper compound, such as copper naphthenate, a cobalt compound, such as cobalt naphthenate, a zinc compound, such as zinc naphthenate, a bismuth compound, such as bismuth neodecanoate, a tin compound, such as di-n-butyl tin dilaurate, triethylamine. triethylenediamine, DABCO, DMEA. or a combination of any two or more of the foregoing.

[0213] Clause 70. The method of one of clause 67 to clause 69, wherein the reacting takes place at a temperature of 10 to 120°C or 25 to 100°C.

[0214] Clause 719. The method of one of clause 67 to clause 70, wherein the reactants are employed in relative amounts to provide a molar ratio of isocyanate-reactive groups to isocyanate groups of at least 1:1, such as more than 1 to less than 1.5.

[0215] Clause 72. The method of clause 68, wherein the converting is carried out in the presence of a catalyst, such as a Bronsted acid, a carboxylic acid, a sulfonic acid, a phenol, or a mixture of any two or more thereof, at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, or 80 to 100°C.

[0216] Clause 73. The ethylenically unsaturated compounds of one of clause 1 to clause 38, wherein the ethylenically unsaturated compound comprises a reaction product of reactants comprising or consisting of: (a) a polyisocyanate; (b) an active-hydrogen-containing ethylenically unsaturated compound; (c) a compound comprising more than one active hydrogen atoms; (d) an active hydrogencontaining aspartate; and (e) a polyaspartate amine.

[0217] Clause 74. Tire ethylenically unsaturated compound of clause 73, wherein the polyisocyanate (a) comprises any of the polyisocyanates identified in clause 31 or clause 32, the active hydrogen-containing ethylenically unsaturated compound (b) comprises an active hydrogen-containing ethylenically unsaturated compound as described in clause 33. the compound comprising more than one active hydrogen atoms (c) comprises a compound comprising more than one active hydrogen atoms as described in clause 34, the active hydrogen-containing aspartate (d) is as described in clause 60, and / or the polyaspartate amine is as described in clause 35 to clause 38.

[0218] Clause 75. A method for making the ethylenically unsaturated compound of one of clause 1 to clause 38, clause 73 or clause 74 comprising reacting (a) a polyisocyanate with (b) an activehydrogen-containing ethylenically unsaturated compound, (c) a compound comprising more than one active hydrogen atoms, (d) an active hydrogen-containing aspartate, and (e) a polyaspartate amine, optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising an aspartate group.

[0219] Clause 76. The method of clause 75, further comprising converting at least some aspartate groups to a hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising a hydantoin group.

[0220] Clause 77. Tire method of clause 76 or clause 77, wherein the reacting is carried out in the presence of a catalyst comprising an organic metal catalyst, an amine catalyst, or a combination thereof, such as where the catalyst comprises a copper compound, such as copper naphthenate, a cobalt compound, such as cobalt naphthenate, a zinc compound, such as zinc naphthenate, a bismuth compound, such as bismuth neodecanoate, a tin compound, such as di-n-butyl tin dilaurate, triethylamine, triethylenediamine, DABCO, DMEA, or a combination of any tw o or more of the foregoing.

[0221] Clause 78. Tire method of one of clause 75 to clause 77, wherein the reacting takes place at a temperature of 10 to 120°C or 25 to 100°C.

[0222] Clause 79. The method of one of clause 75 to clause 78, wherein the reactants are employed in relative amounts to provide a molar ratio of isocyanate-reactive groups to isocyanate groups of at least 1:1, such as more than 1 to less than 1.5.

[0223] Clause 80. Tire method of clause 76, wherein the converting is carried out in the presence of a catalyst, such as a Bronsted acid, a carboxylic acid, a sulfonic acid, a phenol, or a mixture of any two or more thereof, at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, or 80 to 100°C.

[0224] Clause 81. The ethylenically unsaturated compound of one of clause 1 to clause 38, wherein the ethylenically unsaturated compound comprises a reaction product of reactants comprising or consisting of: (a) a polyisocyanate; (b) an isocyanate-containing ethylenically unsaturated compound; (c) a compound comprising more than one active hydrogen atoms; (d) an active hydrogen-containing aspartate; and (e) a polyaspartate amine.

[0225] Clause 82. The ethylenically unsaturated compound of clause 81, wherein polyisocyanate (a) comprises any of the polyisocyanates identified in clause 31 or clause 32, the isocyanate-containing ethylenically unsaturated compound (b) comprises an isocyanate-containing ethylenically unsaturated compounds described in clause 47 to clause 49, the compound comprising more than one active hydrogen atoms (c) comprises a compound comprising more than one active hydrogen atoms as described in clause 34, the active hydrogen-containing aspartate (d) is as described in clause 60, and / or the polyaspartate amine is as described in clause 35 to clause 38.

[0226] Clause 83. A method for making the ethylenically unsaturated compound of one of clause 1 to clause 38, clause 81 or clause 82 comprising reacting (a) a polyisocyanate and (b) an isocyanate-containing ethylenically unsaturated compound w ith (c) a compound comprising more than one active hydrogen atoms, (d) an active hydrogen-containing aspartate, and (e) a polyaspartate amine,optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising an aspartate group.

[0227] Clause 84. Tire method of clause 83, further comprising converting at least some aspartate groups to a hydantoin group, wherein such conversion is carried out optionally in the presence of a catalyst, to produce an ethylenically unsaturated compound comprising a hydantoin group.

[0228] Clause 85. The method of clause 83 or clause 84. wherein the reacting is carried out in the presence of a catalyst comprising an organic metal catalyst, an amine catalyst, or a combination thereof, such as where the catalyst comprises a copper compound, such as copper naphthenate, a cobalt compound, such as cobalt naphthenate, a zinc compound, such as zinc naphthenate, a bismuth compound, such as bismuth neodecanoate, a tin compound, such as di-n-butyl tin dilaurate, triethylamine, triethylenediamine, DABCO, DMEA, or a combination of any two or more of the foregoing.

[0229] Clause 86. The method of one of clause 83 to clause 85, wherein the reacting takes place at a temperature of 10 to 120°C or 25 to 100°C.

[0230] Clause 87. Tire method of one of clause 83 to clause 86, wherein the reactants are employed in relative amounts to provide a molar ratio of isocyanate-reactive groups to isocyanate groups of at least 1:1, such as more than 1 to less than 1.5.

[0231] Clause 88. The method of clause 84, wherein the converting is carried out in the presence of a catalyst, such as a Bronsted acid, a carboxylic acid, a sulfonic acid, a phenol, or a mixture of any two or more thereof, at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, or 80 to 100°C.

[0232] Clause 89. A composition, such as a radiation curable coating composition, comprising: (a) the ethylenically unsaturated compound of any one of clause 1 to clause 38, clause 45 to clause 49, clause 56 to clause 58. clause 65 to clause 66, clause 73 to clause 74, or clause 81 to clause 82, or an ethylenically unsaturated compound produced by the method of any of clause 39 to clause 44. clause 50 to clause 55, clause 59 to clause 64, clause 67 to clause 72, clause 75 to clause 80, or clause 83 to clause 88.

[0233] Clause 90. Tire composition of clause 89, wherein the composition further comprises an ethylenically unsaturated compound (b) that is different from ethylenically unsaturated compound (a), such as where ethylenically unsaturated compound (b) does not contain an aspartate group or a hydantoin group, wherein the sum of the amount of ethylenically unsaturated compound (a) and ethylenically unsaturated compound (b) is 1 to 99% by weight, 10 to 90% by weight, 20 to 50% by weight, 40 to 70% by weight, 60 to 80% by weight, 65 to 99% by weight, or 1 to 30 % by weight, based on the total weight of solids in the composition.

[0234] Clause 91. The composition of clause 89 or clause 90, wherein ethylenically unsaturated compound (a) is present in an amount of 1 to 99% by weight, 1 to 90% by weight, such as 10 to 90% by weight, 20 to 80% by weight, 30 to 70% by weight, or 40 to 60% by weight, based on the total weight of ethylenically unsaturated compound (a) and ethylenically unsaturated compound (b) in the composition.

[0235] Clause 92. The composition of one of clause 89 to clause 91, wherein tire ethylenically unsaturated compound (b) is an oligomer and has a number average molecular weight (Mn) , measured according to the procedure described in this specification, of 1000 g / mol to 35,000 g / mol, 1000 g / mol to 30,000 g / mol, 1000 g / mol to 25,000 g / mol, 1000 g / mol to 20,000 g / mol, 2,200 to 10,000 g / mol, or 2,200 to 5,500 g / mol.

[0236] Clause 93. Tire composition of one of clause 90 to clause 92, wherein the ethylenically unsaturated compound (b) comprises a urethane (meth)acrylate oligomer, comprising a (meth)acrylate group, a urethane group and a backbone, such as where the backbone is a reaction product of: ( 1 ) a polyol, such as a diol, (2) an isocyanate, such as a polyisocyanate, such as a diisocyanate, and (3) a hydroxyl group-containing (meth)acrylate.

[0237] Clause 94. Tire composition of clause 93, wherein the polyol comprises a polyether polyol, a polyester polyol, a polycarbonate polyol, a polycaprolactone polyol, an acrylic polyol, or a mixture of any two or more thereof, such as where the polyol comprises a polypropylene glycol.

[0238] Clause 95. The composition of clause 93 or clause 94, wherein the number average molecular weight derived from the hydroxyl number of the polyol is 50 to 15,000 g / mol or 1,000 to 8,000 g / mol.

[0239] Clause 96. Tire composition of one of clause 93 to clause 95 wherein the polyisocyanate used to prepare tire urethane acrylate oligomer comprises 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5 -naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4' -diphenylmethane diisocyanate, 3,3 '-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexylisocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis(2-isocyanato-ethyl)fumarate, 6-isopropyl-l,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, lysine isocyanate, a hexamethylene diisocyanate trimer, triphenylmethane-4,4',4"-triisocyanate, a hexamethylene diisocyanate trimer, an aromatic polyisocyanate based on toluene diisocyanate, polyisocyanurates of toluene diisocyanate, as well as combinations of any two or more thereof.

[0240] Clause 97. The composition of one of clause 93 to clause 96, wherein the hydroxyl group-containing (meth)acrylate used to prepare the urethane (meth)acrylate oligomer comprises a (meth)acrylate derived from (meth)acrylic acid and / or an epoxy (meth)acrylate comprising an alkylene oxide, such as 2-hydroxy ethyl(meth)acrylate, 2-hydroxypropylacrylate and 2-hydroxy-3-oxyphenyl(meth)acrylate .

[0241] Clause 98. The composition of one of clause 93 to clause 97. wherein the polyol, the polyisocyanate, and the hydroxyl group-containing (meth)acrylate used to prepare the urethane (meth)acrylate oligomer are used in relative amounts such that 0.1 to 0.9 equivalents of a hydroxyl group included in the hydroxyl group-containing (meth)acrylate and 1.0 to 1.5 equivalents of total hydroxyl groups present from the polyol and the hydroxyl group-containing (meth)acrylate are used for one equivalent of isocyanate group included in the polyisocyanate.

[0242] Clause 99. The composition of one of clause 89 to clause 98. wherein the composition further comprises a reactive diluent compound (c) comprising one or more ethylenically unsaturated groups.

[0243] Clause 100. The composition of clause 99, wherein the reactive diluent (c) comprises one double bond, such as an alkyl or hydroxyalkyl (meth)acrylate, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, isobomyl (meth)acrylate, lauryl (meth)acrylate, ethoxylated nonyl-phenol (meth)acrylate. phenoxyethyl (meth)acrylate, diethylene-glycol-ethyl-hexyl acylate (DEGEHA), caprolactone (meth)acrylate, polyglycol (meth)acrylate, acrylonitrile, acrylamide, methacrylamide, an N-substituted (meth)acrylamide, a vinyl ester (such as vinyl acetate), styrene, an alkylstyrene, a halostyrene, a N-vinylpyrrolidone, a N-vinyl caprolactam, a vinyl chloride, a vinylidene chloride, or a mixture of any two or more thereof.

[0244] Clause 101. The composition of clause 99 or clause 100, wherein the reactive diluent (c) comprises more than one double bond, such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexamethylene glycol di(mcth)acrylatc. bisphenol A di(meth)acrylate, 4.4'-bis(2-acryloyloxycthoxy)diphenylpropanc. trimethylolpropane tri(meth)acrylate, pentaerythritol tri (meth)acry late, pentaerythritol tetra(meth)acrylate, vinyl (meth)acrylate, divinyl benzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, tris(2-acryloylethyl)isocyanurate, or a mixture of any two or more thereof.

[0245] Clause 102. The composition of any one of clause 99 to clause 101, wherein the reactive diluent (c) is present in an amount of 5 to 90% by weight, 10 to 90% by weight, 10 to 80% by weight, or, in some cases, 10 to 60% by weight, 10 to 40% by weight, or 10 to 30% by weight, based on the total weight of solids in the composition.

[0246] Clause 103. The composition of any one of clause 90 to clause 102, wherein the composition further comprises a photoinitiator (d).

[0247] Clause 104. The composition of clause 103, wherein the photoinitiator (d) comprises an acylphosphine oxide, such as a bisacylphosphine oxide (BAPO) and / or a monoacylphosphine oxide (MAPO), an a-hydroxy ketone, or a mixture of any two or more thereof.

[0248] Clause 105. The composition of clause 103, wherein the photoinitiator (d) comprises a bisacylphosphine oxide having the structure:in which R5Q is CI -CI 2 alkyl, cyclohcxyl or phenyl, which is unsubstituted or is substituted by 1 to 4 halogen atoms, or Ci-Cs alkyl: R51 and R52 are each independently of the other Ci-Cs alkyl or Ci-Cs alkoxy; R53 is hydrogen or Ci-Cs alkyl; and R54 is hydrogen or methyl, such as where the bisacylphosphine oxide comprises bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-(2,4-bis-pentyloxyphenyl)phosphine oxide, or a mixture thereof.

[0249] Clause 106. The composition of one of clause 103 to clause 105, wherein the photoinitiator (d) is present in an amount of 0.1 to 10% by weight, such as 0.1 to 5% by weight, or, in some cases, 1 to 5 % by weight, based on the total weight of the radiation curable composition.

[0250] Clause 107. The composition of one of clause 89 to clause 106, wherein the composition further comprises (e) a silane-containing adhesion promoter.

[0251] Clause 108. The composition of one of clause 89 to clause 107, wherein the composition has a total silane content (determined as described in the Examples section of this specification) of up to 10 mmol, such as 1 to 10 mmol, 1 to 8 mmol, or, in some cases 2 to 6 mmol, per 100 gram of the radiation curable composition and / or the composition has a total content of urea+urethane (determined as described in the Examples section of this specification) of 20 to 200 mmol, such as 30 to 150 mmol, or. in some cases 40 to 100 mmol, per 100 gram of the composition.

[0252] Clause 109. The composition of one of clause 89 to claim 108, wherein the composition further comprises an additive that comprises a photo sensitizer, a radiation cure amine synergist, a UV absorber, an antioxidant, a UV stabilizer, a thermo stabilizer, a filler material, a train transfer thiolcompound, a surface active compound, a viscosity modifier, an additional addition promoter, a water scavenger, such as TEOS and orthoformate, an oxygen quencher or a functional material, such as pigments, dyes, photochromic dyes, laser dyes, liquid cr stals, light emitting materials, nano materials, quantum dots, fluorescent materials, dichroic dyes, antistatic materials, refractive index modifier and bioactive materials.

[0253] Clause 110. The composition of one of clause 89 to clause 109, wherein the composition further comprises organic solvent.

[0254] Clause 111. The composition of one of clause 89 to clause 110, wherein the composition has a viscosity of >0.1 Pascal seconds (Pa- s), at least 0.2, at least 0.5, at least 1 Pa- s, and / or less than 15 Pa s, less than 12 Pa-s, or less than 10 Pa s, or 1 to 15 Pa s, 2 to 12 Pa s, or 3 to 10 Pa s. wherein viscosity is measured at 25 °C and a shear rate of 50 s-1.

[0255] Clause 112. A cured coating formed from the composition of one of clause 89 to clause 111.

[0256] Clause 113. A substrate at least partially coated with a cured coating of clause 112, such as where the substrate comprises an optical fiber.

[0257] Clause 114. Hie substrate of clause 113, further comprising a secondary- coating in contact with and surrounding the cured coating and, optionally, an ink layer disposed on the secondary coating.

[0258] Clause 115. The substrate of clause 113 or clause 114, wherein the cured coating has a in-situ modulus less than 5 MPa, less than 2 MPa, less than 1.5 MPa, or less than 1.0 MPa.

[0259] Clause 116. The substrate of any one of clause 113 to clause 115, wherein the cured coating exhibits a peel strength at least 40 gram-force / inch ("gf / in"). at least 55 gf / in, at least 70 gf / in, at least, at least 80 gf / in, at least 100 gf / in, at least 150 gf / in, or at least 200 gf / in, in each case optionally up to 300 gf / in. when measured as described in the Examples section of this specification.

[0260] Clause 117. The substrate of any one of clause 113 to clause 116, wherein the cured coating exhibits an elongation at break of at least 35%, such as at least 50%, at least 80%, or at least 100%, in each case optionally up to 200%, up to 150%, or up to 120%, when measured as described in the Examples section of this specification.

[0261] Clause 118. A method for coating an optical fiber comprising: (a) providing a glass optical fiber, such as by drawing a glass optical fiber through a draw tower: (b) applying a primary coating composition onto the surface of the glass optical fiber; (c) optionally, imparting a dose of UV light sufficient to at least partially cure said primary coating composition; (d) applying a secondary coating composition to the primary coating composition; (c) exposing the secondary coating composition to at least one radiation source capable of emitting ultraviolet radiation to affect curing of said secondarycoating composition and, optionally said primary coating composition, wherein the primary coating composition and / or the secondary coating composition comprises a composition of any one of clause 89 to clause 111.

[0262] Clause 119. A coated optical fiber comprising: (a) a glass core and a cladding layer in contact with and surrounding said glass core; and (b) a coating portion at least partially coating the cladding layer, the coating portion comprising: (i) a primary coating layer in contact with said cladding layer; and (ii) a secondary coating layer in contact with and surrounding said primary coating layer, wherein the primary coating layer and / or the secondary coating layer is a cured product of a composition of any one of clause 89 to clause 111.

[0263] Clause 120. Tire coated optical fiber of clause 119, wherein the core comprises pure silica glass (SiCh) or silica glass with one or more dopants, such as where the dopants comprise GeCh, AI2O3. P2O5. TiC>2, ZrCh, NbiOs, Ta^Cri. or a combination of any two or more thereof.

[0264] Clause 121. The method of clause 118 or the coated optical fiber of clause 119 or clause 120, wherein the cured primary coating has a glass transition temperature of less than -10°C, -35°C, less than -40°C, less than -45°C, and more than -100°C , and / or the cured primary coating has a thickness of 20 to 50 pm, 20 to 40 pm, 20 to 30 pm, 25 or 32.5 pm, or 15 to 25 pm.

[0265] Clause 122. The method of clause 118 or clause 121 or the coated optical fiber of one of clause 119 to clause 121, wherein the secondary coating exhibits an in-situ modulus of greater than 800 MPa, greater than 1110 MPa, greater than 1300 MPa, greater than 1400 MPa, or greater than 1500 MPa, 1000 MPa to 8000 MPa, 1200 MPa to 5000 MPa, or 1500 MPa to 3000 MPa, and / or an in-situ Tg of 50°C to 120°C or 50°C to 100°C, and / or a thickness of no more than 40 pm, 20 to 40 pm, or 20 to 30 pm.

[0266] Clause 123. The coated optical fiber of one of clause 119 to clause 122, wherein the coated optical fiber possesses a mode-field diameter from 8 to 10 pm at a wavelength of 1310 nm, a mode-field diameter from 9 to 13 pm at a wavelength of 1550 nm, and / or an effective area of 20 to 200 2

[0267] Clause 124. The coated optical fiber of one of clause 119 to clause 123, wherein the secondary coating may also include an ink to become a colored secondary coating.

[0268] Clause 125. Hie coated optical fiber of one of clause 119 to clause 124, wherein the coated optical fiber comprises one or more additional layers disposed on the secondary layer, such as a standalone "ink" layer which is applied and cured separately from the secondary coating.

[0269] The non-limiting and non-exhaustive examples that follow are intended to further describe various non-limiting and non-exhaustive implementations without restricting the scope of the implementations described in this specification.EXAMPLESTable 1: Materials UsedSupplier / Component Chemical Descriptor Trade nameManufacturer DBTDL Dibutyltin Dilaurate DABCO T-12 EVONIK BUT Butylated hydroxytoluene Acres TDI 2,4-diisocyanato- 1 -methyl -benzene DESMODURT 100 SP Covestro ACCLAIM POLYOL PPG 4000 Polypropylene glycol 4200 Covestro PPG 2000 Polypropylene glycol Desmophen 2061 BD Covestro NH-1423LF Polyaspartic Desmophen NH-1423LF Covestro NH-1523LF Polyaspartic Desmophen NH-1523LF Covestro HEA 2-Hydroxyethyl acrylate BASF IPDA Isophorone diamine Sigma-Aldrich Diethyl maleate Diethyl maleate Acres PEA 2-Propcnoic acid, 2-phcnoxycthyl ester AgiSyn 2832 Covestro ENPA Ethoxylated (4) nonyl phenol acrylate AgiSyn 2895 Covestro 2-mcthyl-4,6- Antioxidant 1520 Irganox 1520 BASF bis(octylsulfanylmethvl)phenolAcrylic acid Acrylic acid Sigma-Aldrich Diphenyl(2,4,6- TPO Omnirad TPO IGMtrimethylbenzoyl)phosphine oxide

[0270] Many materials used herein were made resulting in a mixture having a statistical distribution of molecular weight that can be easily recognized by those skilled in the art. The structures in this section, and elsewhere herein, only show the designed averaged, or "ideal" structure, unless otherwise noted.Example 1: Synthesis of NH-IPDA (Polvaspartic precursor)

[0271] IPDA (738g, 4.3 mol) was added to a four-necked flask (5000 mL). purged with dry air, and cooled to 10°C using an ice bath. Diethyl maleate (1500g, 8.7 mol) was then added dropwise, keeping the mixture below 15°C. Upon addition the mixture was stirred for 4 hours and allowed to warm up to 20-25 °C to yield the final product mixture comprising a compound of structure (A) as a viscous liquid. The product was then available to be used in subsequent formulation without further purification. The structure (A) appears below:•O'.0.(A)Example 2: Synthesis of Oligomer QE-01

[0272] To create Oligomer OE-01, amixture of PPG 4000 (3474g, 0.9 mol), TDI (313g, 1.8 mol), and BHT (4g, 1000 ppm) was placed in a four-necked flask (5000 ml) and purged with dry air. The resulting mixture was then stirred at 20-25°C for 15 mins before the addition of DBTDL (1.6g, 400 ppm). Hie resulting mixture was then stirred without external heat for 15 minutes, then stirred at 60°C for 1-2 hours. HEA (208g, 1.8 mol) was then added to the reaction mixture. While still under the purge of dry¬ air, the reaction mixture was stirred at 85°C for another 1 to 2 hours to yield the final product mixture comprising a compound of structure (B) as a viscous liquid. The product was then available to be used in subsequent formulation without further purification. The structure (B) is shown below:Example 3: Synthesis of Oligomer QE-02

[0273] To create Oligomer OE-02, amixture of PPG 4000 (74.3 kg, 19.1 mol). HEA (2.2 kg, 19.1 mol), BHT (80g, 1000 ppm), acrylic acid (40g, 0.56 mol), TDI (3.3 kg, 19.1 mol), and DBTDL (64g, 800 ppm) were added sequentially to a batch reactor (180 L). The resulting mixture was then stirred at 70°C for 2 to 4 hours to yield the final product mixture comprising a compound having the structure (C) as a viscous liquid. Tire product was then available to be used in subsequent formulation without further purification. Tire structure (C) is shown below:PPG 4000(OExample 4: Synthesis of Oligomer QE-03

[0274] To create Oligomer OE-03, amixture of TDI (6.94g, 0.04 mol) and BHT (0.10g, lOOOppm) was placed in a four-necked flask (250 ml) and then purged with a gaseous mixture consistingof air and nitrogen in a 3: 1 ratio by volume. The resulting mixture was then stirred at 20-25 °C for 10 mins before the addition of mixture of DBTDL (0.03g, 300 ppm), HEA (2.31g, 0.02 mol), and PPG 4000 (23.91g, 0.01 mol). The resulting mixture was then stirred at 60°C for 1-2 hours. Then, amixture of DBTDL (0.03g, 300 ppm), Desmophen NH-1423LF (10.92g, 0.02 mol) and PPG 4000 (55.79g, 0.01 mol) was added dropwise. While still under the purge of the 3:1 air / nitrogen mixture, the reaction mixture was further stirred at 85°C for another 2 hours to yield the final product mixture comprising a compound having the structure (D) as a viscous liquid. The product was then available to be used in subsequent formulation without further purification. The structure (D) is shown below:Example 5: Synthesis of Oligomer QE-04

[0275] To create Oligomer OE-04, a mixture of TDI (36.0g, 0.20 mol) and BHT (0.5g, lOOOppm) was placed in a four-necked flask (1000 ml) and then purged with a gaseous mixture consisting of air and nitrogen in a 3 : 1 ratio by volume. The resulting mixture was then stirred at 20-25 °C for 10 mins before the addition of mixture of DBTDL (0.15g, 300 ppm). EIEA (12.0g, 0.10 mol), and PPG 4000 (119.9g. 0.03mol). The resulting mixture was then stirred at 60°C for 1-2 hours. Then, a mixture of DBTDL (0.15g, 300 ppm), NH-IPDA (16.9g, 0.10 mol) and PPG 4000 (279.7g, 0.07 mol) was added dropwise. While still under the purge of the 3:1 air / nitrogen mixture, the reaction mixture was further stirred at 85°C for another 2 hours to yield the final product mixture comprising a compound having the structure (E) as a viscous liquid. Tire product was then available to be used in subsequent formulation without further purification. The structure (E) is shown below:(E)Example 6: Synthesis of Oligomer QE-05

[0276] To create Oligomer OE-05, a mixture of TDI (32.2g, 0.20 mol) and BHT (0.30g, lOOOppm) was placed in a four-necked flask (500 ml) and then purged with a dry air. Tire resulting mixture was then stirred at 20-25°C for 10 mins before the addition of mixture of DBTDL (0.09g, 300 ppm), HEA (11.4g, 0.10 mol), and PPG 2000 (59.0g, 0.03 mol), lire resulting mixture was then stirred at 60°C for 1-2 hours. Then, amixture of DBTDL (0.09g, 300 ppm). Desmophen NH-1523LF (57.3g. 0.10 mol) and PPG 2000 (137.6g, 0.07 mol) was added dropwise. While still under the purge of dry air, the reaction mixture was further stirred at 85°C for another 4-6 hours to yield the final product mixture comprising a compound having the structure (F) as a viscous liquid. The product was then available to be used in subsequent formulation without further purification. The structure (F) is shown below:Example 7: Synthesis of Oligomer QE-06

[0277] To create Oligomer OE-06. Oligomer OE-03 (200 g) was placed in a four-necked flask (500 ml) and then purged with a gaseous mixture consisting of air and nitrogen in a 3: 1 ratio by volume. The resulting mixture was then heated to 70-80°C before the addition of acrylic acid (2g, 1%). The resulting mixture was then stirred at 85°C for 8 hours to yield the final product mixture with an average structure (G) as a viscous liquid. The product was then available to be used in subsequent formulation without further purification. The structure (G) appears below:OH PPG-2000(G)Example 8: Synthesis of Oligomer OE-07

[0278] To create Oligomer OE-07, amixture of TDI (15.7g, 0.09 mol) and BHT (0.10g, lOOOppm) was placed in a four-necked flask (250 ml) and then purged with a gaseous mixture consisting of air and nitrogen in a 3 : 1 ratio by volume. The resulting mixture was then stirred at 20-25 °C for 10 mins before the addition of mixture of DBTDL (0.03g, 300 ppm). HEA (6.99g, 0.06 mol) and PPG 2000 (60.24g. 0.03 mol). The resulting mixture was then stirred at 60 °C for 1-2 hours. Then. DBTDL (0.03g, 300 ppm)and Desmophen NH-1523LF (16.87g, 0.03 mol) were each added sequentially. While still under the purge of the 3:1 air / nitrogen mixture, the reaction mixture was further stirred at 85°C for another 5-18 hours to yield the final product mixture comprising a compound having the structure (H) as a viscous liquid. The product was then available to be used in subsequent formulation without further purification. The structure (G) is shown below:

[0279] Compositions and test results are included in following Tables. Synthesized oligomers are presented as Oligomers OE-Ol to OE-07. Formulated oligomer mixtures were obtained by mixing of multiple synthesized oligomers and are presented as oligomer mixtures OME-Ol to OME-9. UV curable formulations that contain oligomers are presented in Formulation Examples FE-01 to FE-10.

[0280] Table 2 shows synthesized oligomer raw material compositions, and include non- aspartate-non-hydantoin urethane acrylate Oligomers OE-Ol to OE-02, aspartate Oligomers OE-03, OE- 04, OE-05 and OE-07, and hydantoin Oligomers OE-06. Tables 3A-3B show oligomer mixtures OME-1 to OME-9, which were formulated using the oligomers from Table 2. Tables 4A-4B show raw material compositions for oligomer mixtures OME-1 to OME-9 as a result of adding raw materials from each oligomer component used for making oligomer mixture OME-1 to OME-09. Tables 6A-6B show UV curable formulations FE-01 to FE-10, which were formulated using oligomer mixtures OME-Ol to OME- 09.Table 2: Inventive Oligomer Examples Mole RatiosOligomer OE-Ol OE-02 OE-03 OE-04 OE-05 OE-06 OE-07 TDI 1 1 2 2 2 2 3 PPG 4000 1 1 1 1 — 1 — PPG 2000 — — — — 1 — 1NH-1423LF — — 1 — — 1 —NH-1523LF — — — — 1 — 1 NH-IPDA — — — 1 — — —HEA 1 1 1 1 1 1 2Table 3A: Oligomer Mixture Examples wt%OME-Ol OME-02 OME-03 OME-04 OME-05OE-Ol 100 50 50 50 50OE-02 — 50 — — —OE-03 — — 50 — —OE-04 — — — 50 —OE-06 — — — — 50Table 3B: Oligomer Mixture Examples wt%OME-06 OME-07 OME-08 OME-09OE-01 45 45 — —OE-05 — 55 — 55OE-07 55 — 100 45Table 4A: Oligomer Mixture Examples Mole RatiosOME-01 OME-02 OME-03 OME-04 OME-05HEA 2 2 2 2 2PPG 4000 1.00 1.35 1.31 1.31 1.31NH1423 — — 0.62 — 0.62NH-IPDA — — — 0.61 —TDI 2 2 2.62 2.63 2.62Table 4B: Oligomer Mixture Examples Mole RatiosOME-06 OME-07 OME-08 OME-09HEA 2 2 2 2PPG 2000 1.00 1.47 1.00 1.40NH1523 0.62 0.93 1.00 1.40TDI 2.62 2.93 3.00 3.40Formulation Examples FE-01 to FE-10

[0281] Each of the formulations FE-01 to FE-10 described in Tables 6A-6B (amounts are in parts by weight unless otherwise indicated) was prepared by mixing a 100g sample in a 100 ml mixing cup suitable for use with a SpeedMixer™. Specifically, the oligomer and monomer components, not including the inventive ethylenically unsaturated compound, were mixed in addition to the other components as specified in Tables 6A-6B below. Upon addition to the cup. the cup was closed and mixed in a SpeedMixer ™ DAC150FVZ at 3000 RPM for 3 minutes. After this, the mixing operation was stopped, and the resulting mixture was transferred to a suitable receptacle and then heated to 60°C in an oven and maintained at this temperature for about 6 hours to ensure complete dissolution of all components. Tire sample was then removed from the oven and mixed again for three additional minutes in the SpeedMixer again via the same method, after which the inventive ethylenically unsaturated compound was added, resulting in 100 g total. Finally, the mixture was mixed again for an additional 3 minutes in the SpeedMixer again via the same method.

[0282] These formulations were next characterized according to their respective total urea + urethane content per the methodology described below. Then, all fonnulations were tested according to the methods described below to determine their peel strength, elongation percentage, film modulus, toughness, tensile strength, and viscosity. Unless otherwise shown, values for the urea + urethane content are rounded to the nearest whole number. Film modulus, toughness, and tensile strength values, meanwhile, have been rounded to two decimal places. Viscosity is presented to the nearest one centipoise unit. Finally, elongation percentage values are presented as rounded to the nearest 1%. Values for each of these measured characteristics are reported in Tables 6A-6B below.

[0283] The "Urea + urethane content" (Y) for a given composition was determined by counting the total isocyanate groups present in the composition, represented by:y N^ Wt^L-L MW.-i = lwhere Wt, = mass of isocyanate (i) relative to 100g of the total associated composition; N, = functionality of isocyanate (i); and MW! is the theoretical molecular mass of isocyanate (i) (in g / mol). The urea + urethane content is reported in units of mmol / lOOg. The values for urea + urethane content may be optionally expresses in units of mol / 100g by dividing the summed value by 1000, although unless specifically noted, the values herein arc not reported in this fashion. For clarity, where "equivalents" or "milliequivalents" is specified herein, unless otherwise noted, the value is to be interpreted in reference to 100g of the composition with which it is associated. Urea + urethane content values for each formulation are presented in Table 6A-6B below.

[0284] It should be noted that if the complete recipe of a composition is not known ex ante, the equivalents of isocyanate moieties may be determined analytically via any suitable method as will be appreciated by the skilled artisan to which this invention applies, such as nuclear magnetic resonance (NMR).

[0285] Viscosity was measured using Anton Paar Rheolab QC. The instrument w as set up for the Z3 and Z4 system, both of which were used. Samples for using the Z3 system were weighed out in the amount of 14.7g ± 0.2g and loaded into a disposable aluminum cup, while those for the Z4 system had a mass of 3.5g ± 0.2g. The sample in the cup was examined and if upon visual inspection it was determined to contain bubbles, the sample and cup w ere either subjected to centrifugation or allowed to sit long enough so that the bubbles w ould escape from the bulk of the liquid. Bubbles appearing at the top surface of the liquid were considered to be acceptable. Next, the bob was gently loaded into the liquid in the measuring cup, after which the cup and bob were installed in the instrument. Viscosities were run at 25°C ± 0.1°C and 55°C ± 0.1°C with a five-minute equilibration period to ensure the temperature was constant and at a shear rate of 50 sec1. Ten readings at each temperature were recorded and the reported results represent the average viscosity values of ten different readings. Tire values were recorded as expressed in millipascal seconds (mPa s) and a shear rate of 50 s1unless otherwise specified.

[0286] To create films such that various physical properties could be tested, each sample w as cured under a constant flow of nitrogen gas with a 1 J / cm2UV-dose of Conveyor Fusion Unit Model DRS-10 / 12 QN, 600W UV-lamp system having as lamps 1600M radiator (600 W / inch which equals 240 W / cm, and thus, in total 600 W) fitted with R500 reflector, one with a H bulb and one with a D bulb UV lamp, of w hich the D-bulb w as used to cure the samples. The UV-dose w as then measured with an International Fight IU390 radiometer. Then, individual test strips having a width of approximately 1.27 cm (0.5 inches ±1 / 32"’) and a length of approximately 12.7 cm (5 inches ± 1 / 8”) were then cut from the film. The exact thickness of each specimen was measured with a calibrated micrometer.

[0287] The method for determining film modulus as used herein is adapted from EP2089333B 1, paragraphs

[0132] -

[0133] and

[0135] , The tensile properties (tensile strength, percent elongation at break, and segment modulus) were determined with an MTS Criterion ™ Model 43.104 with respect to test strips of a cured film of each sample having a 3-mil thickness as prepared per the ‘‘Film Sample Preparation” procedure described above. Due to these relatively soft coatings (e.g., those with a modulus of less than about 10 MPa), the coating was drawn down and cured on a glass plate and the individual specimens cut from the glass plate with a scalpel after applying a thin layer of talc. A 0.9 kg (2-lb) load cell was used in an Instron 4442 Tensile Tester, and the modulus was calculated at 2.5% elongation with a least-squares fit of the strcss-strain plot. Cured films were conditioned at 23.0°C ± 0.1 °C and 50.0% ± 0.5% relative humidity for 16 to 24 hours prior to testing. For testing specimens, the gage length was 5.1cm (2-inches), and the crosshead speed was 25.4 mm / min. All testing was performed at a temperature of 23.0°C ± 0.1°C and a relative humidity of 50.0% ± 0.5%. All measurements were determined from the average of at least six test specimens. Values for tensile strength were determined as the highest stress bom by the sample before break. Values for toughness were determined as the total area under the stressstrain curve.

[0288] Adhesive properties were determined with an Instron Tensile Tester Model 4442 using test strips of a cured film of each sample having a 3-mil thickness as prepared per the '‘Film Sample Preparation” procedure described above. Cured films were then conditioned for a minimum of 7 days at 23.0°C ± 2.0°C and 50% ± 5% RH. When peel strength results were too high and untestable after 7 days, new samples were prepared and conditioned for 24 hours at 23.0°C ± 2.0°C and 50% ± 5% RH. Test samples were then cut using a scalpel and 1.00” wide steel bar, placing a 6” cut on either side of the bar with a ! ” gap between cut specimens. To minimize the effects of minor sample defects, sample specimens are cut parallel to the direction in which the drawdown of the cured film was prepared. A thin layer of talc was applied using a cotton-tipped applicator to the first and third strips on each drawdown to reduce blocking during the adhesion test. Tire Instron Tensile Tester Model 4442 was setup with a 21b load cell, 20 psi pneumatic grips, and lO.OO'Vmin crosshead speed fortesting. A clip attached to braided nylon string was run through a pulley with the nylon string clamped into the upper jaw of the Instron testing instrument. The first strip was peeled back from the glass plate about one inch and place horizontally on the table with the peeled-back end of the specimen facing away from the pulley. The binder clip was attached to the peeled-back end of the specimen and allowed to lay flat on the sample. Tire plate was pulled to put tension on the braided nylon string until the load on the Instron reads positive, at which point the software method was started and continued until the average force value became relatively constant. The test is terminated by clicking on the stop button in the software or loosening the tension on the string. Reported peel strength values are the average of the plateau force for eight samples run.

[0289] Size Exclusion Chromatography measurements were performed using Waters GPC (Gel Permeation Chromatography) system with refractive index (RI) detector, a photodiode array detector. For chromatographic separation, chromatographic Size Exclusion columns: 3 x 7.8 mm x 300 mm TSK-GEL MULTIPORE HXL-M, 5 m, TosoHaas or equivalent, were used. Detectors and columns were operated at 40° C. Polystyrene molecular weight standards were used to establish a calibration curve. Prior to conducting SEC, each respective polymer and polystyrene molecular weight standards were dissolved at a concentration ranging from 0.5 to 10 mg / ml in high purity grade tetrahydrofuran (THF) containing BHT stabilizer. This THF solution was also used as an eluent in SEC analysis at a flow rate of 1.0 ml / min.

[0290] With the dissolution complete, the relative molar mass and molar mass distribution were then determined with the above-referenced detection method using the refractive index and absorbance. A calibration curve was generated with a series of polystyrene standards assigning each data slice a molecular weight. With the curve, the relative molar mass and distribution could be obtained. The calibration curve, molecular mass averages, and the molar mass distributions were detennined by integration of the whole refractive index chromatograms.

[0291] Using the above-prescribed method, values Mn, Mw, and Mz were recorded and reported.Table 5 : Molecular weight values for selected inventive oligomersOE-03 OE-05Mn (g / mol) 4225 2656 Mw (g / mol) 8811 9126 Mz (g / mol) 15134 16704PDI 2.08 3.44

[0292] In many of the formulations studied and compared in fonnulation examples, inventive oligomers were used to replace at least partially oligomers being compared with. The oligomers being replaced comprised well-known non-aspartate non-hydantoin difunctional oligomers, monofunctional oligomers, or aspartate / hydantoin difunctional oligomers.

[0293] For optical fiber primary coating, formulation tools for improving properties such as lower viscosity, increased peel strength, increased elongation at break, lower film modulus, increased toughness, increased tensile strength are always desired by formulators. Improvement in some properties often hurts performance in some other properties. Two examples are shown in Table 6A and 6B. In table 6A, the two controls FE-01 and FE-02 did not include any inventive oligomer. To reduce viscosity and reduce film modulus, some difiinctional oligomer OE-01 in FE-01 control was partially replaced by a monofunctional oligomer OE-2 in FE-02 control. The change from difiinctional oligomer to monofunctional oligomer led to reduced viscosity and reduced film modulus, which are all good performance adjustment. However, the change also led to lower peel strength and lower toughness.

[0294] In table 6B for the three control examples, FE-07 and FE-09 had OE-01 in FE-06 partially or totally replaced by OE-07. The change led to desired properties of very high level of peel strength improvement and reduced modulus without sacrificing much of toughness. However, viscosity increased significantly.

[0295] One of the biggest challenges for optical fiber coating is to find the most desired balance of overall coating performances. The unbalance in overall coating performance improvement isformulation dependent. While there is existing formulation know-how that can be considered for balancing properties, new tools are always needed for easier and more efficient balancing of all coating properties.

[0296] Tire newly designed inventive oligomers offer more balanced performance improvement than aspartate and / or hydantoin multifunctional oligomers like OE-07 and non-aspartate non-hydantoin monofunctional hydroxyl containing oligomers like OE-02.

[0297] In table 6A, OE-Ol in FE-01 control was replaced with OE-02 in FE-02, which was used as the second control. OE-Ol in FE-01 control was also replaced by OE-03, OE-04 and OE-06 in inventive formulations FE-03, FE-04 and FE-05. Tire second control FE-02 did not include aspartate in the formulation, but included a hydroxyl monofunctional oligomer OE-02 that had one less acrylate functionality and only 6% lower theoretical molecular weight than OE-01. This tool of partial replacement of oligomer from OE-01 to OE-02 provided a formulation tool for lowering viscosity and modulus, but the new formulation FE-02 control suffered from lower peel strength and lower toughness. Compared with control FE-02, inventive formulations FE-03, FE-04 and FE-05 also had hydroxyl monofunctional oligomers, which additionally comprised an aspartate component in OE-03 and OE-04 and a hydantoin component in OE-06. The inventive oligomers OE-03 and OE-04 had a theoretical molecular weight 9-10% more than control OE-Ol. OE-06 had a theoretical molecular weight 36% less than control OE-01. Surprisingly, having the three new inventive oligomers with different structures and different theoretical molecular weight variations to control oligomer, all three new inventive formulation FE-03, FE-04 and FE-05 demonstrated unexpected overall improvements, including 22-47% lower viscosity, 5-60% lower modulus without sacrificing toughness, 173-517% increased peel strength, and 52-79% improved elongation, relative to FE-01. Hie tensile strength decreased as a result of modulus decrease, but the toughness was not sacrificed with the significant improvement in elongation. The overall performance improvement was much more balanced than FE-02 although the viscosity decrease was not as significant.Table 6A: Inventive oligomer screening, replacing oligomer OE-Ol of OME-Ol or OE-02 of OME-02 control with OE-03, OE-04, and OE-06FE-01* FE-02* FE-03 FE-04 FE-05 OE-Ol 60 30 30 30 30 OE-02 — 30 — — — OE-03 — — 30 — — OE-04 — — — 30 — OE-06 — — — — 30PEA 37.5 37.5 37.5 37.5 37.5ANTIOXIDANT 1520 0.5 0.5 0.5 0.5 0.5 PHOTOINITIATOR TPO 2 2 2 2 2 TOTALS 100 100 100 100 100 Oligomer mixture composition OME-01 OME-02 OME-03 OME-04 OME-05 [Urea+urethane content] (mmol / 100g) 54 41 51 52 51 Viscosity (mPa*s) (25°C) 2136 863 1279 1673 1131 Peel Strength (gf / in) 41 35 196 112 253 Elongation at Break (%) 66 56 118 100 102 Film Modulus (Tensile) (Mpa) 1.97 0.77 0.90 0.78 0.97 Toughness (N*mm / m3) 0.30 0.09 0.36 0.25 0.31Tensile Strength (Mpa) 0.78 0.27 0.53 0.42 0.52 * Formulations FE-01 and FE-02 are both comparative examples comprising no aspartate and no hydantoin.

[0298] In Table 6B, aspartate difunctional oligomers OE-07 in second control FE-07 and third control FE-09 were totally or partially replaced by an inventive aspartate hydroxyl oligomer OE-05 in inventive formulations FE-08 and FE-10. The oligomer mixture was then changed from OME-06 and OME-08 to inventive OME-07 and OME-09 as indicated in the table. As shown in structures of OE-07 and OE-05, OE-05 had one less equivalent of HEA and TDI residue unit. Such difference in structure composition resulted in a free hydroxyl at one end of the oligomer structure and OE-5 had a theoretical molecular weight of 91.4% that of OE-07. The change in molecular weight was not significant, but surprisingly had a significant impact to viscosity and modulus. As a result of oligomer replacement, FE-08 showed a 26.5% decrease in viscosity and 35.4% decrease in film modulus, relative to FE-07. FE-10 showed a 31% decrease in viscosity and 33% decrease in film modulus, relative to FE-09. Both viscosity decrease and film modulus decrease are desired to be used as fiber optical primary coating formulation improvement tools. The benefit of having aspartate in oligomer for better adhesion was reduced when FE-08 is compared with FE-07 and FE-10 is compared with FE-09, however the adhesion of both inventive formulations FE-08 and FE-09 was still much better than the non-aspartate control of FE-06. Other properties were also impacted such as elongation, toughness and tensile strength, but the toughness change is considered very acceptable considering how much modulus is reduced. For the overall impact towards the non-aspartate control of FE-06, inventive formulations FE-08 and FE-10 provided more balanced property improvement than FE-07 and FE-09. This invention of new oligomer design provides an additional fonnulation tool for fiber optical primary coating development.Table 6B: Inventive oligomer screening. OE-05 replacing an aspartate diacrylate control oligomer OE-07.FE-06* FE-07** FE-08 FE-09** FE-10OE-Ol 55 25 25 — — OE-07 — 30 — 55 25 OE-05 — — 30 — 30 PEA 25.5 25.5 25.5 25.5 25.5 ENPA 17 17 17 17 17 ANTIOXIDANT 1520 0.5 0.5 0.5 0.5 0.5 TPO 2 2 2 2 2 Totals 100 100 100 100 100 Oligomer mixture in formulation OME-01 OME-06 OME-07 OME-08 OME-09 [Urea+urethane] (mmol / lOOg formulation) 49 76 62 99 84 Viscosity (mPa*s) (25°C) 1330 2450 1800 4480 3100 Peel Strength (gf / in) 30 116 57 182 135 Elongation (at break) (%) 68 74 80 71 87 Film Modulus (Tensile) (Mpa) 1.77 1.47 0.95 1.26 0.84 Toughness (N*mm / m3) 0.29 0.29 0.21 0.24 0.23Tensile Strength (Mpa) 0.73 0.70 0.45 0.60 0.46 * Formulation FE-06 is a comparative example comprising no aspartate and no hydantoin.** Fonnulation FE-07 and FE-09 are comparative examples comprising aspartate.

[0299] Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.

Claims

1. WHAT IS CLAIMED IS:

1. An ethylenically unsaturated compound comprising:3.(a) a moiety of the structure (1):4.• - N - n - G1- Zp— G1!!6.

7. O (i);8.(bl) a moiety of the structure (2):

10.

11. (2); or12.(b2) a moiety of the structure (3):13.O15.

16. (3); or (b3) a combination of a moiety of the structure (2) and a moiety of the structure (3); and, optionally,17.(c) a moiety of the structure (3 a):

19.

20. in which: (i) each R1, which may be the same or different, represents an organic group that is inert to isocyanate groups at temperatures of 100°C or less;21.(ii) each R2, which may be the same or different, represents hydrogen or an organic group that is inert to isocyanate groups at temperatures of 100°C or less;22.(iii) each - • represents a linkage to another portion of the ethylenically unsaturated compound;23.(iv) each G1is 0 or S;24.(v) m has a value of 1 to 5, such as 1 to 3, or 1;25.(vi) n has a value of 1 to 5, 1 to 3, or 1; and26.(vii) Zprepresents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a Cs-Ce cycloalkylene group.

2. Tire ethylenically unsaturated compound of claim 1, wherein the ethylenically unsaturated compound is an oligomer, such as an oligomer having a number average molecular weight of at least 800 g / mol. 800 to 35,000 g / mol, 1000 g / mol to 35,000 g / mol, 2000 g / mol to 30,000 g / mol, 2000 g / mol to 25,000 g / mol. 2000 g / mol to 20.000 g / mol, 2,200 to 10.000 g / mol, or 2.200 to 5,500 g / mol. determined by size exclusion chromatography.

3. Tire ethylenically unsaturated compound of claim 1 or claim 2, wherein the ethylenically unsaturated compound comprises 1 to 4. 1 to 2, or 1 ethylenically unsaturated group.

4. The ethylenically unsaturated compound of one of claim 1 to claim 3. wherein the ethylenically unsaturated compound comprises an end group of structure (1) and an end group of the structure (la):30.E - • (la)31.in which E represents a group that comprises a polymerizable carbon-carbon double bond, such as an acryloyl, methacryloyl, or vinyl group, and - • represents a linkage to another portion of the ethylenically unsaturated compound.

5. The ethylenically unsaturated compound of one of claim 1 to claim 4, wherein (i) each R1in structures (2) and (3), which may be the same or different, represents an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where each R1in structures (2) and (3), which may bethe same or different, represents a methyl group, an ethyl group, a propyl group or a butyl group, and (ii) each R2in structures (2) and (3), which may be the same or different, represents hydrogen or an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where each R2in structures (2) and (3), which may be tire same or different, represents a hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group.

6. The ethyl enically unsaturated compound of one of claim 1 to claim 5, wherein the moiety of the structure (3a) is present and Zpis a portion of the residue of a polyester polyol, such as where the polyether polyol has a number average molecular weight, derived from the hydroxyl number of the polyol, of 62 to 20,000 g / mol, 500 to 15,000 g / mol, 900 to 9,000 g / mol, 1,800 to 6,000 g / mol or 2,500 to 5,000 g / mol.

7. The ethyl enically unsaturated compound of one of claim 1 to claim 6, wherein the ethylenically unsaturated compound is represented by the structure (4):

36.

37. in which:38.(i) each Y, which may be the same or different, represents a group comprising a branched or straight chain alkylene radical, such as where the branched or straight chain alkylene radical has at least 2, 2 to 8, or 2 to 4 carbon atoms;39.(ii) each G1. which may be the same or different, represents O or S;40.(iii) each G, which may be the same or different, represents O, S, NH, or NR' in which R' is an alkyl radical, such as an alkyl radical having 1 to 6 carbon atoms;41.(iv) Zprepresents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a Cs-Ce cycloalkylene group;42.(v) each R3, which may be the same or different, represents H or CH3,43.(vi) m has a value of 1 to 5, such as 1 to 3, or 1;44.(vii) n has a value of 1 to 5, 1 to 3, or 1;45.(viii) q has a value of at least 1, such as 1 to 20, 1 to 5, or 1 to 3;46.(ix) r is 1, 2 or 3;47.(x) LNis represented by the structure:

48.

49. ' ’m’n, in which Z1represents an organic group. in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a Cs-Ce cycloalkylene group, m and n are each as described above, and - • represents a linkage to another portion of the ethylenically unsaturated compound; and50.(xi) each L2. which may be the same or different, is represented by the structure L1or LB, with the proviso that at least one occurrence of L2is represented by the structure LB, in which L1is represented by structure (4a):

52. 54.in which Zp, G1, m, n and - • are each as described above with respect to structure (4); and LBis represented by structure (4b):

56.

57. in which: (i) ZArepresents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a C -C,. cycloalkylene group; (ii) each R1in structure (4b), which may be the same or different, represents an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where each R1in structure (4b), which may be the same or different, represents a methyl group, an ethyl group, a propyl group or a butyl group; (iii) each R2in structure (4b), which may be the same or different, represents a hydrogen or an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where each R2in structure (4b), which may be the same or different, represents a hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group; (iv) m and n are each as described above with reference to structure (4); and (v) each - • represents a linkage to another portion of the ethylenically unsaturated compound.

8. The ethylenically unsaturated compound of claim 7, wherein Y in structure (4) comprises a linear or branched alkylene radical having 1 to 8 carbon atoms, such as a linear alkylene radical having 2 to 4 or, in some cases 3, carbon atoms (such as a propylene radical), or a branched alkylene radical having 5 to 6 carbon atoms.

9. The ethylenically unsaturated compound of claim 7 or claim 8, wherein each R1in structure (4b), which may be the same or different, represents an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where R1, which may be the same or different, represents a methyl group, an ethyl group, a propyl group or a butyl group and each R2in structure (4b) represents a hydrogen.

10. The ethylenically unsaturated compound of one of claim 7 to claim 9. wherein Zpin structure (4a) is a portion of the residue of a polyether polyol, such as a polyether polyol that has a number average molecular weight, derived from the hydroxyl number of the polyol, of 62 to 20,000 g / mol, 500 to 15,000 g / mol, 900 to 9,000 g / mol, 1,800 to 6,000 g / mol or 2,500 to 5,000 g / mol.

11. The ethylenically unsaturated compound of one of claim 1 to claim 6. wherein the ethylenically unsaturated compound is represented by the structure (5):

62.

63. in which:64.(i) each Y, which may be the same or different, represents a group comprising a branched or straight chain alkylene radical, such as where the branched or straight chain alkylene radical has at least 2, 2 to 8, or 2 to 4 carbon atoms;65.(ii) each G1, which may be the same or different, represents O or S;66.(iii) each G, which may be the same or different, represents O, S, NH. or NR' in which R' is an alkyl radical, such as an alkyl radical having 1 to 6 carbon atoms;67.(iv) Zprepresents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a G-C, cycloalkylcnc group;68.(v) each R3, which may be the same or different, represents H or CH,.69.(vi) m has a value of 1 to 5, such as 1 to 3, or 1;70.(vii) n has a value of 1 to 5, 1 to 3, or 1;71.(viii) q has a value of at least 1, such as 1 to 20, 1 to 5, or 1 to 3;72.(ix) r is 1, 2 or 3;73.(x) LNis represented by the structure:

74.

75. ’n. in which Z1represents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a G-C, cycloalkylene group, m and n are each as described above, and - • represents a linkage to another portion of the ethylenically unsaturated compound; and (xi) each L3, which may be the same or different, is represented by the structure L1or Lc, with the proviso that at least one occurrence of L3is represented by the structure Lc, in which L1is represented by structure (4a):

77.

78. (4a)79.in which Zp. G1. m, and n are each as described above with reference to structure (5) and80.• represents a linkage to another portion of the ethylenically unsaturated compound; and Lcis represented by structure (5b):

82.

83. in which: (i) ZArepresents an organic group, in some cases a divalent organic group, that is inert towards isocyanate groups at temperatures of 100°C or less, such as a hydrocarbon group that optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof and that includes a Ci to Cis alkylene group or a C -Ce cycloalkylene group; (ii) each R1in structure (5b), which may be tire same or different, represents an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where each R1in structure (5b), which may be the same or different, represents a methyl group, an ethyl group, a propyl group or a butyl group; (iii) each R2in structure (5b), which may be the same or different, represents a hydrogen or an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where each R2in structure (5b). which may be the same or different, represents a hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group; (iii) m and n are each as described above with reference to structure (5); and (iv) each - • represents a linkage to another portion of the ethylenically unsaturated compound.

12. The ethylenically unsaturated compound of claim 11, wherein Y in structure (5) comprises a linear or branched alkylene radical having 1 to 8 carbon atoms, such as a linear alkylene radical having 2 to 4 or, in some cases 3, carbon atoms (such as a propylene radical), or a branched alkylene radical having 5 to 6 carbon atoms.

13. The ethylenically unsaturated compound of claim 11 or claim 12, wherein each R1in structure (5b), which may be the same or different, represents an alkyl group, such as an alkyl group having 1 to 9 or 1 to 4 carbon atoms, such as where R1, which may be the same or different, represents a methyl group, an ethyl group, a propyl group or a butyl group and each R2in structure (5b) represents a hydrogen.

14. The ethylenically unsaturated compound of one of claim 11 to claim 13, wherein Zpin structure (5a) is a portion of the residue of a polyether polyol, such as a polyether polyol that has a number average molecular weight, derived from the hydroxyl number of the polyol, of 62 to 20,000 g / mol, 500 to 15,000 g / mol, 900 to 9,000 g / mol, 1,800 to 6,000 g / mol or 2,500 to 5,000 g / mol.

15. A composition comprising :87.(a) the ethylenically unsaturated compound of one of claim 1 to claim 14, and88.(b) an ethylenically unsaturated oligomer different from ethylenically unsaturated compound (a), wherein the sum of the amount of ethylenically unsaturated compound (a) and ethylenically unsaturated oligomer (b) is 1 to 99% by weight, 10 to 90% by weight, 20 to 50% by weight, 40 to 70% by weight, 60 to 80% by weight, 65 to 99% by weight, or 1 to 30% by weight, based on the total weight of solids in the composition.

16. The composition of claim 15. wherein ethylenically unsaturated compound (a) is present in an amount of 1 to 99% by weight, 1 to 90% by weight, such as 10 to 90% by weight, 20 to 80% by weight, 30 to 70% by weight, or 40 to 60% by weight, based on the total weight of ethylenically unsaturated compound (a) and ethylenically unsaturated oligomer (b) in the composition.

17. The composition of claim 15 or claim 16, wherein the ethylenically unsaturated oligomer (b) comprises a urethane (meth)acrylate oligomer.

18. The composition of claim 17, wherein the urethane (meth)acrylate oligomer comprises a reaction product of reactants comprising: (1) a polyol, (2) a polyisocyanatc, and (3) a hydroxyl group -containing (meth)acrylate.

19. The composition of claim 18, wherein tire polyol comprises a diol and the polyisocyanate comprises a diisocyanate.

20. The composition of one of claim 17 to claim 19, wherein the urethane (meth)acrylate oligomer is present in an amount of 30 to 80% by weight, based on the total weight of solids in the composition.

21. The composition of one of claim 15 to claim 20, further comprising:94.(c) a reactive diluent compound comprising one or more ethylenically unsaturated groups, wherein the reactive diluent compound is present in an amount of 5 to 90% by weight, based on tire total weight of solids in the composition.

22. The composition of claim 21, wherein the reactive diluent compound comprises an alkyl or hydroxyalkyl (meth)acrylate, isobomyl acr late, ethoxylated nonyl-phenol acrylate, phenoxyethyl acrylate, diethylene-glycol-ethyl-hexyl acylate (DEGEHA), ethylene glycol diacrylatc. propylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylatc. bisphenol A diacrylatc. 4,4'-bis(2-acryloyloxyethoxy)diphenylpropane, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate and tetraacrylate, caprolactone (meth)acrylate. polyglycol (meth)acrylate, acrylonitrile, acrylamide, methacrylamide, an N-substituted (meth)acrylamide, a vinyl ester, styrene, an alkylstyrene, a halostyrene, a N-vinylpyrrolidone, a N-vinyl caprolactam, a vinyl chloride, a vinylidene chloride, or a mixture of any two or more thereof.

23. The composition of one of claim 15 to claim 22, further comprising:97.(d) a photoinitiator.

24. A cured coating formed from the composition of one of claim 15 to claim 23.

25. A substrate at least partially coated with the cured coating of claim 24, wherein the substrate comprises an optical fiber.

26. A method for coating an optical fiber comprising:101.(a) providing a glass optical fiber;102.(b) applying a primary' coating composition onto a surface of the glass optical fiber; (c) optionally, imparting a dose of ultraviolet light sufficient to at least partially cure said primary coating composition;103.(d) applying a secondary coating composition to the primary coating composition; and104.(e) exposing the secondary coating composition to at least one radiation source capable of emitting ultraviolet radiation to affect curing of said secondary coating composition and, optionally, said primary coating composition,105.wherein the primary coating composition and / or tire secondary coating composition comprises the composition of one of claim 15 to claim 23.

27. A coated optical fiber comprising:107.(a) a glass core and a cladding layer in contact with and surrounding said glass core; and (b) a coating portion at least partially coating the cladding layer, tire coating portion comprising:108.(i) a primary coating layer in contact with said cladding layer; and109.(ii) a secondary coating layer in contact with and surrounding said primary coating layer, wherein the primary coating layer and / or the secondary coating layer is the cured coating of claim 24.

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