HIGH REFRACTIVE INDEX COMPOSITIONS AND THEIR USES.

Abstract

Compositions are described that include a combination of (meth)acryloyl-terminated monomers and oligomers prepared by reacting reagents with active hydrogen groups with an acrylating agent. The polymerizable composition formed using these (meth)acryloyl-terminated monomers and oligomers exhibits high hardness, excellent thermomechanical properties, and a high refractive index. These compositions can be used to manufacture optical components.

Description

HIGH REFRACTIVE INDEX COMPOSITIONS AND THEIR USES CROSS-REFERENCE WITH RELATED APPLICATIONS

[0001] This application claims priority over U.S. Provisional Patent Applications Nos. 62 / 781,344, filed December 18, 2018, and 62 / 931,235, filed November 6, 2019, both of which are incorporated by reference in their entirety. FIELD OF INVENTION

[0002] Compositions comprising a combination of (meth)acryloyl-terminated monomers and oligomers are prepared by the combined reaction of reagents having active hydrogen groups with an acrylating agent. The polymers formed using the combinations of (meth)acryloyl-terminated monomers and oligomers exhibit high hardness, excellent thermomechanical properties, and a high refractive index. The compositions can be used to manufacture optical components. BACKGROUND OF THE INVENTION

[0003] Polymerizable compositions with a high sulfur content are useful for forming optical components. Polymerizable compositions typically contain (meth)acryloyl-terminating monomers that react in the presence of free radicals. (meth)acryloyl-terminating monomers can be prepared by reacting individual reagents containing terminal active hydrogens with an acrylating agent. The yield of this reaction can be low due to the formation of insoluble oligomers resulting from the reaction of the active hydrogen groups with the alkenyl group of the (meth)acryloyl acryloyl group of the acrylating agent.

[0004] Improved polymerizable compositions are described for use in the formation of polymers that have high hardness, useful thermomechanical properties, and a high refractive index. BRIEF DESCRIPTION OF THE INVENTION

[0005] According to the present invention, the compositions comprise: (a) a first monomer terminated in (meth) acryloyl, wherein the first monomer terminated in (meth) acryloyl has the structure of Formula (1): oo (1) where each R1 is independently selected from hydrogen or methyl; (b) is selected from 0 or 1; and pRz / nn / Lznz / E / Yii a is an integer from 1 to 6; and (b) a second (meth) acryloyl-terminated monomer comprising two or more (meth) acryloyl groups, wherein each of the two or more (meth) acryloyl groups is independently selected from an (meth) acryloyloxy group and an (meth) acryloylthio group; at least one of the (meth) acryloyl groups is a (meth) acryloylthio group; and the second (meth) acryloyl-terminated monomer (b) is different from the first (meth) acryloyl-terminated monomer.

[0006] According to the present invention, the compositions comprise the reaction product of reagents comprising: (i) a first reagent, having two active hydrogen groups, the first reagent having the structure of Formula (5): pRz / nn / Lznz / B / Yi where b is selected from 0 or 1; and is an integer from 1 to 6; (ii) a second reagent comprising two or more active hydrogen groups, wherein each of the two active hydrogen groups is independently selected from hydroxyl or thiol; at least one of the two or more active hydrogen groups is a thiol; and the second reagent is different from the first reagent; and (iii) a third reagent comprising an acrylating agent.

[0007] According to the present invention, the polymerizable compositions comprise a composition according to the present invention; and a free radical initiator.

[0008] According to the present invention, the articles comprise a polymerization according to the present invention.

[0009] According to the present invention, the methods of manufacturing an article comprise: forming the polymerizable composition according to the present invention into a shape; and curing the applied composition to provide the article.

[0010] According to the present invention, the articles are manufactured using methods according to the present invention.

[0011] According to the present invention, the methods for synthesizing a compound comprise: (A) combining the reagents (i), (ii) and (iii) to form a mixture, wherein the reagents comprise: (i) a first reagent, having two active hydrogen groups, the first reagent having the structure of Formula (5): where b is selected from 0 or 1; and is an integer from 1 to 6; and (ii) a second reagent comprising two or more active hydrogen groups, where each of the two or more active hydrogen groups is independently selected from hydroxyl or thiol; at least one of the two or more active hydrogen groups is a thiol; and the second reagent is different from the first reagent; and (iii) a third reagent, wherein the third reagent comprises an acrylating agent; and (B) reacting the mixture in the presence of a base to provide the combination of (meth) acryloyl-terminated monomers and (meth) acryloyl-terminated oligomers. BRIEF DESCRIPTION OF THE FIGURES

[0012] The figures described herein are for illustrative purposes only. The figures are not intended to limit the scope of this description.

[0013] Figure 1 shows a gel permeation chromatography chromatogram of a combination of (met) acryloyl-terminated monomers and oligomers provided for the present intent.

[0014] Figure 2 shows an example of a synthesis scheme for preparing a combination of (meth) acryloyl-terminated monomers and oligomers provided by the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] For the purposes of the following detailed description, it should be understood that the embodiments provided herein may assume variations of several alternatives and sequences of steps, except where expressly stated otherwise. Furthermore, except in any example of operation or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims shall be understood as modified in all cases by the term "approximately." Accordingly, unless otherwise stated, the numerical parameters cited in the following specification and appended claims are approximations that may vary depending on the desired properties to be obtained by the present invention.Finally, and without intending to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be interpreted at least in light of the number of significant digits reported and using common rounding techniques.

[0016] Notwithstanding that the numerical intervals and parameters that establish the broad scope of the invention are approximations, the numerical values ​​cited in the examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in its respective test measurements.

[0017] It should also be understood that any numerical interval cited herein is intended to include all subintervals contained within it. For example, an interval from “1 to 10” is intended to include all subintervals between (and including) the cited minimum value of 1 and the cited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.

[0018] A hyphen not between two letters or symbols is used to indicate a point of attachment of a substituent or between two atoms. For example, -CONH2 attaches through the carbon atom.

[0019] “Alkanedyl” refers to a diradical of a saturated or unsaturated, branched or linear acyclic hydrocarbon group having, for example, 1 to 18 carbon atoms (C1-is), 1 to 14 carbon atoms (C1-u), 1 to 6 carbon atoms (C1-β), 1 to 4 carbon atoms (C1,4), or 1 to 3 hydrocarbon atoms (C1-3). It will be noted that a branched alkanedyl has a minimum of three carbon atoms. An alkanedyl group can be a C2-14 alkanedyl, a C2-10 alkanedyl, a C2-8 alkanedyl, a C2-6 alkanedyl, a C2-4 alkanedyl, or a C2-3 alkanedyl. Examples of alkanedyl groups include methane-diyl (-CH2-), ethane-1,2-diyl (-CH2CH2-), propane-1,3-diyl and isopropane-1,2-diyl (e.g., -CH2CH2CH2- and -CH(CH3)CH2-), butane-1,4-diyl (-CH2CH2CH2CH2-), pentane-1,5-diyl (-CH2CH2CH2CH2CH2-), hexane-1,6-diyl (-CH2CH2CH2CH2CH2CH2-), heptane-1,7-diyl, octane-1,8-diyl, nonane-l,9-diyl, decane-1,10-diyl and dodecane-l,12-diyl.Alkanedyl groups can include single, double and / or triple bonds between carbon atoms.

[0020] “Alkanecycloalkane” refers to a saturated hydrocarbon group having one or more cycloalkyl and / or cycloalkanediyl groups and one or more alkyl and / or alkanediyl groups, where cycloalkyl, cycloalkanediyl, alkyl, and alkanediyl are defined herein. Each of the cycloalkyl and / or cycloalkanediyl groups may be C3-6, C5-6, cyclohexyl, or cyclohexanediyl. Each alkyl and / or alkanediyl group may be C1-6, Cm, C1-3, methyl, methanediyl, ethyl, or ethanol-1,2-diyl. An alkanecycloalkane group can be a C4-18 alkanecycloalkane, a C4-16 alkanecycloalkane, a C4-12 alkanecycloalkane, a C4-8 alkanecycloalkane, a C4-12 alkanecycloalkane, a C4-10 alkanecycloalkane, or a C4-10 alkanecycloalkane. Examples of alkanecycloalkane groups include 1,1,3,3-tetramethylcyclohexane and cyclohexylmethane.

[0021] “Alkanecycloalkanediyl” refers to a diradical of an alkanecycloalkane group. An alkanecycloalkanediyl group can be a C4-16 alkanecycloalkanediyl, a C4-16 alkanecycloalkanediyl, a C4-12 alkanecycloalkanediyl, a C4-8 alkanecycloalkanediyl, a C4-10 alkanecycloalkanediyl, or a C4-9 alkanecycloalkanediyl. Examples of alkanecycloalkanediyl groups include 1,1,3,3-tetramethylcyclohexane-1,5-diyl and cyclohexylmethane-4,4'-diyl.

[0022] “Alkanarene” refers to a hydrocarbon group having one or more aryl and / or arenoyl groups and one or more alkyl and / or alkanediyl groups, where aryl, arenoyl, alkyl, and alkanediyl are defined herein. Each of the aryl and / or arenoyl groups may be C1-2, C1-10, phenyl, or benzenediyl. Each of the alkyl and / or alkanediyl groups may be C1-6, C1-4, C1-3, methyl, methanediyl, ethyl, or ethanol-1,2-diyl. An alkanarene group can be a C4-18 alkanarene, a C4-16 alkanarene, a C4-12 alkanarene, a C4-8 alkanarene, a Ce-n alkanarene, a Ce-io alkanarene, or a Ce9 alkanarene. Examples of alkanarene groups include diphenylmethane.

[0023] “Alkanarenediyl” refers to a diradical of an alkanarene group. An alkanarenediyl group is an alkanarenediyl of C4-16, alkanarenediyl of C4-12, alkanarenediyl of C4-8, alkanarenediyl of C4-12, alkanarenediyl of C4-11, or alkanarenediyl of C4-g. Examples of alkanarenediyl groups include diphenylmethane-4,4'-diyl.

[0024] The “Alkenyl” group refers to the structure -CR=C(R)2 where the alkenyl group is a terminal group and is attached to a larger molecule. In these embodiments, each R can independently comprise, for example, hydrogen or a C1-3 alkyl group. Each R can be hydrogen and the alkenyl group has the structure -CH=CH2.

[0025] “Alkoxy” refers to an -OR group where R is alkyl as defined herein. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy. An alkoxy group may be a Ci-s alkoxy, a Ci-6 alkoxy, a Cm alkoxy, or a C1.3 alkoxy.

[0026] “Alkyl” refers to a monoradical of a saturated or unsaturated, branched or straight-chain acyclic hydrocarbon group having, for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. It will be noted that a branched alkyl has a minimum of three carbon atoms. An alkyl group may be C1-6 alkyl, C1-4 alkyl, or C1-3 alkyl. Examples of aryl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-decyl, and tetradecyl. An alkyl group is C1-6 alkyl, C1-4 alkyl, and C1-3 alkyl.

[0027] “Arenediyl” refers to a diradical of a monocyclic or polycyclic aromatic group. Examples of arenodiyl groups include benzene-diyl and naphthalene-diyl. An arenodiyl group may be arenodiyl of C12, arenodiyl of C10, arenodiyl of C9, or benzene-diyl. ΓΑζ / ηη / ίζηζ / Ε / γι

[0028] “Cycloalkanediyl” refers to a diradical of a saturated monocyclic or polycyclic hydrocarbon group. A cycloalkanediyl group can be a C312 cycloalkanediyl, a C3s cycloalkanediyl, a C36 cycloalkanediyl, or a C56 cycloalkanediyl. Examples of cycloalkanediyl groups include cyclohexane-1,4-diyl, cyclohexane-1,3-diyl, and cyclohexane-1,2-diyl.

[0029] “Cycloalkyl” refers to a saturated monocyclic or polycyclic hydrocarbon monoradical group. A cycloalkyl group can be a C3-12 cycloalkyl, a C3-8 cycloalkyl, a C3-6 cycloalkyl, or a C5-6 cycloalkyl.

[0030] “Heteroalkanediyl” refers to an alkanediyl group in which one or more of the carbon atoms are replaced with a heteroatom, such as N, O, S, or P. In the heteroalkanediyl, one or more heteroatoms may comprise N or O.

[0031] “Heterocycloalkanediyl” refers to a cycloalkanediyl group in which one or more of the carbon atoms are replaced with a heteroatom, such as N, O, S, or P. In a heterocycloalkanediyl, one or more heteroatoms may comprise N or O.

[0032] “(Heterocycloalkane) alkanediyl” refers to an alkanecycloalkanediyl group in which one or more of the carbon atoms of the cycloalkane are replaced with a heteroatom, such as N, O, S or P.

[0033] “Heteroarenodiyl” refers to an arenodiyl group in which one or more of the carbon atoms are replaced with a heteroatom, such as N, O, S, or P. In a heteroarenodiyl, one or more of the heteroatoms may comprise N or O.

[0034] “Formed from” or “prepared from” openly denotes, for example, comprising, in claim language. Therefore, a composition “formed from” or “prepared from” a list of cited components is purported to be a composition comprising at least one of the cited components or the reaction product of at least one of the cited components and may further comprise other unlisted components used to form or prepare the composition.

[0035] “Reaction product of” means a product of a chemical reaction of at least the stated reactants and may include partial reaction products, as well as products that fully regenerate or other reaction products present in a minor amount. For example, a “prepolymer comprising reaction products of reactants” refers to a prepolymer or combination of prepolymers that are the reaction product of at least the stated reactants. The reactants may further comprise additional reactants.

[0036] The term “equivalent” refers to a number of functional reactive groups of the substance. The “equivalent weight” is effectively equal to the molecular weight of a substance, divided by the valency or number of functional reactive groups of the substance. ΓΑζ / ηη / ίζηζ / Ε / γι

[0037] A “core” of a compound or polymer refers to the segment between the reactive terminal groups. For example, the core of a polythiol HS-R-SH will be -R-. A core of a compound or prepolymer may also be referred to as a skeleton of a compound or a skeleton of a prepolymer. A core of a polyfunctionalizing agent may be an atom or structure such as a cycloalkane, substituted cycloalkane, heterocycloalkane, substituted heterocycloalkane, arene, substituted arene, heteroarene, or substituted heteroarene to which the parts having a functional reagent are attached.

[0038] “Substituted” refers to a group in which one or more hydrogen atoms are each independently replaced with the same or different substituents. A substituent may comprise halogen, -S(O)2OH, -S(O)2, -SH, -SR where R is a C1-6 alkyl, -COOH, -NO2, NR2 where each R independently comprises hydrogen and a C1-3 alkyl, -CN, -O, C1-6 alkyl, -CF3, -OH, phenyl, C2-6 heteroalkyl, C5-6 heteroaryl, C1-6 alkoxy, or -COR where R is a C1-6 alkyl. A substituent may be -OH, -NH2, or a C1-3 alkyl.

[0039] “Derived from” as in “a derived part of a compound” refers to a part that is generated after the reaction of a parent compound with a reagent. For example, a bis(alkenyl) compound CH2=CH-R-CH=CH2 can react with another compound, such as two compounds having thiol groups, to produce the part or portion -(CH2)2-R-(CH2)2- derived from the reactions of alkenyl groups with thiol groups. For example, a parent diisocyanate has the structure O=C=NR-N=C=O; a derived part of the diisocyanate has the structure -C(O)-NH-R-NH-C(O)-. As another example, a parent nonlinear short-chain diol has the structure HO-R-OH; a derived part of a nonlinear short-chain diol has the structure -ORO-.

[0040] “Derivative of the reaction of -V with a thiol” refers to a -V'- part resulting from the reaction of a thiol group with a part comprising a terminal group reactive with a thiol group. For example, a V- group may comprise CH2=CH-CH2-O-, where the terminal alkenyl group CH2=CH reacts with a thiol group -SH. After the reaction with a thiol group, the -V'- part is -CH2-CH2CH2-O-.

[0041] “Composition” is intended to encompass a product comprising the specified components in the specified quantities, as well as any product resulting, directly or indirectly, from the combination of the specified ingredients in the specified quantities.

[0042] “Molecular weight” refers to a theoretical molecular weight estimated from the chemical structure of a compound as a monomeric compound, or a numerical average molecular weight as appropriate for a given prepolymer, e.g., using gel permeation chromatography using polystyrene standards.

[0043] “Thioether” refers to a compound having one or more thioether groups, -S-. A thioether may also be referred to as a thiaalkylene. A polythioether refers to a compound having two or more thioether groups, -S-. A polythioether may be referred to as a polythiaalkylene.

[0044] The “microindentation hardness”, also referred to as Martens hardness, is measured according to ISO 14577-07 using a Fischerscope H-100SMC, available from Fischer Technology, Inc.

[0045] The “Fischer microhardness” or “Fischer Hardness” is measured using a Fischerscope H100SMC, available from Fischer Technology, Inc. at a load of 300 milliNewtons (mN), after the application of a load of 0-300 mN in 15 seconds.

[0046] The “Abbe Number” is measured using a Metricon Model 2010M prism coupler in accordance with ASTM C1648.

[0047] The “refractive index” is determined using a Metricon Model 2010M prism coupler in accordance with ASTM C1648 at 20 degrees Celsius (°C) at a wavelength of 546.07 nanometers (nm) (mercury e line) and is reported as ne20.

[0048] The “storage modulus E'” is measured in accordance with ASTM D5023 “Standard Test Method for Plastics. Dynamic Mechanical Properties: In Flexure (Three-Point Bending)” using a Perkin Elmer Diamond Dynamic Mechanical Analysis (DMA) analyzer.

[0049] The “yellowing index” is measured using a HunterLab UltraScan PRO in accordance with ASTM E313.

[0050] Compounds can be identified by either their chemical structure and / or chemical name. Certain compounds are named using the nomenclature program ChemBioDraw Ultra 14.0.0.117 (CambridgeSoft, Cambridge, MA). When the chemical structure and chemical name conflict, the chemical structure determines the identity of the compound. The compounds described herein may comprise one or more stereogenic centers and / or double bonds and may therefore exist as stereoisomers such as double-bond isomers (i.e., geometric isomers), enantiomers, diastereomers, or atropisomers.Consequently, any chemical structure within the scope of the described specification, in whole or in part, with a relative configuration, encompasses all possible enantiomers or stereoisomers of the illustrated compounds, including the stereoisomerically pure form (e.g., geometrically pure, enantiomerically pure, or diastereomerically pure) and enantiomeric and stereoisomeric mixtures. Enantiomeric and stereoisomeric mixtures can be resolved into their component enantiomers or stereoisomers using separation techniques or chiral synthesis techniques.

[0051] Reference is now made to certain compounds, compositions, and methods of the present invention. The compounds, compositions, and methods described are not intended to limit the claims. Rather, the claims are intended to cover all alternatives, modifications, and equivalents. PR7 / nn / L7n7 / E / YI!

[0052] The compositions provided in this description comprise a combination of (meth)acryloyl-terminated monomers and oligomers. The compositions can be used to form polymers exhibiting high hardness and a high refractive index.

[0053] The combination of monomers and oligomers terminated in (meth)acryloyl may comprise a first monomer terminated in (meth)acryloyl, a second monomer terminated in (meth)acryloyl, wherein the second monomer terminated in (meth)acryloyl is different from the first monomer, and an oligomer terminated in (meth)acryloyl.

[0054] A first (meth)acryloyl-terminated monomer may comprise a (meth)acryloyl-terminated monomer having the structure of Formula (1): ° O (1) where each R1 can be selected independently of hydrogen or methyl; b is selected from 0 or 1; ya is an integer from 1 to 6.

[0055] In the monomers of Formula (1) each R1 can be hydrogen or each R1 can be methyl.

[0056] In the monomers of Formula (1), b can be 0 or ob can be 1.

[0057] In the monomers of Formula (1), a can be an integer from 1 to 5, from 1 to 4, from 1 to 3 or from 1 to 2.

[0058] In the monomers of Formula (1), a can be 1, 2, 3, 4, 5 or 6.

[0059] In the monomers of Formula (1), a can be selected from 1 or 2.

[0060] In the monomers of Formula (1), each R1 can be hydrogen; b can be 0 or can be 1 or 2.

[0061] In the monomers of Formula (1), each R1 can be methyl; b can be 0 or can be 1 or 2.

[0062] In the monomers of Formula (1), each R1 can be hydrogen; b can be 1 and can be 1 or 2.

[0063] In the monomers of Formula (1), each R1 can be methyl; b can be 1 and can be 1 or 2.

[0064] A first (meth)acryloyl terminated monomer may include a combination of monomers having the structure of Formula (1).

[0065] Examples of Formula (1) monomers include bis(2-methacryloylthioethyl)sulfide, bis(2-acryloylthioethyl)sulfide, 2-acryloyloxyethyl-2'-acryloylthioethyl sulfide, 2-methacryloyloxyethyl2'-methacryloylthioethyl sulfide, or combinations thereof.

[0066] The first monomer terminated in (meth)acryloyl may comprise bis(2methacryloylthioethyl)sulfide (a). pRz / nn / Lznz / B / Yi (the)

[0067] A second monomer terminated in (meth)acryloyl has a different structure from that of the first monomer terminated in (meth)acryloyl.

[0068] The second (meth)acryloyl-terminated monomer may comprise two or more (methyl)acryloyl groups, wherein each of the two or more (meth)acryloyl groups is independently selected from either a (meth)acryloyloxy group or a (meth)acryloylthio group; at least one of the (meth)acryloyl groups is a (meth)acryloylthio group; and the second (meth)acryloyl-terminated monomer is different from the first (meth)acryloyl-terminated monomer.

[0069] The second monomer terminated in (meth)acryloyl may comprise: (4c)

[0070] The second monomer ending in (meth)acryloyl may include 2,5bis(methacryloylthiomethyl)1,4-dithiano (4a), 2-ethyl-2-((meth)acryloylthiomethyl)-1,3-bis[(meth)acryloylthio]propane (4b), l,2,3-tris[(meth)acryloylthio]propane (4c), 2,2-bis[(meth)acryloylthiomethyl]-l,3-bis[(meth)acryloylthio]propane (4d), 4-(meth)acryloylthiomethyl-3,6-dithia-l,8-bis[(meth)acryloylthio]octane (4e), l,3-bis[(meth)acryloylthio]-2(meth)acryloyloxypropane (4f), l-(meth)acryloylthio-2,3-bis[(meth)acryloylthio]propane (4g), 1,2bis[(meth)acryloylthio]-3-(meth)acryloylthiopropane (4h), 7-(meth)acryloylthiomethyl-3,6,9,12-tetrathia-1,14bis[(meth)acryloylthio]tetradecane (4i), 7-[2-(meth)acryloylthioethyl]-3,6,8,l l-tetrathia-1,13bis[(meth)acryloylthio]tridecane, 4,8-bis[(meth)acryloylthiomethyl]-3,6,9-trithia-l,ll-bis[(meth)acryloylthio]undecane (4j) o regioisómeros de (4j) como los regioisomeros 4,7- or 5,7 or a combination of any of the previous ones.

[0071] The second (meth)acryloyl-terminated monomer may comprise a cyclic (meth)acryloyl-terminated monomer having the structure of Formula (2), a branched (meth)acryloyl-terminated monomer having the structure of Formula (3), or a combination thereof: R1R oo(2) B(-R3-XC(=O)-C(-R1)=CH2)z(3) where z is an integer from 3 to 6; each R1 is selected independently of hydrogen or methyl; Each X is selected independently of O or S; and at least one X is S; R2 is selected from (heterocycloalkane)alkane-diyl, heteroalkanearene-diyl of Có2o, (heterocycloalkane)alkane-diyl substituted or heteroalkanearene-diyl of Ce 20 substituted; R3 is selected from C112 alkane-diyl, C212 heteroalkane-diyl, Cs12 heterocycloalkane-diyl, Ce-12 heteroarene-diyl, (heterocycloalkane)alkane-diyl, Ce-2o heteroalkanearene-diyl, substituted C2^ alkanediyl, substituted C212 heteroalkane-diyl, substituted C512 heterocycloalkane-diyl, substituted C6-12 heteroarene-diyl, substituted (heterocycloalkane)alkane-diyl, or substituted Ce20 heteroalkanearene-diyl; and B is a multifunctional part.

[0072] In the monomers of Formula (2) and Formula (3) one or more heteroatoms may be S.

[0073] In the monomers of Formula (2) and branched monomers of Formula (3), each R1 can be hydrogen or each R1 can be methyl.

[0074] In the monomers of Formula (2) and Formula (3), each X can be S.

[0075] In the monomers of Formula (2), an X can be O and an X can be S.

[0076] In the monomers of Formula (2), R2 can be (heterocycloalkane)alkane-diyl.

[0077] In the monomers of Formula (2), R2 can have the structure: pRz / nn / Lznz / B / Yi

[0078] Examples of suitable cyclic monomers of Formula (2) include 2,5bis(methacryloylthiomethyl) 1,4-dithian.

[0079] In the monomers of Formula (3), one X can be S and each of the other X's can be EITHER.

[0080] In the monomers of Formula (3), two X's can be S and each of the other X's can be O.

[0081] In the monomers of Formula (3), z can be an integer from 3 to 5 or from 3 to 4.

[0082] In the monomers of Formula (3), z can be 3, 4, 5 or 6.

[0083] In the monomers of Formula (3), R3 can be selected from C2-12 alkane-diyl or C5-12 heteroalkane-diyl.

[0084] In the branched monomers of Formula (3), B can be HC(-)3 or another polyfunctional part.

[0085] The (meth)acryloyl-terminating second monomer may comprise a polythioether (polythiaalkylene) portion. For example, the (meth)acryloyl-terminating second monomer may comprise an aliphatic polythiaalkylene portion. A polythiaalkylene portion may be a cyclic polythiaalkylene portion or a branched polythiaalkylene portion. Examples of suitable (meth)acryloyl-terminating second monomers comprising cyclic polythiaalkylene portions include 2,5-bis(methacryloylthiomethyl)l,4-dithian. Examples of suitable (meth)acryloyl-terminating second monomers comprising branched polythiaalkylene portions include monomers having three or more (meth)acryloyl groups, such as 3 to 6 (meth)acryloyl groups.Examples of suitable (meth)acryloyl-terminated second monomers comprising branched polythiaalkylene parts include 4-(meth)acryloylthiomethyl-3,6-dithia-1,8-bis[(meth)acryloylthio]octane, 7-(meth)acryloyloxymethyl-3,6,9,12-tetrathia-1,14-bis[(meth)acryloylthio]tetradecane, 4,8-bis[(meth)acryloylthiomethyl]-3,6,9-trithia-1,11-bis[(meth)acryloylthio]undecane or regioisomers thereof such as the regioisomers 4,7- and 5,7-, 2-ethyl-2((meth)acryloylthiomethyl)-1,3-bis[(meth)acryloylthio]propane or combinations of any of the foregoing.

[0086] The second monomer terminated in (meth)acryloyl may comprise two or more (meth)acryloylthio groups such as 2 to 6, 2 to 5, 2 to 4 or 2 to 3 (meth)acryloylthio groups.

[0087] The second monomer terminated in (meth)acryloyl may comprise at least one (meth)acryloylthio group and at least one (meth)acryloyloxy group. For example, the second monomer terminated in (meth)acryloyl may comprise one (meth)acryloylthio group and from 1 to 5 (meth)acryloyloxy groups. The second monomer terminated in (meth)acryloyl may comprise two (meth)acryloylthio groups and from 1 to 4 (meth)acryloyloxy groups; the second monomer terminated in (meth)acryloyl may comprise three (meth)acryloylthio groups and from 1 to 3 (meth)acryloyloxy groups; the second monomer terminated in (meth)acryloyl may comprise four (meth)acryloylthio groups and from 1 to 2 (meth)acryloyloxy groups; or the second monomer terminated in (meth)acryloyl may comprise five (meth)acryloylthio groups and one (meth)acryloyloxy group.

[0088] Examples of second monomers terminated in (meth) acryloyl of Formula (2) or nn / Lznz / E / YiAi Formula (3) includes those with Formula (4a)-(4j) structures, as described above.

[0089] Each of the first monomer terminated in (meth) acryloyl and the second monomer terminated in (meth) acryloyl may independently comprise, for example, more than 15 percent by weight (% wt) of sulfur, more than 20 percent by weight or more than 25 percent by weight of sulfur where the % wt is based on the molecular weight of the respective monomer.

[0090] The relative amounts of the (meth) acryloyl-terminated monomers and oligomers may be selected so that a composition has a sulfur content greater than 15% by weight, greater than 25% by weight, greater than 28% by weight, or greater than 30% by weight, wherein the % by weight is based on the total weight of the monomers and oligomers in the composition.

[0091] The relative amounts of the (meth)acryloyl-terminated monomers and oligomers can be selected so that a composition has a sulfur content of 15 wt% to 55 wt% sulfur, such as 20 wt% to 50 wt%, 25 wt% to 50 wt%, or 25 wt% to 45 wt% sulfur, where the wt% is based on the total weight of the monomers and oligomers in the composition.

[0092] Each of the first monomer terminated in (meth) acryloyl and the second monomer terminated in (meth) acryloyl may independently comprise, for example, from 15% by weight to 55% by weight of sulfur, as well as from 20% by weight to 50% by weight, from 25% by weight to 50% by weight or from 25% by weight to 45% by weight of sulfur, wherein the % by weight is based on the molecular weight of the respective monomer.

[0093] The compositions provided herein comprise amounts of the first (meth)acryloyl-terminated monomer and the second (meth)acryloyl-terminated monomer such that the composition comprises an excess of (meth)acryloyl equivalents associated with the first (meth)acryloyl-terminated monomer compared to the number of (meth)acryloyl equivalents associated with the second (meth)acryloyl-terminated monomer. Furthermore, the number of (meth)acryloyl equivalents associated with the first (meth)acryloyl-terminated monomer may be greater than the number of (meth)acryloyl equivalents associated with the second (meth)acryloyl-terminated monomer, regardless of the (meth)acryloyl functionality of the second (meth)acryloyl-terminated monomer.

[0094] For example, in the compositions provided by the present invention, the first (meth)acryloyl-terminated monomer may comprise first (meth)acryloyl equivalents; the second (meth)acryloyl-terminated monomer may comprise second (meth)acryloyl equivalents; and a ratio of the first (meth)acryloyl equivalents to the second (meth)acryloyl equivalents may be greater than 1:1, such as greater than 1.1:1, greater than 2:1, greater than 3:1, greater than 5:1, greater than 10:1, or greater than 20:1. For example, the ratio of (meth) acryloyl equivalents associated with the first (meth) acryloyl-terminated monomer to the second (meth) acryloyl-terminated monomer can be from 1:1 to 25:1, from 1.1:1 to 20:1, from 2:1 to 15:1, from 3:1 to 10:1, or from 5:1 to 10:1.

[0095] The compositions provided by this description may further comprise an (meth)acryloyl-terminated oligomer or a combination of (meth)acryloyl-terminated oligomers. As described in the context of the reaction products, a (meth)acryloyl-terminated oligomer is derived from the reaction of a first reagent, a second reagent that is different from the first reagent, and an acrylating agent. The (meth)acryloyl-terminated oligomer has a molecular weight that is greater than the molecular weight of the first and second reagents.

[0096] The compositions provided by the present invention may comprise the reaction product of reagents comprising: (a) a first reagent, having two active hydrogen groups, a first reagent having the structure of Formula (5): (5) where b is selected from 0 or 1; it is already an integer from 1 to 6; (b) a second reagent, comprising two or more active hydrogen groups, wherein each of the two or more active hydrogen groups is independently selected from hydroxyl or thiol; at least one of the two or more active hydrogen groups is a thiol; and the second reagent is different from the first reagent; and (c) a third reagent comprising an acrylating agent.

[0097] In the reagents of Formula (5), b can be 0 or ob can be 1.

[0098] In the reagents of Formula (5), a can be an integer from 1 to 5, from 1 to 4, from 1 to 3 or from 1 to 2.

[0099] In Formula (5) reagents, a can be selected from 1 or 2.

[0100] In the reagents of Formula (5), a can be 1, 2, 3, 4, 5 or 6.

[0101] Examples of Formula (5) reagents include bis(2-mercaptoethyl) sulfide (5a). SH (5a)

[0102] The second reagent may comprise, for example, 2 to 6 active hydrogen groups, such as 2 to 5, 2 to 4, or 2 to 3 active hydrogen groups. The second reagent may comprise, for example, 2, 3, 4, 5, or 6 active hydrogen groups. The second reagent may be a combination of reagents having different functionalities such that the average functionality of the active hydrogen groups may be a non-integer value from 2 to 6, 2 to 5, 2 to 4, or 2 to 3.

[0103] Examples of suitable active hydrogen groups include hydroxyl groups and thiol groups.

[0104] The second reagent may comprise a cyclic reagent having the structure of Formula (6), a branched reagent having the structure of Formula (7), or a combination thereof: X ^X H R2H(6) B(-R3-XH)z(7) where z is an integer from 3 to 6; each X is selected independently of O or S; and at least one X is S; and R2 is selected from (heterocycloalkane)alkane-diyl, C6-20 heteroalkane-diyl, substituted (heterocycloalkane)alkane-diyl, or substituted Ce 20 heteroalkane-diyl; R3 is selected from C12 alkane-diyl, C212 heteroalkane-diyl, C512 heterocycloalkane-diyl, Ce12 heteroarene-diyl, (heterocycloalkane)alkane-diyl, Ce20 heteroalkanearene-diyl, C2-12 alkane-diyl, substituted C212 heteroalkane-diyl, substituted C5-12 heterocycloalkane-diyl, Ce12 heteroarene-diyl, substituted (heterocycloalkane)alkane-diyl, or C6-20 heteroalkanearene-diyl; and B is a multifunctional part.

[0105] In the reagents of Formula (6) and Formula (7), each of one or more of the heteroatoms X can be S.

[0106] In the reagents of Formula (6) and Formula (7), each of one or more of the substituent groups can be independently selected from either thiol (-SH) or hydroxyl (-OH).

[0107] The second reagent may comprise, for example, 4,8-dimercaptoethyl-l,l 1-dimercapto3,6,9-trithiaundecane, 4-mercaptomethyl-3,6-dithia-l,8-octanedithiool (2,2'-((3-mercaptopropane-l,2diyl)bis(sulfanediyl))bis(ethane-l-thiol)), 7-hydroxymethyl-3,6,9,12-tetrathia-l,14-tetradecanedithiool (2,3-bis((2((2-mercaptoethyl)thio)ethyl)thio)propan-l-ol) and / or isomers thereof, 2,5-dimercaptomethyl-l,4-dithiano ((l,4-dithiano-2,5-diyl)dimethanethiol) or combinations of any of the above.

[0108] The second reagent may comprise, for example, 2,5-dimercaptomethyl-l,4-dithiane (8a), 2-ethyl-2-(mercaptomethyl)propane-l,3-dithiol (8b), 1,2,3-trimercaptopropane (8c), 2,2-bis(mercaptomethyl)propane-l,3-dithiol (8d), 4-mercaptomethyl-3,6-dithial-l,8-octanedithiol (8e), 1,3-dimercapto-2-propanol (8f), 3-mercapto-l,2-propanediol (8g), 2,3-dimercapto-1-propanol (8h), 7-hydroxymethyl-1,14-dimercapto-3,6,9,12-tetrathiatetradecane (8i), 7-[2-(hydroxyethyl)] -1,13-dimercapto-3,6,8,11-tetrathiatridecane, 4,8-bis(mercaptomethyl)-1,1-dimercapto-3,6,9-trithiaundecane (8j) or regioisomers of (8j) such as the regioisomers 4,7- or 5,7-, 2-mercapto-1,3-propanediol (8k) or combinations of any of the foregoing. These compounds have the structure of Formula (8a)(8k): nn / Lznz / E / YiAi (8a) (8b) (8c) (8d) (8e) (8f) (8g) (8h) (8i) (8j) SH (8k)

[0109] The thiol-containing reagents provided by this description may comprise partially alkoxylated reagents in which at least one or more of the thiol groups have been extended, for example, with a -CH2-CH2-OH, -CH(-CH3)-CH2-OH, or -CH(-CH3)2-CH2-OH group. The thiol groups may be hydroxylated by reaction with, for example, an ethylene oxide. For example, the partially ethoxylated reagents of formula (8j) may have the structure: > NC£

[0112] In reagents, the ratio of active hydrogen group equivalents (i.e., the sum of hydroxyl and thiol equivalents) of the first reagent to the active hydrogen group equivalents of the second reagent is greater than 1:1.

[0113] For example, the ratio of active hydrogen group equivalents of the first reactant to the second reactant may be greater than 2:1, greater than 3:1, greater than 4:1, greater than 5:1, greater than 6:1, greater than 7:1 or greater than 8:1.

[0114] The ratio of active hydrogen group equivalents of the first reagent to the second reagent can be, for example, from 2:1 to 10:1, from 3:1 to 9:1, from 4:1 to 8:1 or from 5:1 to 7:1.

[0115] The reaction products may comprise a first (meth) acryloyl-terminated monomer, a second (meth) acryloyl-terminated monomer that differs from the first (meth) acryloyl-terminated monomer, and a combination of (meth) acryloyl-terminated oligomers.

[0116] The first monomer terminated in (meth) acryloyl can be derived from the first reagent, the second monomer terminated in (meth) acryloyl can be derived from the second reagent, and the combination of oligomers terminated in (meth) acryloyl can be derived from the reaction of the first reagent, the second reagent, and the acrylating agent.

[0117] The first (meth) acryloyl-terminated monomer derived from the first reagent may comprise a reagent having the structure of Formula (1).

[0118] The second (meth)acryloyl-terminated monomer derived from the second reagent may comprise the second reagent terminated in (meth)acryloyl groups. The second (meth)acryloyl-terminated monomer derived from the second reagent may comprise a (meth)acryloyl-terminated monomer of Formula (2), Formula (3), or a combination thereof.

[0119] The combination of oligomers terminated in (meth) acryloyl can be derived from the reaction of the active hydrogen groups of the first reagent and the active hydrogen groups of the second reagent with the acrylating agent and via Michael addition with the activated alkenyl of (meth) acrylate.

[0120] The oligomer terminated in (meth)acryloyl may comprise parts derived from the first and second reactants. For example, an oligomer terminated in (meth)acryloyl may comprise from 1 to 50 parts derived from the first reactant and from 1 to 50 parts derived from the second reactant. An oligomer terminated in (meth)acryloyl may independently comprise from 1 to 40, from 1 to 30, from 1 to 20, from 1 to 10, or from 1 to 5 parts derived from the first and second reactants.

[0121] Each of the first reagent and the second reagent may independently comprise, for example, from 15% by weight to 55%, such as from 20% by weight to 50% by weight, from 25% by weight to 50% by weight, or from 25% by weight to 45% by weight of sulfur, where the % by weight is based on the molecular weight of the respective reagent.

[0122] The combination of oligomers terminated in (meth)acryloyl may have an average (meth)acryloyl functionality greater than the functionality of the second reagent. For example, the combination of oligomers may have an average (meth)acryloyl functionality greater than 3, greater than 5, greater than 7, or greater than 9. The combination of oligomers may have an average (meth)acryloyl functionality, for example, of 3 to 10, 4 to 10, or 6 to 10.

[0123] The combination of oligomers terminated in (meth) acryloyl may comprise, for example, from 1 to 50 parts derived from the first reagent and from 1 to 50 parts derived from the second reagents.

[0124] An oligomer terminated in (meth) acryloyl may comprise, for example, from 15 wt to 55 wt sulfur, such as from 20 wt to 50 wt, from 25 wt to 50 wt or from 25 wt to 45 wt sulfur, wherein the wt % is based on the molecular weight of the oligomer or combinations of oligomers.

[0125] Methods for synthesizing a composition comprising a combination of (meth) acryloyl-terminated monomers and (meth) acryloyl-terminated oligomers may comprise: (A) combining the reagents (i), (ii) and (iii) to form the mixture, wherein the reagents comprise: (i) a first reagent, having two active hydrogen groups, the first reagent having the structure of Formula (5): where b is selected from 0 or 1; it is already an integer from 1 to 6; (ii) a second reagent comprising two or more active hydrogen groups, wherein each of the two or more active hydrogen groups is selected from hydroxyl or thiol; at least one of the two or more active hydrogen groups is a thiol; and the second reagent (ii) is different from the first reagent (i); and (iii) a third reagent, wherein the third reagent comprises an acrylating agent; and (B) reacting the mixture in the presence of a base to provide the combination of (meth) acryloyl-terminated monomers and (meth) acryloyl-terminated oligomers.

[0126] The methods of synthesis of the compositions provided by the present description may include the steps of (1) forming salts of the reagents containing active hydrogen (i) and (ii), individually or combined, by reacting with at least a quantitative amount of a strong base such as, but not limited to, sodium hydroxide (NaOH), potassium hydroxide (KOH) or an alkoxide in relation to the amount of equivalents of active hydrogen; (2) combining the salts with a clarifying agent (iii), for example, by adding the clarifying agent to the salts, adding the salts to the clarifying agent or simultaneously combining the salts and the clarifying agent; and (3) removing the water-soluble salt by-products.

[0127] The synthesis methods of the compositions provided by the present invention may include (1) combining reagents containing active hydrogen and an acrylating agent; (2) adding a quantitative amount of a strong base such as NaOH, KOH, or an alkoxide in relation to the amount of active hydrogen equivalents; and (3) removing soluble salt by-products.

[0128] The synthetic methods for the compositions provided herein may include partially alkoxylating the second reagent to form the corresponding alcohols on a portion of the thiol groups by reaction with an alkoxylating agent before the addition of the strong base, which forms a partially alkoxylated second reagent. For example, a polythiol reagent may be partially ethoxylated so that a portion of the thiol groups is extended with less than 1 equivalent of oxirane functional material as ethylene oxide relative to the number of thiol equivalents. For example, less than 0.9 equivalents, less than 0.75 equivalents, or less than 0.5 equivalents of the thiols may be alkoxylated.

[0129] The acrylating agent may comprise (meth)acryloyl chloride or (meth)acrylic anhydride. For example, the acrylating agent may be (meth)acryloyl chloride.

[0130] Suitable bases include alkaline bases, non-limiting examples of which include sodium hydroxide and potassium hydroxide, an alkoxide such as sodium alkoxide, or a combination of any of the above.

[0131] The reaction can be carried out in the presence of a solvent such as, for example, chlorinated hydrocarbons including dichloromethane and chloroform; ethers including diethyl ether, dibutyl ether and 1 / 8-butyl methyl ether; esters including ethyl acetate and butyl acetate or combinations of any of the above.

[0132] The reaction mixture may also include water.

[0133] The reaction mixture may further comprise free radical inhibitors. Non-limiting examples of suitable free radical inhibitors include phenols such as 4-methoxyphenol, 4-erg-butylcatechol, or combinations of any of the foregoing.

[0134] In the reaction mixture, the ratio of acrylating agent equivalents to active hydrogen group equivalents may be, for example, 1:1 or greater than 1:1 such as greater than 1.05:1, greater than 1.08:1, greater than 1.1:1, greater than 1.15:1, greater than 1.2:1, greater than 1.4:1, greater than 1.6:1, greater than 1.8:1 or greater than 1.9:1.

[0135] In the reaction mixture, the ratio of equivalents of acrylating agent to equivalents of active hydrogen groups can be, for example, from 1:1 to 2:1, from 1:1 to 1.5:1, from 1:1 to 1.25:1 or from 1:1 to 1.1:1.

[0136] In the reaction mixture, the ratio of base equivalents to equivalents of active hydrogen groups may be, for example, 1:1 or greater than 1:1 such as greater than 1.05:1, greater than 1.08:1, greater than 1.1:1, greater than 1.15:1, greater than 1.2:1, greater than 1.4:1, greater than 1.6:1, greater than 1.8:1 or greater than 1.9:1.

[0137] In the reaction mixture, the ratio of base equivalents to equivalents of active hydrogen groups can be, for example, from 1:1 to 2:1, from 1:1 to 1.5:1, from 1:1 to 1.25:1 or from 1:1 to 1.1:1.

[0138] The ratio of active hydrogen group equivalents of the first reactant to the second reactant may be greater than 1:1, greater than 2:1, greater than 3:1, greater than 4:1, greater than 5:1, greater than 6:1, greater than 7:1 or greater than 8:1.

[0139] The ratio of active hydrogen group equivalents of the first reagent to the second reagent can be, for example, from 1:1 to 25:1, from 1:1 to 20:1, from 1:1 to 15:1, from 1:1 to 10:1, from 2:1 to 10:1, from 3:1 to 8:1 or from 5:1 to 7:1.

[0140] The synthetic methods provided herein yield compositions having a combination of (meth)acryloyl-terminated monomers and (meth)acryloyl-terminated oligomers with a yield, for example, greater than 60%, greater than 70%, greater than 80%, greater than 90%, or greater than 95%. The synthetic methods provided herein yield compositions having a combination of (meth)acryloyl-terminated monomers and (meth)acryloyl-terminated oligomers with a yield, for example, of 70% to 100%, 75% to 98%, or 80% to 95%.

[0141] A polymerizable composition may comprise the combination of (meth)acryloyl-terminated monomers and (meth)acryloyl-terminated oligomers, a curing initiator, and optionally one or more additives.

[0142] The polymerizable compositions provided herein may comprise a curing initiator such as a free radical initiator. The polymerizable pRz / nn / Lznz / B / Yi compositions may comprise one or more free radical initiators such as thermally activated free radical initiators or actinic radiation-activated free radical initiators. A thermally activated free radical initiator may become active at elevated temperatures, such as above 25°C.

[0143] Examples of suitable thermally activated free radical initiators include peroxyorganic compounds such as azobis(organonitrile) compounds, / V-acyloxyamine compounds, O-imino-isourea compounds, or combinations of any of the above.Examples of suitable peroxyorganic compounds that can be used as initiators of thermal polymerization include peroxymonocarbonate esters, such as 2-ethylhexyl tertiary butylperoxy carbonate and isopropyl tertiary butylperoxy carbonate; peroxycetals, such as l,l-di-(yer-butyl peroxy)-3,3,5-trimethylcyclohexane; peroxydicarbonate esters, such as di(2-ethylhexyl)peroxydicarbonate, di(butyl)peroxydicarbonate and diisopropylperoxydicarbonate; diacylperoxides such as 2,4-dichlorobenzoyl peroxide, isobutyryl peroxide, decanoyl peroxide, lauryl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide and p-chlorobenzoyl peroxide; peroxyesters such as tert-butylperoxy pivalate, tert-butylperoxy octylate and tert-butylperoxyisobutyrate; methyl ethyl ketone peroxide, acetylcyclohexane sulfonyl peroxide or combinations of any of the above.Other examples of suitable peroxy compounds include 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane and / or 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane. Examples of suitable azobis(organonitrile) compounds that can be used as initiators of thermal polymerization include azobis(isobutyronitrile), 2,2'-azobis(2-methylbutanenitrile), and / or azobis(2,1-dimethylvaleronitrile). A thermally activated free-radical initiator may comprise 1,3-acetoxy-2,2,6,6-tetramethylpiperidine and / or 1,3-dicyclohexyl-O(A-cyclohexylideneaminoj-isourea.

[0144] A free radical initiator may comprise a photoinitiator.

[0145] The polymerizable compositions provided by this description may include a photoinitiator or combination of photoinitiators. The radiation may be actinic radiation that can apply energy capable of generating an initiator species from a photopolymerization initiator after irradiation with it, and broadly includes alpha rays, gamma rays, X-rays, ultraviolet (UV) light (including UVA, UVB, and UVC spectra), visible light, blue light, infrared, near-infrared, or an electron beam. For example, the photoinitiator may be a UV photoinitiator.

[0146] Examples of suitable UV photoinitiators include α-hydroxyketones, benzophenones, α,α.-diethoxyacetophenone, 4,4-diethylaminobenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-isopropylphenyl 2hydroxy-2-propyl ketone, 1-hydroxycyclohexyl phenyl ketone, p-isoamyl dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, methyl O-benzoylbenzoate, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-hydroxy-2-methyl-l-phenylpropan-l-one, 2-isopropylthioxantone, pR7 / nn / L7nz / E / Yii dibenzosuberone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bisacyclophosphine oxide.

[0147] Examples of suitable benzophenone photoinitiators include 2-hydroxy-2-methyl-l-phenyl-1-propanone, 2-hydroxy-1,4,4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, α-dimethoxy-α-phenylacetophenone, 2-benzyl-2-(dimethylamino)-l-[4-(4-morpholinyl)phenyl]-l-butanone, and 2-methyl-l-[4(methylthio)phenyl]-2-(4-morpholinyl)-l-propanone.

[0148] Examples of suitable oxime photoinitiators include (hydroxyimino)cyclohexane, l-[4-(phenylthio)phenyl]-octane-l,2-dione-2-(O-benzoyloxime), l-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-l-(O-acetyloxime), trichloromethyl-triazine derivatives), 4-(4-methoxystyryl)-2,6-trichloromethyl-l,3,5triazine), 4-(4-methoxyphenyl)-2,6-trichloromethyl-l,3,5-triazine and α-aminoketone (l-(4-morpholinophenyl)-2dimethylamino-2-benzyl-butan-1 -one).

[0149] Examples of suitable phosphine oxide photoinitiators include diphenyl (2,4,6-trimethylbenzoyl)-phosphine oxide (TPO) and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO).

[0150] Other examples of suitable UV photoinitiators include BASF's Irgacure™ products, for example Irgacure™ 184, Irgacure™ 500, Irgacure™ 1173, Irgacure™ 2959, Irgacure™ 745, Irgacure™ 651, Irgacure™ 369, Irgacure™ 907, Irgacure™ 1000, Irgacure™ 1300, Irgacure™ 819, Irgacure™ 819DW, Irgacure™ 2022, Irgacure™ 2100, Irgacure™ 784 or Irgacure™ 250; In addition, BASF's Irgacure™ products are used, for example Irgacure™ MBF, Darocur™ 1173, Darocur™ TPO, and Darocur™ 4265.

[0151] A UV photoinitiator may comprise, for example, 2,2-dimethoxy-l,2-diphenylethan-lone (Irgacure® 651, Ciba Specialty Chemicals), 2,4,6-trimethylbenzoyl-diphenyl-phosphinoxide (Darocur® TPO, Ciba Specialty Chemicals) or a combination thereof.

[0152] Other examples of suitable photoinitiators include Darocur® TPO (available from Ciba Specialty Chemicals), Lucirin® TPO (available from BASF), Speedcure® TPO (available from Lambson), Irgacure® TPO (available from Ciba Specialty Chemicals) and Omnirad® (available from IGM Resins) or combinations of any of the above.

[0153] The compositions provided by the present description may comprise from 0.05 wt to 5 wt, from 0.1 wt to 4.0 wt, from 0.25 wt to 3.0 wt or from 0.5 wt to 1.5 wt of a photoinitiator or combination of photoinitiators, wherein the wt % is based on the total weight of the polymerizable composition.

[0154] Polymerizable compositions may further comprise a free radical inhibitor, a thermal stabilizer, a UV stabilizer, a UV absorber, a hindered amine photostabilizer, a dichroic material, a photochromic material, a polymerization moderator, a polymerization accelerator, a monomer having a single ethylenically unsaturated radical polymerizable group, a monomer having two or more ethylenically unsaturated radical polymerizable groups, a pigment, a dye, or a combination of any of the foregoing.

[0155] The polymerizable compositions provided by this description may comprise a free radical inhibitor or a combination of free radical inhibitors. Examples of suitable free radical inhibitors include 4-methoxyphenol, hydroxyquinone, pyrogallol, 2,4-dimethyl-6-tert-butylphenol, butylated hydroxytoluene (BHT), or 4-tert-butylcatechol.

[0156] The polymerizable compositions provided by the present description may comprise a thermal stabilizer or a combination of thermal stabilizers.

[0157] The polymerizable compositions provided by this description may comprise a UV stabilizer or a combination of UV stabilizers. UV stabilizers include UV absorbers and hindered amine photostabilizers. Examples of suitable UV stabilizers include products under the trade names Cyasorb® (Solvay), Uvinul® (BASF), and Tinuvin® (BASF).

[0158] The polymerizable compositions provided by this description may comprise a dichroic material or a combination of dichroic materials. Examples of suitable dichroic materials include azomethines, indigoids, thioindigoids, merocyanines, indanes, quinophthalene dyes, perylenes, phthaloperines, triphenodioxazines, indoloquinoxalines, imidazotriazines, tetrazines, azo and (poly)azo dyes, benzoquinones, naphthoquinones, anthraquinone, (poly)anthraquinones, anthropyrimidinones, iodine, and iodates.

[0159] The polymerizable compositions provided by the present description may comprise a photochromic material or a combination of photochromic materials. A photochromic material may be a reversible photochromic material or a non-reversible photochromic material. A photochromic material may be a thermally reversible photochromic material or a thermally non-reversible photochromic material.

[0160] The polymerizable compositions provided by the present description may comprise a third monomer or combination of third monomers having ethylenically unsaturated radical polymerizable groups or a combination of monomers having ethylenically unsaturated radical polymerizable groups, wherein the third monomer is different from the first monomer and the second monomer.

[0161] A third monomer may have one group polymerizable by ethylenically unsaturated radicals or more than one group polymerizable by ethylenically unsaturated radicals. For example, a third monomer may comprise two groups polymerizable by ethylenically unsaturated radicals, three groups polymerizable by ethylenically unsaturated radicals, or more than three groups polymerizable by ethylenically unsaturated radicals.

[0162] The polymerizable compositions provided by the present description may comprise at least one third (meth)acryloyl-terminated monomer, wherein at least one third (meth)acryloyl-terminated monomer is different from the first (meth)acryloyl-terminated monomer and the second (meth)acryloyl-terminated monomer.

[0163] Examples of suitable third monomers having a single ethylenically unsaturated radical polymerizable group include mono(meth)acrylates such as cyclohexyl (meth)acrylate, butyl (meth)acrylate, methyl (meth)acrylate, isobornyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, ethyl (meth)acrylate; vinyl ethers, styrene, or combinations of any of the above.

[0164] Examples of suitable third monomers having more than one ethylenically unsaturated radical polymerizable group include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, poly(ethylene glycol) di(meth)acrylate, trimethylolpropane poly(meth)acrylates, pentaerythritol poly(meth)acrylates, ditrimethylolpropane poly(meth)acrylates, dipentaerythritol poly(meth)acrylates, glycerol poly(meth)acrylates, bisphenol A di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, cyclohexanediol di(meth)acrylates, and poly(meth)acrylates of tris(2-hydroxyethyl) isocyanurate, divinyl benzene or combinations of any of the above.

[0165] The polymerizable compositions provided by the present description may comprise a polymerization moderator or a combination of polymerization moderators. A polymerization moderator may minimize the formation of any distortion or defects, for example, striations and / or cracks / fissures, in the polymerized products obtainable from the polymerizable compositions of the present invention. Examples of suitable polymerization moderators include dilauryl thiodipropionate, l-isopropyl-4-methyl-l,4-cyclohexadiene (γ-terpinene); l-isopropyl-4-methyl-l,3-cyclohexadiene (α-terpinene); l-methyl-4-(propan-2-ylidene)cyclohex-1-ene (terpinolene); and alpha-methylstyrene dimer, 1,1-diphenylethylene, cis-l,2-diphenylethylene, 3,7,7-trimethylbicyclo[4.1.0]hept-3-ene (3carene), 4-isopropenyl-1-methylcyclohexene (dipentene), (S)-(4-isopropenyl-l-methylcyclohexene ((S)limonene), 2,6-dimethyl-2,4,6-octatriene, 4-tert-butylpyrocatechol, triphenylmethane or combinations of any of the above.

[0166] A polymerization moderator may comprise l-isopropyl-4-methyl-l,4-cyclohexadiene; 1-isopropyl-4-methyl-1,3-cyclohexadiene; 1-methyl-4-(propan-2-ylidene)cyclohex-1-ene; 2,6-dimethyl-2,4,6-octatriene; an α-methylstyrene dimer; or a combination of any of the foregoing. An α-methylstyrene dimer refers to a polymerization moderator as 2,4-diphenyl-4-methyl-l-pentene and optionally at least one of 2,4-diphenyl-4-methyl-2-pentene and / or 2-phenyl-1-propene (which is also referred to as α-methylstyrene). With some embodiments, the α-methylstyrene dimer polymerization moderator includes 90 to 93 wt percent of 2,4-diphenyl-4-methyl-l-pentene, 6 to 8 wt percent of 2,4-diphenyl-4-methyl-2-pentene and 0.25 to 0.75 wt percent of 2-phenyl-l propene, based on the wt percents in each case in the total wt of α-methylstyrene.

[0167] A composition may comprise, for example, from 0.01 wt to 15 wt or from 0.1 wt to 8 wt or from 0.3 wt to 5 wt, of a polymerization moderator, wherein the wt % is based on the total weight of the composition.

[0168] The polymerizable compositions provided by the present description may comprise a polymerization accelerator (or incorporation percentage) or combinations of polymerization accelerators. A polymerization accelerator may increase the polymerization rate of the polymerizable composition of the present invention when exposed to actinic radiation. Examples of suitable polymerization accelerators include organophosphines, organophosphites, amines, or combinations thereof. Examples of suitable polymerization accelerators may include compounds with aliphatic substitution, cycloaliphatic substitution, aryl substitution, or combinations thereof. Examples of suitable organophosphine polymerization accelerators include triethylphosphine, tripropylphosphine, tributylphosphine, triphenylphosphine, or a combination thereof.For example, the accelerator for organophosphine polymerization can be triphenylphosphine. Examples of suitable organophosphite polymerization accelerators include triethylphosphite, tripropylphosphite, tributylphosphite, triphenylphosphite, or combinations thereof. For example, the accelerator for organophosphite polymerization is triethylphosphite. In one example, the accelerator for organophosphite polymerization can be triphenylphosphite. Examples of suitable amine polymerization accelerators include tertiary amines, such as triethylamine, N-methyldiethanolamine, N,N-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, tribenylamine, and 1,4-diazabicyclo[2.2.2]octane. For example, the accelerator for amine polymerization is triethylamine.

[0169] The compositions presented in this description may comprise, for example, from 0.001 wt% to 10 wt%, from 0.01 wt% to 5 wt% or from 0.05 wt% to 2 wt% of a polymerization accelerator or combination of polymerization accelerators, wherein the wt% is based on the total weight of the polymerizable composition.

[0170] The polymerizable compositions provided by this description may comprise pigments, dyes, or combinations thereof.

[0171] Examples of suitable inorganic pigments include metal-containing inorganic pigments such as those containing cadmium, carbon, chromium, cobalt, copper, iron oxide, lead, mercury, titanium, tungsten, and zinc. Examples include ultramarine blue, ultramarine violet, reduced tungsten oxide, cobalt aluminate, cobalt phosphate, manganese ammonium pyrophosphate, and / or metal-free inorganic pigments. In particular embodiments, inorganic pigment nanoparticles comprise ultramarine blue, ultramarine violet, Prussian blue, cobalt blue, and / or reduced tungsten oxide. Examples of specific organic pigments include indanthrone, quinacridone, phthalocyanine blue, copper phthalocyanine blue, and perylene anthraquinone.

[0172] Additional examples of suitable pigments include iron oxide pigments, in shades of yellow, brown, red, and black; in all their physical forms and grain categories; titanium oxide pigments in all their different inorganic surface tetramers; chromium oxide pigments also coprecipitated with nickel and nickel titanates; organic combustion black pigments (e.g., carbon black); blue and green pigments derived from copper phthalocyanine, also chlorinated and brominated, in the various alpha, beta, and epsilon crystalline forms; yellow pigments derived from lead sulfochromate; yellow pigments derived from lead vanadate and lead bismuth; orange pigments derived from lead sulfochromate molybdate; yellow pigments of organic nature based on arylamides; orange pigments of organic nature based on naphthol; orange pigments of organic nature based on diketo-pyrrolo-pyrrole;red pigments based on manganese salts of azo dyes; red pigments based on manganese salts of beta-oxynaphthoic acid; red organic quinacridone pigments; and red organic anthraquinone pigments.

[0173] The polymerizable compositions provided by the present description may be cured by activating a free radical reaction, for example, by exposing the polymerizable composition to actinic radiation. A cured polymerizable composition is referred to as a polymerize.

[0174] The polymers provided by the present description may have a Fischer microhardness, for example, greater than 90 Newtons per square millimeter (N / mm2), greater than 100 N / mm2, greater than 110 N / mm2, greater than 120 N / mm2, greater than 130 N / mm2, greater than 140 N / mm2 or greater than 150 N / mm2, wherein the Fischer microhardness is measured using a Fischerscope H100SMC, available from Fischer Technology, Inc. at a load of 300 mN, after an application of a load of 0-300 mN in 15 seconds.

[0175] The polymers provided by the present description may have a Fischer microhardness, for example, of 90 N / mm2 to 160 N / mm2, 100 N / mm2 to 150 N / mm2, 110 N / mm2 to 140 N / mm2 or 120 N / mm2 to 140 N / mm2, wherein the Fischer microhardness is measured using a Fischerscope H-100SMC, available from Fischer Technology, Inc., at a load of 300 mN, after an application of a load of 0-300 mN in 15 seconds.

[0176] The polymerized products provided by this description may have an Abbe number, for example, greater than or equal to 30, greater than or equal to 32, greater than or equal to 34, or greater than or equal to 36, wherein the Abbe number is measured using a Metricon Model 2010M prism coupler in accordance with ASTM C1648. The Abbe number Vd may be calculated in accordance with Equation 1, pRz / nn / Lznz / B / Yi Equation 1 where no, np and nc are the refractive indices of the material at the wavelengths of the Fraunhofer D-, F- and C- spectral lines, i.e., 589.3 nm, 486.1 nm and 656.3 nm, respectively.

[0177] The polymers provided by the present description may have an Abbe number, for example, of 30 to 50, 32 to 45, or 33 to 42, where the Abbe number is measured using a Metricon Model 2010M prism coupler in accordance with ASTM C1648.

[0178] The polymers provided by the present description may have a refractive index, for example, greater than 1.50, greater than 1.54, greater than 1.58, greater than 1.62, greater than 1.66, greater than 1.70 or greater than 1.74, wherein the refractive index is measured using a Metricon Model 2010M prism coupler in accordance with ASTM C1648 at 20°C at a wavelength of 546.07 nm (the e line of mercury) and are reported as ne20.

[0179] The polymers provided by the present description may have a refractive index, for example, of 1.50 to 1.75, 1.52 to 1.73, 1.54 to 1.71, 1.56 to 1.69, 1.58 to 1.67, 1.60 to 1.65, or 1.61 to 1.64, wherein the refractive index is measured using a Metricon Model 2010M prism coupler in accordance with ASTM C1648 at 20°C at a wavelength of 546.07 nm (the e line of mercury) and are reported as ne20.

[0180] The polymers provided by the present description may have a storage modulus (E'), for example, greater than 1.5 Gigapascals (GPa) at 25°C or greater than 2.0 GPa, greater than 2.5 GPa, greater than 3.0 GPa or greater than 3.5 GPa, wherein the storage modulus E' is measured at 25°C on samples 3.5 millimeters (mm) thick according to ASTM D5023 “Standard Test Method for Plastics. Dynamic Mechanical Properties: In Flexure (Three-Point Bending)” using the Perkin Elmer DMA Diamond analyzer.

[0181] The polymers provided by the present description may have a storage modulus E', for example, greater than 0.5 at 75°C, greater than 10 GPa, greater than 1.5 GPa or greater than 2.0 GPa, wherein the storage modulus E' is measured at 75°C on 3.5 mm thick samples according to ASTM D5023 “Standard Test Method for Plastics. Dynamic Mechanical Properties: In Flexure (Three-Point Bending)” using a Perkin Elmer Diamond DMA analyzer.

[0182] The polymers provided by the present description may have a yellowing index, for example, less than 5, less than 4, less than 3, less than 2.8, less than 2.6, less than 2.4 or less than 2.2, where the yellowing index is measured using a HunterLab UltraScan PRO in accordance with ASTM E313 on samples 3.5 mm thick.

[0183] The polymers provided by the present description may have a yellowing index, for example, of 1.0 to 5.0, 1.0 to 4.0, 1.0 to 3.0, 1.5 to 2.8, 1.75 to 2.6, or 2.0 to 2.5, where the yellowing index is measured using a HunterLab UltraScan PRO apparatus in accordance with ASTM E313 on samples 3.5 mm thick.

[0184] The polymerizable compositions provided by the present description can be used to manufacture articles such as optical components.

[0185] Articles that can be manufactured from the curable compositions provided by the present description using any suitable method such as by casting, additive manufacturing such as three-dimensional printing and inkjet printing, transfer printing or stereolithography.

[0186] For example, an article may be manufactured by forming a polymerizable composition into a shape and curing the polymerizable composition. Curing may comprise initiating a free-radical reaction to cause the (meth) acryloyl groups to react and form a polymer. Initiating a free-radical reaction may comprise, for example, exposing the polymerizable composition to actinic radiation such as visible or UV radiation. The polymerizable composition may be exposed to actinic radiation before the article is formed, while the article is being formed, after the article is formed, or a combination of any of the above. After the free-radical reaction has been initiated, the article may be subjected to heat treatment to accelerate the completion of curing. For example, the formed article may be exposed to a temperature greater than 50°C, greater than 75°C, or greater than 100°C for 30 minutes to 2 hours.

[0187] Three-dimensional printing can be used to manufacture an item.

[0188] Three-dimensional printing may involve the deposition of sequential layers of a material to form an article. The polymerizable compositions provided herein may be supplied as a one-part system which can be pumped into a mixer and extruded under pressure through a nozzle. An article may be constructed by depositing sequential layers of polymerizable composition in the shape of the article. The free radical reaction may be initiated by exposing the polymerizable composition to heat or actinic radiation as the composition passes through the pump, mixer, and / or nozzle and / or after the polymerizable composition has been deposited. A free radical initiator may be combined with a composition comprising a combination of (meth)acryloyl-terminated monomers and / or (meth)acryloyl-terminated oligomers, mixed, and then sequentially deposited to construct an article.The free radical reaction can be initiated by exposing the polymerizable composition to heat and / or actinic radiation or after mixing.

[0189] The polymerizable compositions and methods provided by the present description can be used to manufacture a wide variety of optical components including, for example, optical displays, shields, windows, transparencies, windscreens, eyeglasses, visors, ophthalmic lenses, optical lenses, sports masks, face shields, goggles, imaging systems, cameras, optical components, optoelectronic devices, light-emitting diodes, lasers, photodetectors, photovoltaic energy, LIDAR imaging, telecommunication devices, and infrared communication devices.

[0190] Optical components manufactured using the compositions and methods provided by this description may include one or more coatings.

[0191] One or more of the coatings may include where one or more of the surface coatings comprises a scratch-resistant coating, an anti-reflective coating, a wavelength-selective reflective coating, a wavelength-selective absorbing coating, a planarizing coating, a polarizing coating, or a combination of any of the foregoing. ASPECTS OF THE INVENTION

[0192] The invention is further defined by the following aspects of the invention.

[0193] Aspect 1. A composition comprising: (a) a first monomer terminated in (meth) acryloyl, wherein the first monomer terminated in (meth) acryloyl has the structure of Formula (1): OO (1) where each R1 is independently selected from hydrogen or methyl; (b) is selected from 0 or 1; is an integer from 1 to 6; and (b) a second (meth) acryloyl-terminated monomer comprising two or more (meth) acryloyl groups, wherein each of the two or more (meth) acryloyl groups is independently selected from an (meth) acryloyloxy group and an (meth) acryloylthio group; at least one of the (meth) acryloyl groups is a (meth) acryloylthio group; and the second (meth) acryloyl-terminated monomer (b) is different from the first (meth) acryloyl-terminated monomer.

[0194] Aspect 2. The composition of aspect 1, where each R1 is hydrogen.

[0195] Aspect 3. The composition of aspect 1, where each R1 is methyl.

[0196] Aspect 4. The composition of any of aspects 1 to 3, where b is 0.

[0197] Aspect 5. The composition of any of aspects 1 to 3, where b is 1.

[0198] Aspect 6. The composition of any of aspects 1 to 5, where a is sectioned from 1 or pRz / nn / Lznz / B / Yi 2.

[0199] Aspect 7. The composition of aspect 1, wherein the first monomer terminated in (meth) acryloyl comprises bis(2-methacryloylthioethyl) sulfide:

[0200] Aspect 8. The composition of any of aspects 1 to 7, wherein the second (meth) acryloyl-terminated monomer comprises a polythiaalkylene portion.

[0201] Aspect 9. The composition of aspect 8, wherein the polythiaalkylene part is an aliphatic polythiaalkylene part.

[0202] Aspect 10. The composition of aspect 8, wherein the polythiaalkylene part is a cyclic polythiaalkylene part or a branched polythiaalkylene part.

[0203] Aspect 11. The composition of aspect 8, wherein the polythiaalkylene part is a branched polythiaalkylene part and the second (meth) acryloyl-terminated monomer comprises 3 to 6 (meth) acryloyl groups.

[0204] Aspect 12. The composition of any of aspects 1 to 11, wherein the second (meth) acryloyl-terminated monomer comprises two or more (meth) acryloylthio groups.

[0205] Aspect 13. The composition of any of aspects 1 to 11, wherein the second (meth) acryloyl-terminated monomer comprises at least one (meth) acryloylthio group and at least one (meth) acryloyloxy group.

[0206] Aspect 14. The composition of any of aspects 1 to 7, wherein the second monomer terminated in (meth)acryloyl comprises 2,5-bis(methacryloylthiomethyl)l,4-dithian, 4(meth)acryloylthiomethyl-3,6-dithia-l,8-bis[(meth)acryloylthio]octane, 7-(meth)acryloyloxymethyl-3,6,9,12-tetrathia-1,14-bis[(meth)acryloylthio]tetradecane, 4,8-bis[(meth)acryloylthiomethyl]-3,6,9-trithia-1,11 bis[(meth)acryloylthio]undecane or regioisomers thereof such as the 4,7- and 5,7- regioisomers, 2-ethyl-2((meth)acryloylthiomethyl)-l,3-bis[(meth)acryloylthio]propane, l,2,3-tris[(meth)acryloylthio]propane or combinations of any of the above.

[0207] Aspect 15. The composition of any of aspects 1 to 7, wherein the second monomer terminated in (meth) acryloyl comprises 2,5-bis(methacryloylthiomethyl)l,4-dithian: EITHER

[0208] Aspect 16. The composition of any of aspects 1 to 7, wherein the second monomer terminated in (meth) acryloyl comprises 4-(meth) acryloylthiomethyl-3,6-dithia-1,8bis[(meth) acryloylthio] octane:

[0209] Aspect 17. The composition of any of aspects 1 to 16, wherein the composition further comprises an oligomer terminated in (meth) acryloyl.

[0210] Aspect 18. The composition of any of aspects 1 to 17, wherein the composition comprises from 15% by weight to 60% by weight of sulfur, as well as from 15% by weight to 55% by weight of sulfur, wherein % by weight is based on the total weight of the composition.

[0211] Aspect 19. The composition of any of aspects 1 to 17, wherein the composition comprises from 25% by weight to 45% by weight of sulfur, where % by weight is based on the total weight of the composition.

[0212] Aspect 20. The composition of any of aspects 1 to 19, wherein the first (meth) acryloyl-terminated monomer comprises a first (meth) acryloyl equivalent; the second (meth) acryloyl-terminated monomer comprises a second (meth) acryloyl equivalent; and a ratio of the first (meth) acryloyl equivalents to the second (meth) acryloyl equivalents is greater than 1:1.

[0213] Aspect 21. The composition of aspect 20, where the ratio is greater than 1:1:1.

[0214] Aspect 22. The composition of aspect 20, where the ratio is from 1:1 to 25:1.

[0215] Aspect 23. A composition comprising the reaction product of reactants comprising: (i) a first reagent, having two active hydrogen groups, the first reagent having the structure of Formula (5): where b is selected from 0 or 1; and is an integer from 1 to 6; (ii) a second reagent comprising two or more active hydrogen groups, wherein each of the two active hydrogen groups is independently selected from hydroxyl or thiol; at least one of the two or more active hydrogen groups is a thiol; and the second reagent is different from the first reagent; and (iii) a third reagent comprising an acrylating agent.

[0216] Aspect 24. The composition of aspect 23, where b is 0.

[0217] Aspect 25. The composition of aspect 32, where b is 1.

[0218] Aspect 26. The composition of any of aspects 23 to 25, where a is selected from 1 or 2.

[0219] Aspect 27. The composition of aspect 23, wherein the first reagent comprises bis(2-mer captoethyl)sulfate:

[0220] Aspect 28. The composition of any of aspects 23 to 27, wherein the second reagent comprises 2,5-dimercaptoethyl-1,4-dithian: SH

[0221] Aspect 29. The composition of any of aspects 23 to 27, wherein the second reagent comprises 4-dimercaptoethyl-3,6-dithia-l,8-octanedithiaol: SH

[0222] Aspect 30. The composition of any of aspects 23 to 27, wherein the second reagent comprises 7-hydroxymethyl-1,14-dimercapto-3,6,9,12-tetrathiatetradecane.

[0223] Aspect 31. The composition of any of aspects 23 to 27, wherein the second reagent comprises 2,5-dimercaptomethyl-1,4-dithiol, 2-ethyl-2-(mercaptomethyl)propane-1,3-dithiol, 1,2,3-trimercaptopropane, 2,2-bis(mercaptomethyl)propane-1,3-dithiol, 4-mercaptomethyl-3,6-dithiol-1,8-octanedithiol, 1,3-dimercapto-2-propanol, 3-mercapto-1,2-propanediol, 2-mercapto-1,3-propanediol, 2,3-dimercapto-1-propanol, 7-hydroxymethyl-1,14-dimercapto-3,6,9,12-tetrathiatetradecane, 4,8-bis(mercaptomethyl)-l, 11-dimercapto-3,6,9-trithiaundecane or regioisomers thereof, the 4,7- or 5,7- regioisomers, or combinations of any of the above.

[0224] Aspect 32. The composition of any of aspects 23 to 31, wherein the first reagent, the second reagent, or both of the first and second reagents comprise at least one ethoxylated thiol group.

[0225] Aspect 33. The composition of any of aspects 23 to 32, wherein the acrylating agent comprises (meth) acryloyl chloride or (meth) acrylate anhydride.

[0226] Aspect 34. The composition of any of aspects 23 to 33, wherein the ratio of active hydrogen group equivalents of the first reagent to the second reagent may be greater than 1:1.

[0227] Aspect 35. The composition of any of aspects 23 to 33, wherein the ratio of active hydrogen group equivalents of the first reagent to the second reagent is from 1:1 to 25:1.

[0228] Aspect 36. The composition of any of aspects 23 to 35, wherein the reaction product comprises a first (meth)acryloyl-terminated monomer, wherein the first (meth)acryloyl-terminated monomer is derived from the first reagent, a second (meth)acryloyl-terminated monomer, wherein the second (meth)acryloyl-terminated monomer is derived from the second reagent; and a combination of (meth)acryloyl-terminated oligomers, wherein the combination of the (meth)acryloyl-terminated oligomers is derived from the reaction of the first reagent, the second reagent, and the acrylating agent.

[0229] Aspect 37. The composition of any of aspects 23 to 36, wherein the composition comprises from 15% by weight to 60% by weight of sulfur, as well as from 15% by weight to 55% by weight of sulfur, wherein % by weight is based on the total weight of the composition.

[0230] Aspect 38. The composition of any of aspects 23 to 36, wherein the composition comprises from 25% by weight to 45% by weight of sulfur, where % by weight is based on the total weight of the composition.

[0231] Aspect 39. A polymerizable composition, wherein the polymerizable composition comprises: the composition of any of aspects 1 to 38; and a free radical initiator.

[0232] Aspect 40. The polymerizable composition of aspect 39, the free radical initiator comprises a photoinitiator or a thermally activated free radical initiator.

[0233] Aspect 41. The polymerizable composition of any of aspects 39 to 40, ΓΑζ / ηη / ίζηζ / Ε / γι further comprises a third monomer, wherein the third monomer comprises one or more groups polymerizable by ethylenically unsaturated radicals; and the third monomer is different from the first monomer terminated in (meth) acryloyl and from the second monomer terminated in (meth) acryloyl.

[0234] Aspect 42. The polymerizable composition of any of aspects 39 to 41 further comprises at least a third (meth) acryloyl-terminated monomer, wherein the at least third (meth) acryloyl-terminated monomer is different from the first (meth) acryloyl-terminated monomer and the second (meth) acryloyl-terminated monomer.

[0235] Aspect 43. The polymerizable composition of any of aspects 39 to 42, wherein the polymerizable composition further comprises one or more of a thermal stabilizer, a UV stabilizer, a UV absorber, a hindered amine photostabilizer, a dichroic material, a photochromic material, a polymerization moderator, a polymerization accelerator, a pigment, a dye, or a combination of any of the foregoing.

[0236] Aspect 44. A polymerizable composition of aspect 43, wherein polymerization accelerator may comprise an organophosphine, an organophosphate, an amine or a combination of any of the foregoing.

[0237] Aspect 45. A polymerized product prepared from the polymerizable composition of any of aspects 39 to 44.

[0238] Aspect 46. The polymer of aspect 45, wherein the polymer has a refractive index of 1.50 to 1.75, wherein the refractive index is measured using a Metricon Model 2010M prism coupler in accordance with ASTM C1648 at 20°C at a wavelength of 546.07 nm (the e-line of mercury) and is reported as ne20

[0239] Aspect 47. The polymer of aspect 45, wherein the polymer has a refractive index of 1.60 to 1.65, wherein the refractive index is measured using a Metricon Model 2010M prism coupler in accordance with ASTM C1648 at 20°C at a wavelength of 546.07 nm (the e-line of mercury) and is reported as ne20

[0240] Aspect 48. The polymerization of any of aspects 45 to 47, wherein the polymerization has a Fischer microhardness greater than 90 N / mm2, wherein the Fischer microhardness is measured using a Fischerscope H-100SMC, available from Fischer Technology, Inc. at a load of 300 mN, after an application of a 0-300 mN load in 15 seconds.

[0241] Aspect 49. The polymerization of any of aspects 45 to 47, wherein the polymerization has a Fischer microhardness greater than 120 N / mm2, wherein the Fischer microhardness is measured using a Fischerscope H-100SMC, available from Fischer Technology, Inc. at a load of 300 mN, after an application of a 0-300 mN load in 15 seconds.

[0242] Aspect 50. The polymerization of any of aspects 45 to 49, wherein the polymerization pR7 / nn / L7nz / E / Yii has a storage modulus E' greater than 1.5 GPa at 25°C, wherein the storage modulus E' is measured on 3.5 mm thick samples according to ASTM D5023 “Standard Test Method for Plastics. Dynamic Mechanical Properties: In Flexure (Three-Point Bending)” using the Perkin Elmer DMA Diamond analyzer

[0243] Aspect 51. The polymerization of any of aspects 45 to 49, wherein the polymerization has a storage modulus E' greater than 2.0 GPa at 25°C, wherein the storage modulus E' is measured on 3.5 mm thick samples according to ASTM D5023 “Standard Test Method for Plastics. Dynamic Mechanical Properties: In Flexure (Three-Point Bending)” using the Perkin Elmer DMA Diamond analyzer

[0244] Aspect 52. The polymerization of any of aspects 45 to 51, wherein the polymerization has a storage modulus E' greater than 0.5 GPa at 75°C, wherein the storage modulus E' is measured on 3.5 mm thick samples according to ASTM D5023 “Standard Test Method for Plastics. Dynamic Mechanical Properties: In Flexure (Three-Point Bending)” using the Perkin Elmer DMA Diamond analyzer

[0245] Aspect 53. The polymerization of any of aspects 45 to 51, wherein the polymerization has a storage modulus E' greater than 1.0 GPa at 75°C, wherein the storage modulus E' is measured on 3.5 mm thick samples according to ASTM D5023 “Standard Test Method for Plastics. Dynamic Mechanical Properties: In Flexure (Three-Point Bending)” using the Perkin Elmer DMA Diamond analyzer

[0246] Aspect 54. The polymerization of any of aspects 45 to 53, wherein the polymerization has an Abbe number greater than or equal to 30, wherein the Abbe number is measured using a Metricon Model 2010M prism coupler in accordance with ASTM C1648.

[0247] Aspect 55. The polymerization of any of aspects 45 to 53, wherein the polymerization has an Abbe number greater than or equal to 34, wherein the Abbe number is measured using a Metricon Model 2010M prism coupler in accordance with ASTM C1648.

[0248] Aspect 56. An article comprising the polymerization of any of aspects 45 to 55.

[0249] Aspect 57. The article of aspect 56, wherein the article comprises one or more surface coatings.

[0250] Aspect 58. The article of aspect 57, wherein one or more surface coatings comprises a scratch-resistant coating, an anti-reflective coating, a wavelength-selective reflective coating, a wavelength-selective absorbing coating, a planarizing coating, a polarizing coating, or a combination of any of the foregoing. pRZinn / Lznz / E / Yii

[0251] Aspect 59. A method of manufacturing an article comprising: forming the polymerizable composition of aspect 39 into a shape; and curing the applied composition to provide the article.

[0252] Aspect 60. The method of aspect 59, wherein the forming comprises casting, additive manufacturing, three-dimensional printing, inkjet printing, transfer printing, or stereolithography.

[0253] Aspect 61. The method of any of aspects 59 to 60; wherein the method comprises exposing the composition to actinic radiation before the formation of the form, after the formation of the form, during the formation of the form, or a combination of any of the foregoing.

[0254] Aspect 62. An article manufactured using the method of any of aspects 59 to 61.

[0255] Aspect 63. The article of aspect 63, wherein the article comprises an optical display, a cover, a window, a transparency, a windscreen, sunglasses, eyeglasses, an optical lens, a sports mask, a face shield, protective goggles, an optical component, or an optoelectronic device.

[0256] Aspect 64. A method for synthesizing a composition comprising: (A) combining the reagents (i), (ii) and (iii) to form a mixture, wherein the reagents comprise: (i) a first reagent, having two active hydrogen groups, the first reagent having the structure of Formula (5): where b is selected from 0 or 1; and is an integer from 1 to 6; and (ii) a second reagent comprising two or more active hydrogen groups, where each of the two or more active hydrogen groups is independently selected from hydroxyl or thiol; at least one of the two or more active hydrogen groups is a thiol; and the second reagent is different from the first reagent; and (iii) a third reagent, wherein the third reagent comprises an acrylating agent; and (B) reacting the mixture in the presence of a base to provide the combination of (meth) acryloyl-terminated monomers and (meth) acryloyl-terminated oligomers.

[0257] Aspect 65. A method of aspect 64, wherein the acrylating agent comprises (meth) acryloyl chloride or (meth) acrylate anhydride. EXAMPLES

[0258] The modalities provided by this description are best illustrated by reference to the following examples, which describe compositions, methods, and uses provided herein. It will be evident to those skilled in the art that modifications to both the materials and methods may be made without departing from the scope of the description. Part 1 Synthesis of monomers and oligomers terminated in (meth)acryloyl

[0259] The compositions comprising (meth)acryloyl-terminated monomers and oligomers were prepared using the amounts described in Table 1. First, a polythiol salt solution was prepared by dropwise addition of 100 equivalents of the indicated polythiol or polythiol mixture to a solution of 1.03 equivalents of NaOH in water, with stirring, under a nitrogen atmosphere.

[0260] The polythiol salt solution was then added dropwise to a solution of 100% equivalent of methacryloyl chloride in dichloromethane under a nitrogen atmosphere, mixing and cooling to a reaction temperature of 0°C to 5°C. For Example 6, the polythiol salt solution was added dropwise to a solution of 100% equivalent of methacryloyl chloride in ethyl acetate under a nitrogen atmosphere, mixing and cooling to a reaction temperature of 0°C to 5°C. The solution was brought to 25°C for an additional 2 to 3 hours, until iodine titration indicated that the reaction was complete. The organic layer was collected and washed three times using (i) water, (ii) saturated sodium bicarbonate solution, and (iii) saturated sodium chloride solution. 250 parts per million (ppm) of 4-methoxyphenol and 250 ppm of 4-yer-butylcatechol were added to the organic phase.The volatile compounds were removed by vacuum distillation, and the product was filtered to provide a composition comprising a combination of (meth)acryloyl-terminated monomers and (meth)acryloyl-terminated oligomers. Table 1. Reagents used to prepare monomers and oligomers terminated in (meth)acryloyl. ρβζ / ηη / ίζηζ / Ε / γι Number of Equivalents of Reagent Reagents Comparative Example 1 Comparative Example 2 Example 3 Example 4 Example 5 Example 6 bis(2-mercaptoethyl)sulfide1 “first polythiol” 1.0 - 0.865 0.818 0.72 0.865 4-mercaptomethyl-3,6-dithiol-1,8-octanedithiol2 “second polythiol” - 1.0 0.135 0.182 - 0.135 7-Hydroxymethyl-1,14-dimercapto-3,6,9,12tetrathiatetradecane3 “second polythiol” - - - - 0.28 - Methacryloyl Chloride4 1.0 1.0 1.0 1.0 1.0 - Methacrylic Anhydride4 1.0 Sodium Hydroxide 1.03 1.03 1.03 1.03 1.03 1.03 4-Methoxyphenol 250 ppm 250 ppm 250 ppm 250 ppm 250 ppm 250 ppm 4-tert-Butylcatechol 250 ppm 250 ppm 250 ppm 250 ppm 250 ppm 250 ppm 250 ppm Active hydrogen ratio (first polythiol:second polythiol) N / A 0 6.41 4.49 2.26 6.41 Viscosity (cP) at 25°C - - 50-70 - - 50-70 Performance after filtration 80-95 535 85-90 71 71 85-90 'Bis(2-mercaptoethyl) sulfide was acquired from Bruno Bock Chemische Fabrik GmbH & Co., in Marschacht, Germany under the trade name Thiocure® DMDS. 2E1 4-Mercaptomethyl-3,6-dithia-l,8-octanedithiool was acquired from Miwon Commercial Co., Ltd. in Danwon-gu, Ansan-si, Gyeonggi-do, South Korea, under the trade name Optimer 530. 3E1 7-Hydroxymethyl-l,14-dimercapto-3,6,9,12-tetrathiatetradecane was synthesized using the methods described in US 7,687,597 B2. 4E1 Methacryloyl chloride and methacrylic anhydride were acquired from Bimax Inc. in Glen Rock, PA, under the trade names BX-MAN and BX-MAC, respectively. 5For Comparative Example 2, a significant amount of gelatinous by-product was produced. Part 2 Lens Molding

[0261] Each polymerizable composition of Comparative Examples 1 and 2 and Examples 3 through 5 was used to prepare a corresponding (“polymerizable”) lens mold according to the following procedure.

[0262] Each polymerizable composition was transferred to a polypropylene container, to which 0.1 wt% of Darocure® 1173 photoinitiator (available from BASF) was added. The resulting mixture was stirred at 25 °C until homogeneous. The polymerizable composition containing the photoinitiator was filtered and dispensed into a mold consisting of two UV-transparent, disc-shaped glass molds with a plastic gasket (separator) to control lens thickness. The internal dimensions of the mold cavity were designed to produce a final cured lens with a diameter of 75 mm and a thickness of 3.5 mm. The filled molds were exposed to UV light via a LESCO Incorporated UV irradiation device equipped with a Fusion UV Curing Systems F-300 focused-beam microwave-driven lamp, fitted with a D bulb in which 64% of the emitted energy was between 300 and 400 nm. The UV intensities and dosed energies are shown in Table 2. ΓΑζ / ηη / ίζηζ / Ε / γι Table 2. UV Curing Parameters. Parameter uve (200-280 nm) UVB (280-320 nm) UVA (320-395 nm) UW (395-455 nm) Intensity (Watt / cm2) 0.057 0.48 1.1 0.62 Dose (Joule / cm2) 0.72* 5.9* 12.4* 7.3* * Value is measured for one pass through the UV irradiation device.

[0263] A linear speed of 1.5 feet per minute (ft / min) (0.45 meters per minute (m / min)) was used, and each filled mold assembly was passed under UV light three times. Between passes, the mold was turned over to expose the opposite side to the UV light source. After exposing the polymerizable composition to UV radiation, a disc-shaped lens was retrieved from the mold assembly and heated to 100°C for 1 hour. It was then used to measure the physical properties. Part 3 Measurement of Physical Properties

[0264] The following procedure was used to evaluate the properties of the polymers and the results are presented in Table 3. Fischer Microhardness

[0265] Microindentation hardness (also referred to as Martens hardness, ISO 1457707) was measured using a Fischerscope H-100SMC, available from Fischer Technology, Inc. The Fischer microhardness (or “Fischer Hardness”) of the polymerized materials, within (±) 3 N / mm², was measured at a 300 mN load, after a load application from 0 mN to 300 mN over 15 seconds. In general, a higher Fischer microhardness is desirable for improved lens energy retention and / or improved resistance to distortion during the processing of optical materials. Storage Module E'

[0266] Dynamic Mechanical Analysis (DMA) was performed in accordance with ASTM D5023 “Standard Test Method for Plastics. Dynamic Mechanical Properties: In Flexure (Three-Point Bending)” using a Perkin Elmer Diamond DMA analyzer. The storage modulus was reported as “DMA Storage Modulus E'” at 25°C, 75°C, or 95°C on 3.5 mm thick samples. In general, a higher storage modulus E' is desirable for improved lens energy retention and / or better resistance to distortion during optical material processing. Refractive index and Abbe number

[0267] The refractive index and Abbe number were measured using a Metricon Model 2010M prism coupler in accordance with ASTM C1648. Refractive index values ​​were measured at 20°C at a wavelength of 546.07 nm (i.e., the e line of mercury) and reported as ne20. The Abbe number Vd was calculated according to Equation 1, pRz / nn / Lznz / B / Yi VI Σ' Klsv .. . - . Equation 1 where ud, uf, and nc are the refractive indices of the material at the wavelengths of the Fraunhofer D-, F-, and C- spectral lines, namely 589.3 nm, 486.1 nm, and 656.3 nm, respectively. The Abbe number was reported as “Abbe”.

[0268] A higher refractive index is generally advantageous, as it may allow the use of thinner, cosmetically pleasing lenses for a given prescription. A larger Abbe number is generally advantageous, as it may result in clearer, less distorted images for the end user of the optical lens. Table 3. Summary of Results. Polymeric Properties of the Molded Lens Storage Modulus E' DMA, GPa Polymerized Polymerizable Composition Fischer Microhardness 25°C 75°C 95°C ne20 Abbe Comparative Example 7 Comparative Example 1 60-90 1-1.5 0.3-0.6 0.2-0.5 1.627 35-36 Comparative Example 8 Comparative Example 2 108 NA1 1.636 35 Example 9 Example 3 140-150 2.2-2.3 1.1-1.2 0.8-1 1.636 36 Example 10 Example 4 140 2.6 1.5 1.1 1.635 35 Example 11 Example 5 124 2.2 1.2 0.9 1.638 35 Example 12 Example 6 140 2.6 1.4 1.1 1.628 36 1The E' DMA storage module could not be measured because an extensive amount of lens cracking occurred during the UV curing process. Part 4 Molecular weight distribution analysis by GPC

[0269] The molecular weight of the (meth)acryloyl-terminated monomer and oligomer combination of Example 3 was determined using gel permeation chromatography (GPC), using a Waters 2695 Liquid Chromatography (LC) Instrument equipped with a Waters 2414 refractive index detector, two 5-micrometer (µm) MIXED-C 300 x 7.5 mm PL gel columns, and a PerkinElmer TotalChrom C / S Chromatography Data System. The sample was prepared as a solution in tetrahydrofuran (THF), and the mobile phase consisted of (isocratic) THF, with a flow rate of 10 milliliters / minute (mL / minute) and a column temperature of 35 °C. Eight (8) polystyrene standards were used with peak molecular weights (Mp) ranging from 1,000 to 1,200,000 Dalton (Da).The results are shown in Table 4 and Figure 1, where RT is the retention time in minutes, Mw is the weight average molecular weight, Mn is the numerical average molecular weight, and Mw / Mn is the polydispersity index. Figure 1 is a GPC chromatogram where the relative peak intensity is a function of time, in minutes.

[0270] The GPC peak at 18.03 minutes with a peak molecular weight of 240 Da corresponds to bis(2-methacryloylthioethyl)sulfide. The broader GPC peak at 17.93 minutes with a peak molecular weight of 539 Da indicates the presence of oligomeric byproducts in addition to 4-methacryloylthiomethyl-3,6-dithia-1,8-bis(methacryloylthio)octane as described in the Synthetic Scheme shown in Figure 2. Table 4. Analysis of a combination of (meth)acryloyl-terminated monomers and oligomers of GPC. Peak RT Area % Mp Mw Mn Mw / Mn 1 17.93 43.8 539 1040 664 1.57 2 18.03 56.2 240 227 216 1.05

[0271] Finally, it should be noted that there are alternative ways of implementing the modalities described herein. Accordingly, the modalities herein should be considered illustrative and not restrictive. Furthermore, the claims are not limited to the details provided herein and are entitled to their full scope and equivalents.

Claims

1. A composition comprises: (a) a first (meth)acryloyl-terminated monomer, wherein the first (meth)acryloyl-terminated monomer has the structure of Formula (1): oo (1) wherein each R1 is independently selected from hydrogen or methyl; b is selected from 0 or 1; a is an integer from 1 to 6; and (b) a second (meth)acryloyl-terminated monomer comprising two or more (meth)acryloyl groups, wherein each a of the two or more (meth)acryloyl groups is independently selected from an (meth)acryloyloxy group and an (meth)acryloylthio group; at least one of the (meth)acryloyl groups is an (meth)acryloylthio group; and the second (meth)acryloyl-terminated monomer (b) is different from the first (meth)acryloyl-terminated monomer.

2. The composition of claim 1, wherein selected from 1 or 2.

3. The composition of claim 1, wherein the first monomer terminated in (meth) acryloyl comprises bis(2-methacryloylthioethyl) sulfide: OO / 4. The composition of claim 1, wherein the second (meth) acryloyl-terminated monomer comprises a polythiaalkylene portion.

5. The composition of claim 4, wherein the polythiaalkylene part is a cyclic polythiaalkylene part or a branched polythiaalkylene part.

6. The composition of claim 4, wherein the polythiaalkylene part is a branched polythiaalkylene part and the second (meth)acryloyl-terminated monomer comprises 3 to 6 (meth)acryloyl groups.

7. The composition of claim 1, wherein the second monomer terminated in (meth) acryloyl comprises at least one (meth) acryloylthio group and at least one (meth) acryloyloxy group.

8. The composition of claim 1, wherein the second monomer terminated in (meth)acryloyl comprises 2,5-bis[(meth)acryloylthiomethyl]-1,4-dithian, 4-(meth)acryloylthiomethyl-3,6-dithia-1,8bis[(meth)acryloylthio]octane, 7-(meth)acryloyloxymethyl-3,6,9,12-tetrathia-1,14-bis[(meth)acryloylthio]tetradecane, 4,8-bis[(meth)acryloylthiomethyl]-3,6,9-trithia-1,11-bis[(meth)acryloylthio]undecane and regioisomers thereof such as the 4,7- and 5,7-, 2-ethyl-2-((meth)acryloylthiomethyl)-1,3bis[(meth)acryloylthio]propane regioisomers, l,2,3-tris[(meth)acryloylthio]propane or combinations of any of the above.

9. The composition of claim 1, wherein the composition further comprises an oligomer terminated in (meth) acryloyl.

10. The composition of claim 1, wherein the composition comprises from 15% by weight to 60% by weight of sulfur, wherein the % by weight is based on the total weight of the composition.

11. The composition of claim 1, wherein the first (meth) acryloyl-terminated monomer comprises a first (meth) acryloyl equivalent; the second (meth) acryloyl-terminated monomer comprises a second (meth) acryloyl equivalent; and a ratio of the first (meth) acryloyl equivalents to the second (meth) acryloyl equivalents is greater than 1:

1.

12. The polymerizable composition of claim 1 further comprises a free radical initiator, wherein the free radical initiator comprises a photoinitiator or a thermally activated free radical initiator.

13. The polymerizable composition of claim 1 further comprises a third monomer, wherein the third monomer comprises one or more groups polymerizable by ethylenically unsaturated radicals; and the third monomer is different from the first monomer terminated in (meth) acryloyl and the second monomer terminated in (meth) acryloyl.

14. The polymerizable composition of claim 1, wherein the polymerizable composition further comprises one or more of a thermal stabilizer, a UV stabilizer, a UV absorber, a hindered amine photostabilizer, a dichroic material, a photochromic material, a polymerization moderator, a polymerization accelerator, a pigment, a dye, or a combination of any of the foregoing.

15. The polymerizable composition of claim 14, wherein the polymerization accelerator may comprise an organophosphine, an organophosphate, an amine, or combinations thereof.

16. A composition comprising the reaction product of reagents comprising: (i) a first reagent, having two active hydrogen groups, the first reagent having the structure of Formula (5): where b is selected from 0 or 1; and is an integer from 1 to 6; (ii) a second reagent comprising two or more active hydrogen groups, where each of the two active hydrogen groups is independently selected from hydroxyl or thiol; at least one of the two or more active hydrogen groups is a thiol; and the second reagent is different from the first reagent; and (iii) a third reagent comprising an acrylating agent.

17. The composition of claim 16, wherein a is selected from 1 or 2 18. The composition of claim 16, wherein the first reagent comprises bis(2-mer captoethyl)sulfate: HS\ ^SH 19. The composition of claim 16, wherein the second reagent comprises 2,5-dimercaptomethyl-1,4-dithiol, 2-ethyl-2-(mercaptomethyl)propane-1,3-dithiol, 1,2,3-trimercaptopropane, 2,2-bis(mercaptomethyl)propane-1,3-dithiol, 4-mercaptomethyl-3,6-dithiol-1,8-octanedithiol, 1,3-dimercapto-2-propanol, 3-mercapto-1,2-propanediol, 2-mercapto-1,3-propanediol, 2,3-dimercapto-1-propanol, 7-hydroxymethyl-1,14-dimercapto-3,6,9,12-tetrathiatetradecane, 4,8-bis(mercaptomethyl)-l,ll-dimercapto-3,6,9tritiaundecane and regioisomers thereof such as the 4,7- or 5,7- regioisomers or a combination of any of the above.

20. The composition of claim 16, wherein the acrylating agent comprises (meth) acryloyl chloride or (meth) acrylate anhydride.

21. The composition of claim 16, wherein the ratio of active hydrogen group equivalents of the first reagent to the second reagent is greater than 1:

1.

22. The composition of claim 16, wherein the reaction product comprises: a first (meth)acryloyl-terminated monomer, wherein the first (meth)acryloyl-terminated monomer is derived from the first reagent; a second (meth)acryloyl-terminated monomer, wherein the second (meth)acryloyl-terminated monomer is derived from the second reagent; and a combination of (meth)acryloyl-terminated oligomers, wherein the combination of the (meth)acryloyl-terminated oligomers is derived from the reaction of the first reagent, the second reagent, and the acrylating agent.

23. The composition of claim 16, wherein the composition comprises from 15% by weight to 60% by weight of sulfur, wherein % by weight is based on the total weight of the composition.

24. The polymerizable composition of claim 16, further comprising a free radical initiator, wherein the free radical initiator comprises a photoinitiator or a thermally activated free radical initiator.

25. A method of manufacturing an article, comprising: forming the polymerizable composition of claim 24 into a shape, wherein the forming comprises casting, additive manufacturing, three-dimensional printing, inkjet printing, transfer printing or stereolithography; and curing the applied composition to provide the article.

26. The method of claim 25, wherein the method comprises exposing the composition to actinic radiation before the formation of the shape, after the formation of the shape, during the formation of the shape, or a combination of any of the foregoing.