Multi-(meth)acrylate functionalized oligomers and methods of making and using such oligomers

Abstract

The multi-(meth)acrylate functionalized oligomer has a polyurethane backbone, a plurality of (meth)acrylate groups pendant to the polyurethane backbone, and one or more terminal (meth)acrylate groups. The oligomer contains: a) at least one multi-(meth)acrylate functionalized segment having at least two pendant (meth)acrylate groups, b) a urethane-containing segment, c) at least one terminal end-capping segment having at least one (meth)acrylate group, and optionally, d) a chain-extending segment (such as a non-polymeric aliphatic segment, a polyether-containing segment, a polyester-containing segment, a polydiene-containing segment, a polycarbonate-containing segment, or a polyorganosiloxane-containing segment). At least one multi-(meth)acrylate functionalized segment is in a pendant position, and at least one (meth)acrylate group is present at one or more terminal positions of the oligomer. The multi-(meth)acrylate functionalized oligomer can be used in a composition that can be cured (including by photocuring) to provide a polymeric article. The oligomer may be the reaction product of a diisocyanate, a diol or triol compound containing two or three (meth)acrylate groups, respectively, and a terminal capping compound.

Description

Technical Field

[0001] The present invention relates to multi-(meth)acrylate functionalized oligomers, methods of preparing such oligomers, curable compositions based on the oligomers, methods of using the oligomers, and compositions and articles containing the oligomers in cured form. Background Art

[0002] Many different types of (meth)acrylate functionalized oligomers are known in the art, including (meth)acrylate functionalized urethane oligomers characterized by having one or more (meth)acrylate functional groups substituted at the terminal end of the oligomeric polyurethane backbone. (Meth)acrylate functionalized urethane oligomers can be synthesized by various methods, including, for example, reacting a polymeric polyol (such as a polyether polyol, a polycarbonate polyol, or a polyester polyol) with an excess of a polyisocyanate to form an isocyanate functionalized urethane prepolymer, and then reacting the isocyanate functionalized urethane prepolymer with a reagent (such as hydroxyethyl (meth)acrylate, which contains both isocyanate-reactive functional groups and (meth)acrylate functional groups). Such (meth)acrylate functionalized urethane oligomers have been found to be useful components of compositions that can be cured (polymerized) using UV radiation or other methods to form cured compositions useful as coatings, adhesives, sealants, resins for additive manufacturing, molding resins, and the like.

[0003] Conventional terminally functional ("telechelic") (meth)acrylated urethane oligomers are a versatile class of reactive materials, but suffer from certain limitations due to their molecular architecture. In particular, because the reactive (meth)acrylate functionality is located at the terminal end of the oligomer, when such an oligomer is cured, the level of (meth)acrylate functionality and the resulting crosslink density is inversely related to the backbone molecular weight of the oligomer. Higher molecular weight backbones inherently lead to lower crosslink density cured materials, and lower molecular weight backbones necessarily lead to high crosslink density. It would be beneficial to decouple this relationship so that certain combinations of cured properties that are currently difficult to achieve can be achieved through the use of conventional telechelic oligomers, thereby making the curable composition more tunable. It is also known that localized functionality (such as that generated through the use of telechelic oligomers) can produce non-uniform crosslinked networks. Such "non-uniform" networks can have a negative impact on the properties of the cured material, and can, for example, result in brittleness and / or high vapor permeability. Thus, it would be of great interest to develop oligomers that facilitate the production of more uniform crosslinks. Summary of the invention

[0004] The present invention provides oligomers having multiple (meth)acrylate functional groups, the multiple (meth)acrylate functional groups being located both along the backbone of the oligomer and at the terminal positions of the oligomer. In particular, such oligomers have a polyurethane backbone, multiple (meth)acrylate functional groups pendant to the polyurethane backbone, and one or more terminal (meth)acrylate functional groups. The oligomers comprise: a) at least one multi-(meth)acrylate functionalized segment having at least two pendant (meth)acrylate groups, b) a urethane-containing segment, c) at least one terminal end-capping segment having at least one (meth)acrylate group, and optionally, d) at least one chain-extending segment (containing at most one (meth)acrylate functional group), such as a non-polymeric aliphatic segment or a polymer-containing segment selected from a polyether-containing segment, a polyester-containing segment, a polydiene-containing segment, a polycarbonate-containing segment, and a polyorganosiloxane-containing segment. At least one multi-(meth)acrylate functionalized segment is positioned at a position along the polyurethane backbone of the oligomer that is different from a terminal position of the oligomer, and at least one (meth)acrylate functional group is present at one or more terminal positions of the oligomer. The oligomers according to the present invention allow for flexible regulation of the crosslink density and resulting mechanical properties of cured compositions prepared using such oligomers by decoupling the level and position of curable functionality from the backbone molecular weight of the oligomer. The reactive oligomers of the present invention (which contain both pendant and telechelic (meth)acrylate functionalities) are capable of curing to produce more uniformly crosslinked materials, thereby avoiding or ameliorating the above-mentioned disadvantages that are sometimes encountered with the "clustered" crosslinking characteristics of conventional telechelic oligomers.

[0005] The multi-(meth)acrylate functionalized oligomer according to aspects of the present invention may be a reaction product comprising the following reactants: a) at least one diisocyanate, b) at least one diol compound (which comprises at least two (meth)acrylate functional groups) or at least one triol compound (which comprises at least three (meth)acrylate functional groups) or a mixture thereof, c) at least one terminal capping compound (which comprises a single isocyanate-reactive hydroxyl group and at least one (meth)acrylate functional group), and optionally, d) at least one chain-extending diol, which either has no (meth)acrylate functional group or has at most one (meth)acrylate functional group, and which may be a non-polymeric diol (such as a non-polymeric aliphatic diol) and / or a polymeric diol, such as a polymeric diol selected from the following: polyether polyols, polyester polyols, polydiene polyols, polycarbonate polyols, and polyorganosiloxane polyols).

[0006] The present invention also provides a method of making a multi-(meth)acrylate functionalized oligomer having a polyurethane backbone, a plurality of (meth)acrylate functional groups pendant to the polyurethane backbone, and one or more terminal (meth)acrylate functional groups. Such a method comprises reacting: a) at least one diisocyanate, b) at least one diol compound (which comprises at least two (meth)acrylate functional groups) or at least one triol compound (which comprises at least three (meth)acrylate functional groups) or a mixture thereof, c) at least one terminal capping compound (which comprises a single isocyanate-reactive hydroxyl group and at least one (meth)acrylate functional group), and optionally, d) at least one chain-extending diol (which either has no (meth)acrylate functional group or has at most one (meth)acrylate functional group, and which may be a non-polymeric diol and / or a polymeric diol, such as a polymeric diol selected from the group consisting of polyether polyols, polyester polyols, polydiene polyols, polycarbonate polyols, and polyorganosiloxane polyols). These components may be reacted with one another either all at once or using different sequential steps, as will be explained in more detail subsequently.

[0007] The present invention also provides a curable composition, wherein such a curable composition comprises at least one multi-(meth)acrylate functionalized oligomer according to the present invention and at least one of the following: a) a photoinitiator, or b) a curable compound different from the multi-(meth)acrylate functionalized oligomer according to the present invention.

[0008] The multi-(meth)acrylate functionalized oligomers of the present invention and curable compositions containing such oligomers can be cured by various mechanisms, including photocuring, to provide cured compositions having useful properties, such as improved tensile strength. The multi-(meth)acrylate functionalized oligomers can be formulated with other reactive components and other additives to obtain curable compositions useful as curable coatings, adhesives, sealants, resins for additive manufacturing, and the like. DETAILED DESCRIPTION

[0009] definition

[0010] In the present application, the term "comprise(s) a / an" means "comprise(s) a / an)".

[0011] Unless otherwise stated, weight % in a compound or composition is expressed based on the weight of the compound (respectively composition).

[0012] The term "(meth)acrylate functional group" refers to an acrylate functional group (-OC(=O)-CH=CH 2 ), or refers to the methacrylate functional group (-OC(=O)-C(CH 3 )=CH 2 ). When not followed by the word "functional group," the term "(meth)acrylate" refers to a chemical compound containing at least one acrylate functional group per molecule or at least one methacrylate functional group per molecule. "(Meth)acrylate" may also refer to a chemical compound having both at least one acrylate functional group and at least one methacrylate functional group. "Functionality" refers to the number of (meth)acrylate functional groups per molecule. It does not refer to any other functional groups besides the (meth)acrylate functional groups unless explicitly stated. For example, a difunctional monomer is understood to mean a monomer having two (meth)acrylate functional groups per molecule. On the other hand, a trifunctional alcohol is understood to mean a compound having three hydroxyl groups per molecule without a (meth)acrylate group. In the absence of further description, "monomer" and "oligomer" are understood to mean a (meth)acrylate monomer and a (meth)acrylate oligomer, respectively.

[0013] The term "urethane (meth) acrylate" refers to a compound comprising at least one urethane bond and at least one (meth) acrylate functional group. Such compounds may also be referred to as urethane (meth) acrylate oligomers. The term "urethane bond" means a -NH-C(=O)-O- or -OC(=O)-NH- bond.

[0014] The term "polyester" means a compound or moiety having more than one ester bond. The term "ester bond" means a -C(=O)-O- or -OC(=O)- bond.

[0015] The term "polyether" means a compound or moiety having more than one ether linkage. The term "ether linkage" means an -O- linkage.

[0016] The term "polycarbonate" means a compound or moiety having more than one carbonate linkage. The term "carbonate linkage" means a -OC(=O)-O- linkage.

[0017] The term "polydiene" means a compound or moiety obtained by polymerizing a conjugated diene.

[0018] The term "polyorganosiloxane" means a compound or moiety having more than one siloxane bond. The term "siloxane bond" means a -Si-O- or -O-Si- bond.

[0019] The term "diol" means a compound with two hydroxyl groups.

[0020] The term "triol" means a compound having three hydroxyl groups.

[0021] The term "hydroxy group" means an -OH group.

[0022] The term "diisocyanate" means a compound bearing 2 isocyanate groups.

[0023] The term "isocyanate group" means a -N=C=O group.

[0024] The term "polyoxyethylene" means a compound or moiety having more than one oxyethylene unit. The term "oxyethylene unit" means -(O-CH 2 -CH 2 )-unit.

[0025] The term "polyoxypropylene" means a compound or moiety having more than one oxypropylene unit. The term "oxypropylene unit" means -(O-CH(CH 3 )-CH 2 )- and / or -(O-CH 2 -CH(CH 3 ))-unit.

[0026] The term "polyoxytetramethylene" means a compound or moiety having more than one oxytetramethylene unit. The term "oxytetramethylene unit" means -(O-CH 2 -CH 2 -CH 2 -CH 2 )-unit.

[0027] The term "organo", "hydrocarbon" or "hydrocarbyl" means a monovalent or polyvalent (divalent, trivalent, tetravalent, pentavalent, hexavalent) group containing carbon and hydrogen atoms. It may be linear or branched; saturated or unsaturated; cyclic or acyclic; aliphatic, aromatic or araliphatic. It may contain 1 to 200 carbon atoms. 2 -C 12 Hydrocarbyl means a hydrocarbon group having 2 to 12 carbon atoms. It may be arbitrarily substituted. It may contain, in addition to carbon and hydrogen atoms, one or more heteroatoms selected from O, N, S, Si and mixtures thereof.

[0028] The term "aliphatic" means an optionally substituted non-aromatic compound or moiety. It may be linear or branched, saturated or unsaturated. It may be acyclic, or contain one or more alicyclic rings (i.e., non-aromatic rings). It may contain one or more heteroatoms, such as O, N, S and / or halogen.

[0029] The term "aromatic" means an optionally substituted compound or moiety comprising an aromatic ring (which means obeying the Hückel aromaticity rule), in particular a compound comprising a phenyl group. It may contain one or more heteroatoms such as O, N, S and / or halogen.

[0030] The term "araliphatic" means an optionally substituted compound or moiety containing aliphatic and aromatic moieties. It may contain one or more heteroatoms such as O, N, S and / or halogen.

[0031] The term "alkylene" means a radical consisting of a radical having the formula C n H 2n+2 A divalent moiety obtained by removing two hydrogen groups from an alkane. It may be linear or branched. 2 -C 4 The term "dialkylene" means a dialkylene group having 2 to 4 carbon atoms. Examples of suitable dialkylene groups are ethylene, propylene, isopropylene, butylene and isobutylene.

[0032] The term "optionally substituted" means a compound substituted with one or more groups selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, alkylaryl, haloalkyl, hydroxy, halogen, isocyanate, nitrile, amine, carboxylic acid, -C(=O)-R', -C(=O)-OR', -C(=O)NH-R', -NH-C(=O)R', -OC(=O)-NH-R', -NH-C(=O)-O-R', -C(=O)-OC(=O)-R', and -SO 2 -NH-R', each R' is independently an optionally substituted group selected from alkyl, aryl and alkylaryl.

[0033] The term "alkyl" refers to a group having the formula -C n H 2n+1 The alkyl group may be linear or branched. 1 -C 6 The term “alkyl group” means an alkyl group having 1 to 20 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl.

[0034] The term "cycloalkyl" means a monovalent saturated alicyclic hydrocarbon moiety comprising a ring. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl and isobornyl.

[0035] The term "aryl" means an aromatic hydrocarbon group.

[0036] The term "phenylene" means a polyvalent moiety obtained by removing two or more hydrogen radicals from substituted or unsubstituted benzene.

[0037] The term "heteroaryl" means an aromatic group containing heteroatoms such as O, N, S and mixtures thereof.

[0038] The term "alkoxy" refers to a group having the formula -O-alkyl.

[0039] The term "alkylaryl" refers to an alkyl group substituted with an aryl group. Examples of alkylaryl groups are benzyl (-CH 2 -phenyl).

[0040] The term "haloalkyl" refers to an alkyl group substituted with one or more halogen atoms.

[0041] The term "halogen" means an atom selected from Cl, Br and I.

[0042] The term "ethylenically unsaturated compound" means a compound containing a polymerizable carbon-carbon double bond. A polymerizable carbon-carbon double bond is a carbon-carbon double bond that can react with another carbon-carbon double bond in a polymerization reaction. Polymerizable carbon-carbon double bonds are generally contained in a group selected from the following: acrylates (including cyanoacrylates), methacrylates, acrylamides, methacrylamides, styrenes, maleates, fumarates, itaconates, allyls, propenyls, vinyls and combinations thereof, preferably selected from acrylates, methacrylates and vinyls, more preferably selected from acrylates and methacrylates. The carbon-carbon double bonds of phenyl rings are not considered polymerizable carbon-carbon double bonds.

[0043] As used herein, the term "alkoxylated" refers to compounds in which one or more epoxides (such as ethylene oxide and / or propylene oxide) have reacted with active hydrogen-containing groups (e.g., hydroxyl groups) of a base compound (e.g., a polyol) to form one or more oxyalkylene moieties. For example, 1 to 25 moles of epoxides may be reacted per mole of base compound.

[0044] Multi-(meth)acrylate functionalized oligomers

[0045] The multi-(meth)acrylate functionalized oligomer according to aspects of the present invention may be characterized as follows: an oligomer containing a polyurethane backbone, a plurality of (meth)acrylate functional groups suspended to the polyurethane backbone, and one or more terminal (meth)acrylate functional groups. Thus, the oligomer carries a plurality of (meth)acrylate functional groups both along its backbone and at the terminal ends of the oligomer. As used herein, the term "(meth)acrylate" refers to both acrylate and methacrylate functional groups. According to certain embodiments, each (meth)acrylate functional group in an oligomer molecule may be of the same type (i.e., all (meth)acrylate functional groups in the oligomer may be acrylate functional groups, or all (meth)acrylate functional groups in the oligomer may be methacrylate functional groups). The oligomer may contain both acrylate functional groups and methacrylate functional groups. For example, the terminal (meth)acrylate functional groups may be acrylate functional groups, while the (meth)acrylate functional groups pendant to the polyurethane backbone may be methacrylate functional groups, or vice versa.

[0046] The oligomers according to the present invention contain at least three (meth)acrylate functional groups per molecule (at least two of which are associated with a multi-(meth)acrylate functionalized segment and at least one of which is associated with a terminal end of the oligomer). However, in embodiments of the present invention, the oligomer may contain a total of four, five, six, seven, eight, nine, ten or more (meth)acrylate functional groups per molecule. The number of (meth)acrylate functional groups per molecule can be easily controlled or varied as desired by, for example, varying the number average molecular weight of the oligomer, the number of multi-(meth)acrylate functionalized segments in the oligomer, and / or the type of reactants used to prepare the oligomer, as will be explained in more detail subsequently.

[0047] According to certain embodiments, the multi-(meth)acrylate functionalized oligomer structure is linear (wherein the (meth)acrylate functional groups associated with the multi-(meth)acrylate functionalized segments are not considered branches). However, in other embodiments, the oligomer may have a star-shaped, comb-shaped, radial or branched structure.

[0048] The multi-(meth)acrylate functionalized oligomer may comprise, consist essentially of, or consist of: a) at least one multi-(meth)acrylate functionalized segment having at least two pendant (meth)acrylate groups, b) a urethane-containing segment, c) at least one terminal end-capping segment having at least one (meth)acrylate group, and optionally, d) at least one chain extender segment. The chain extender segment may be one or more of a non-polymeric segment and / or a polymeric segment. Such optional chain extender segments are different from the multi-(meth)acrylate functionalized segments in that each segment contains no more than one (meth)acrylate functional group (i.e., either no (meth)acrylate functional group or at most one (meth)acrylate functional group). They are also different from urethane-containing segments in that they do not contain a urethane lingkage. If present, the polymeric segments may be, for example, selected from segments containing polyethers, segments containing polyesters, segments containing polydienes, segments containing polycarbonates, and segments containing polyorganosiloxanes. If present, the non-polymeric segments may be aliphatic, aromatic, or araliphatic (containing both aliphatic and aromatic moieties). Thus, in certain embodiments, the oligomer contains one or more such chain-extending segments, but in other embodiments, the oligomer does not contain any such chain-extending segments. The oligomers of the present invention are characterized in that at least one multi-(meth)acrylate functionalized segment is located at a position along the polyurethane backbone of the oligomer (i.e., pendant to the polyurethane backbone, which is different from being at a terminal position), and at least one (meth)acrylate functional group is present at one or more terminal positions of the oligomer.

[0049] The number average molecular weight of the multi-(meth)acrylate functionalized oligomer can be varied as desired to impart certain properties to the oligomer itself and to the cured composition prepared from the oligomer. Generally speaking, if the oligomer comprises at least one polymer-containing segment, the number average molecular weight is typically slightly higher. For example, the oligomer may comprise one or more polymer-containing segments (i.e., a segment for chain extension as a polymer-type segment) and have a number average molecular weight of 3000 g / mol to 20,000 g / mol. An oligomer that does not comprise one or more polymer-containing segments may have, for example, a number average molecular weight of 500 g / mol to 5000 g / mol. As used herein, the number average and weight average molecular weight resins are obtained as follows: using an Agilent 1260GPC with a refractive index detector, and using polystyrene standards (samples) for calibration.

[0050] According to certain aspects of the present invention, the chain extending segments (eg, non-polymeric segments and / or polymeric segments) and the multi-(meth)acrylate functionalized segments may be present in the oligomer in a molar ratio of 0:1 to 10:1 (eg, 0.1:1 to 10:1).

[0051] In embodiments where one or more chain extender segments are present, the chain extender segments and multi-(meth)acrylate functionalized segments may be randomly arranged along the polyurethane backbone and connected together by segments containing urethane. By varying the synthetic process used to prepare the oligomer, the polymer may also have a more ordered structure. For example, the chain extender segments may be clustered near the center of the polyurethane backbone, with the multi-(meth)acrylate functionalized segments positioned toward the ends of the polyurethane backbone, or vice versa.

[0052] The carbamate-containing segments are segments containing carbamate functional groups (i.e., -OC(=O)-NH-), and are generally used to connect multi-(meth)acrylate functional segments and / or chain extender segments (if such chain extender segments are present in the oligomer) together. For example, a carbamate-containing segment may connect two multi-(meth)acrylate functional segments together, or may connect two chain extender segments together, or may connect a multi-(meth)acrylate functional segment to a chain extender segment. A carbamate-containing segment may also be present at one or more terminal terminations of the oligomer and provide a means of connecting the polyurethane backbone of the oligomer to the terminal (meth)acrylate functional groups.

[0053] The segments containing carbamate can be positioned between the multi-(meth)acrylate functionalized segments and connect the multi-(meth)acrylate functionalized segments together. As used herein, "segment L can be positioned between segments M and connects segments M together" means that both sides of segment L are directly connected to segment M to form the sequence -MLM-. The segments containing carbamate can be positioned between the multi-(meth)acrylate functionalized segments and the segment for chain extension and connect the multi-(meth)acrylate functionalized segments and the segment for chain extension together. As used herein, "segment L can be positioned between segment M and segment N and connects segment M and segment N together" means that one side of segment L is directly connected to segment M, and the other side of segment L is directly connected to segment N to form the sequence -MLN-. The carbamate-containing segments may be positioned between and link the terminal end-capping segments and the multi-(meth)acrylate functionalized segments together, and / or, if one or more chain extender segments are present, the carbamate-containing segments may be positioned between and link the terminal end-capping segments and the chain extender segments together. The chain extender segments and the multi-(meth)acrylate functionalized segments may be randomly arranged along the polyurethane backbone and linked together by the carbamate-containing segments.

[0054] Representative and non-limiting examples of multi-(meth)acrylate functionalized oligomers according to the present invention can be schematically depicted as follows:

[0055] ECS-UCS-MMFS-UCS-MMFS-UCS-MMFS-UCS-ECS

[0056] ECS-UCS-MMFS-UCS-CES-UCS-CES-UCS-MMFS-UCS-ECS

[0057] ECS-UCS-CES-UCS-MMFS-UCS-CES-UCS-MMFS-UCS-MMFS-UCS-ECS

[0058] ECS-UCS-MMFS-UCS-CES-UCS-ECS

[0059] Wherein, MMFS = multi-(meth)acrylate functionalized segment, UCS = urethane containing segment, ECS = terminal capping segment, and CES = chain extending segment.

[0060] Typically, because of their general method of synthesis, the oligomers according to the invention will be obtained as mixtures of oligomers having a range of different molecular weights, different numbers of multi-(meth)acrylate functionalized segments, numbers of urethane containing segments, numbers of terminal capping segments, and numbers of optional chain extending segments, as well as different sequences of such segments.

[0061] In certain aspects of the invention, the carbamate-containing segment may correspond to formula (I):

[0062] [-OC(=O)-NH-R 1 -NH-C(=O)-O-] (I)

[0063] Among them, R 1 is a divalent organic (e.g., hydrocarbyl) moiety. The hydrocarbyl moiety may be an aliphatic moiety (which may be linear, branched, or cyclic), an aromatic moiety, or an araliphatic moiety (which contains both aliphatic and aromatic components). The organic moiety may contain one or more heteroatoms (e.g., O, N, halogens) in addition to carbon and hydrogen atoms.

[0064] The urethane-containing segment may comprise, for example, a residue of a diisocyanate selected from the group consisting of tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3-(isocyanatemethyl)cyclohexane, isophorone diisocyanate, Isocyanates, trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, dianisidine diisocyanate, phenyl diisocyanate, halogenated phenyl diisocyanate, methylene diisocyanate, ethylene diisocyanate, butylene diisocyanate, propylene diisocyanate, octadecylene diisocyanate, 1,5-naphthylene diisocyanate, polymethylene polyphenylene diisocyanate, tolylene diisocyanate polymer (polymer type tolylene diisocyanate), diphenylmethane diisocyanate polymer (polymer type diphenylmethane diisocyanate isocyanate, PMDI), hexamethylene diisocyanate polymer (polymer hexamethylene diisocyanate), 3-phenyl-2-ethylene diisocyanate, cumene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 2,4'-diisocyanate diphenyl ether, 5,6-dimethyl-1,3-phenylene diisocyanate, 4,4'-diisocyanate diphenyl ether, benzidine diisocyanate, 9,10-anthracene diisocyanate, 4,4'- diisocyanate benzyl, 3,3'-dimethyl-4,4'-diisocyanate diphenylmethane, 2,6'-dimethyl-4,4'-diisocyanate diphenyl, 3,3'-dimethoxy-4,4'-diisocyanate diphenyl, 1,4-anthracene diisocyanate, phenylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 4,4'-methylene-bis(cyclohexyl isocyanate), and combinations thereof. 1 Also possible are residues of higher functionality polyisocyanates, such as triisocyanates (eg, triphenylmethane triisocyanate, 2,4,6-tolylene triisocyanate, 2,4,4'-triisocyanate diphenyl ether), but care should be taken when using such higher functionality polyisocyanates to avoid problems with gelling of the oligomers.

[0065] According to certain aspects of the present invention, the oligomer may comprise one or more multi-(meth)acrylate functionalized segments corresponding to formula (IIa):

[0066] [-CHR 2 -R3 -CHR 4 -] (IIa)

[0067] Among them, R 2 and R 4 are the same or different and correspond to -CH 2 -OC(=O)-CR 5 =CH 2 , where R 5 H or CH 3 , and R 3 is a divalent organic moiety. For example, R 3 Can be -R 3’ -or-CH 2 -OR 3’ -O-CH 2 -, where R 3’ is a divalent hydrocarbon moiety. Suitable divalent hydrocarbon moieties include: aliphatic divalent hydrocarbon moieties (whose structure may be linear, branched or cyclic), aromatic divalent hydrocarbon moieties, and aromatic aliphatic divalent hydrocarbon moieties. 3 and R 3’ In addition to carbon and hydrogen atoms, it may contain one or more heteroatoms (e.g., N, O, S, halogens). Exemplary divalent hydrocarbon moieties include, but are not limited to, one of the following:

[0068] -(Alk-O) m’ -(CH 2 ) m -(O-Alk) m ”-

[0069] -(Alk-O) m’ -Ar-CR 8 R 9 -Ar-(O-Alk) m ”-

[0070] wherein m is an integer of at least 2 (e.g., 2-10),

[0071] m' and m" are independently integers from 0 to 20,

[0072] Each Alk is independently C 2 -C 4 Alkylene, typically ethylene or 1,2-propylene or 1,4-butylene;

[0073] each Ar is the same or different and is a substituted or unsubstituted aromatic moiety (such as a substituted or unsubstituted phenylene moiety); and

[0074] R 8 and R 9are the same or different and are selected from H, aryl and alkyl.

[0075] According to certain aspects of the present invention, the oligomer may comprise one or more multi-(meth)acrylate functionalized segments corresponding to formula (IIb):

[0076]

[0077] Where R 2 , R 4 and R 10 are the same or different and correspond to -CH 2 -OC(=O)-CR 5 =CH 2 , where R 5 H or CH 3 ; R 3 is a trivalent organic moiety; and the wavy line represents the point of attachment to the additional segments of the oligomer, particularly to the segment containing the urethane. For example, R 3 Can be -R 3’ -,or

[0078]

[0079] Among them, R 3’ is a trivalent hydrocarbon moiety. Suitable trivalent hydrocarbon moieties include aliphatic trivalent hydrocarbon moieties (whose structure may be linear, branched, or cyclic), aromatic trivalent hydrocarbon moieties, and aromatic aliphatic trivalent hydrocarbon moieties. 3 and R 3’ In addition to carbon and hydrogen atoms, it may contain one or more heteroatoms (e.g., N, O, S, halogens). Exemplary trivalent hydrocarbon moieties include, but are not limited to, one of the following:

[0080]

[0081] wherein p, p' and p" are independently integers from 0 to 10;

[0082] q, q' and q" are independently integers from 0 to 20;

[0083] Each Alk is independently C2-C4 alkylene, typically ethylene or 1,2-propylene or 1,4-butylene;

[0084] each Ar is the same or different and is a substituted or unsubstituted aromatic moiety (such as a substituted or unsubstituted phenylene moiety);

[0085] R 8 and R 9 are the same or different and are selected from H and alkyl.

[0086] As mentioned above, the oligomer may optionally contain at least one polymer segment as a chain extension segment. The polymer segment may be selected from: a segment containing polyether, a segment containing polyester, a segment containing polydiene, a segment containing polycarbonate, and a segment containing polyorganosiloxane. Although different types of polymer segments may be present in the oligomer, according to certain embodiments, the oligomer contains only one type of polymer segment.

[0087] The polymer segment may correspond to formula (III):

[0088] [-R 6 -] (III)

[0089] Among them, R 6 is a divalent polymeric moiety, such as a divalent polyether moiety, a divalent polyester moiety, a divalent polydiene moiety, a divalent polycarbonate moiety, or a divalent polyorganosiloxane moiety. According to certain aspects of the present invention, the divalent polymeric moiety may have a number average molecular weight of 200 g / mol to 6000 g / mol.

[0090] Suitable divalent polyether moieties include aliphatic divalent polyether moieties such as divalent polyoxyethylene moieties, divalent polyoxypropylene moieties, divalent polyoxyethylene / oxypropylene moieties, and divalent polyoxytetramethylene moieties.

[0091] The polymeric segment may be the residue of a dihydroxy-functionalized polymer such as a polyether diol, polyester diol, polydiene diol, polycarbonate diol, or polyorganosiloxane diol. Typically, the hydroxyl groups in such polymers are in terminal positions and are primary or secondary hydroxyl groups that will react readily with the diisocyanate used to make the oligomer.

[0092] As mentioned previously, the oligomer may optionally include at least one non-polymeric segment as a chain-extending segment. As used herein, the term "non-polymeric" refers to a substance containing up to four repeating monomeric units (e.g., segments derived from ethylene glycol, which has a single oxyethylene unit, and triethylene glycol, which has three repeating oxyethylene units, would both be considered non-polymeric). Although different types of non-polymeric segments may be present in the oligomer, according to certain embodiments, the oligomer contains only one type of non-polymeric segment.

[0093] The non-polymeric segment may correspond to formula (IIIa):

[0094] [-R 6a -] (IIIa)

[0095] Among them, R 6a is a divalent aliphatic, aromatic or araliphatic moiety, such as a divalent C 2 -C 30 Aliphatic moieties which may be linear or branched or contain one or more alicyclic rings. The divalent aliphatic, aromatic or araliphatic moieties may contain one or more heteroatoms such as O, N, S and / or halogens. Such non-polymeric segments are distinguished from the multi-(meth)acrylate functionalized segments in that they contain at most a single (meth)acrylate functional group. They are distinguished from the terminal end-capped segments in that they are divalent rather than monovalent. Furthermore, the non-polymeric segments are different from the urethane-containing segments in that they do not contain urethane groups which serve as connecting moieties between segments in the oligomer.

[0096] The non-polymeric segment may be a non-polymeric aliphatic segment that is a residue of an aliphatic diol (linear, branched, or containing a ring structure), such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 1,3-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, and the like, and short-chain oligomers thereof (containing up to four oxyalkylene repeating units). Typically, the hydroxyl groups in such aliphatic diols are primary or secondary hydroxyl groups, which will react readily with the diisocyanate used to make the oligomers.

[0097] At least one terminal capping block present in the oligomer may have a structure corresponding to formula (IV):

[0098] -OR 7 -[OC(=O)-CR 8 =CH 2 ] n (IV)

[0099] Among them, R 7 is an n+1 valent organic part, R 8 H or CH 3 , and n is an integer from 1 to 5. Each end of the oligomer may have a terminal capping segment corresponding to formula (IV). 7 R may be a residue of a polyol, such as a diol, a triol or a tetraol (e.g., ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, triethylolpropane, pentaerythritol, dipentaerythritol, ditrimethylolpropane). 7 -CH 2 CH 2 -or-(CH 2) 5 -C(=O)-[O-(CH 2 ) 5 -C(=O)] x -O-CH 2 -CH 2 -, wherein x is an integer from 0 to 9, and n = 1. When n = 1, R 7 =CH 2 CH 2 , and R 8 =H, such terminal end-block is derived from hydroxyethyl acrylate. When n=1, R 7 =-(CH 2 ) 5 -C(=O)-[O-(CH 2 ) 5 -C(=O)] x -O-CH 2 -CH 2 -, and R 8 =H, such a terminal end-block can be derived from hydroxyethyl acrylate modified with caprolactone

[0100] The oligomers according to the invention may comprise one or more units of formula (A2):

[0101] [-OC(=O)-NH-R 1 -NH-C(=O)-O-CHR 2 -R 3 -CHR 4 -] (A2)

[0102] Among them, R 1 is a divalent hydrocarbon part, R 2 and R 4 are the same or different and correspond to -CH 2 -OC(=O)-CR 5 =CH 2 , where R 5 H or CH 3 , and R 3 is a divalent organic moiety. Thus, the unit of formula (A2) may be a urethane-containing segment as described above coupled to a multi-(meth)acrylate-functional segment as described above.

[0103] In addition to one or more units of formula (A2), the oligomer may optionally further comprise one or more units of formula (B):

[0104] [-OC(=O)-NH-R 1 -NH-C(=O)-OR 6-] (B)

[0105] Among them, R 1 is a divalent hydrocarbon moiety, and R 6 is a divalent polymeric moiety selected from the group consisting of a divalent polyether moiety, a divalent polyester moiety, a divalent polydiene moiety, a divalent polycarbonate moiety, and a divalent polyorganosiloxane moiety. Thus, the unit of formula (B) may be a urethane-containing segment as described above coupled to a polymeric segment as described above. Alternatively, R 6 It may be a divalent non-polymeric moiety, such as C 2 -C 12 A divalent hydrocarbon moiety (e.g., -(CH 2 ) m -, wherein m is an integer from 2 to 12).

[0106] The oligomers according to the invention may comprise one or more units of formula (A3):

[0107]

[0108] Among them, R 1 is a divalent hydrocarbon part, R 2 , R 4 and R 10 are the same or different and correspond to -CH 2 -OC(=O)-CR 5 =CH 2 , where R 5 H or CH 3 ; R 3 is a trivalent organic moiety; and the wavy line represents an attachment point to an additional segment of the oligomer, in particular to a segment containing a urethane. Thus, the unit having formula (A3) may be a segment containing a urethane as described above, coupled to a segment functionalized with a multi-(meth)acrylate as described above.

[0109] In addition to one or more units of formula (A3), the oligomer may optionally further comprise one or more units of formula (B) as described above.

[0110] The oligomer may comprise a mixture of one or more units of formula (A2) and one or more units of formula (A3) as described above, and optionally further comprise one or more units of formula (B) as described above.

[0111] A further aspect of the invention provides a multi-(meth)acrylate functionalized oligomer having a polyurethane backbone, a plurality of (meth)acrylate functional groups pendant to the polyurethane backbone, and one or more terminal (meth)acrylate functional groups, wherein the oligomer is the reaction product of reactants comprising: a) at least one diisocyanate, b) at least one diol compound comprising at least two (meth)acrylate functional groups or at least one triol compound comprising at least three (meth)acrylate functional groups, or mixtures thereof, c) at least one terminal capping compound comprising a single isocyanate-reactive hydroxyl group and at least one (meth)acrylate functional group, and optionally, d) at least one chain-extending diol containing no more than one (meth)acrylate functional group and which may be non-polymeric or polymeric, such as a polymeric diol selected from the group consisting of polyether polyols, polyester polyols, polydiene polyols, polycarbonate polyols, and polyorganosiloxane polyols.

[0112] In order to prepare the (meth)acrylate functionalized oligomer according to the present invention, one diisocyanate or a mixture of different diisocyanates can be used. As used herein, the term "diisocyanate" means an organic compound containing two isocyanate (-NCO) functional groups per molecule. In certain embodiments, the diisocyanate is an aliphatic diisocyanate (including alicyclic diisocyanates) or an aromatic diisocyanate.

[0113] According to certain embodiments of the present invention, the diisocyanate may be represented by the following formula (I'):

[0114] OCN-R 1 -NCO (I')

[0115] Among them, R 1 is a divalent organic moiety, such as a divalent hydrocarbon moiety. The divalent hydrocarbon moiety may, for example, be aliphatic (such as a linear, branched, or cyclic aliphatic moiety), aromatic, or aromatic aliphatic. The divalent organic moiety may contain one or more heteroatoms, such as N, O, or halogen, in addition to carbon and hydrogen atoms.

[0116] Illustrative examples of suitable diisocyanates include, without limitation, isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), dicyclohexylmethane 4,4'-diisocyanate (also known as methylene dicyclohexyl diisocyanate, or hydrogenated MDI (HMDI)), hexamethylene diisocyanate (1,6-hexamethylene diisocyanate), 4,4'-methylenebis(phenyl isocyanate), xylene diisocyanate, bis-tolylene diisocyanate (o-tolidine diisocyanate), 1,5-naphthylene diisocyanate, naphthylene diisocyanate, and dianisidine diisocyanate, as well as polymethylene polyphenyl isocyanates. Examples of preferred diisocyanates include toluene diisocyanate (e.g., 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (e.g., 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate), xylylene diisocyanate (1,3-diisocyanatomethylbenzene), hydrogenated xylylene diisocyanate (sometimes referred to as 1,3-diisocyanatomethylcyclohexane), methylene bis(4-isocyanatocyclohexane) (sometimes referred to as hydrogenated MDI, or methylene-biscyclohexane diisocyanate), and combinations thereof.

[0117] The polyol compound used to prepare the multi-(meth)acrylate functionalized oligomer of the present invention contains at least two (meth)acrylate functional groups in addition to at least two isocyanate-reactive hydroxyl groups. In certain embodiments, the polyol compound is a diol compound, that is, it contains only two isocyanate-reactive hydroxyl groups in addition to at least two (meth)acrylate functional groups. According to certain aspects of the present invention, the polyol compound is a diol compound corresponding to formula (II'a):

[0118] HO-CHR 2 -R 3 -CHR 4 -OH (II'a)

[0119] Among them, R 2 and R 4 are the same or different and correspond to -CH 2 -OC(=O)-CR 5 =CH 2 , where R 5 H or CH 3 , and R 3 is a divalent organic moiety. For example, R 3 Can be -R 3’ -or-CH 2 -OR 3’ -O-CH2 -, where R 3’ is a divalent hydrocarbon moiety. Suitable divalent hydrocarbon moieties include: aliphatic divalent hydrocarbon moieties (whose structure may be linear, branched, or cyclic), aromatic divalent hydrocarbon moieties, and aromatic aliphatic divalent hydrocarbon moieties. 3 In addition to carbon and hydrogen atoms, it may contain one or more heteroatoms (e.g., N, O, S, halogens). Exemplary divalent hydrocarbon moieties include, but are not limited to, one of the following:

[0120] -(Alk-O) m’ -(CH 2 ) m -(O-Alk) m ”-

[0121] -(Alk-O) m’ -Ar-CR 8 R 9 -Ar-(O-Alk) m ”-

[0122] wherein m is an integer of at least 2 (e.g., 2-10);

[0123] m' and m" are independently integers from 0 to 20,

[0124] Each Alk is independently C 2 -C 4 Alkylene, typically ethylene or 1,2-propylene or 1,4-butylene;

[0125] Each Ar is the same or different and is a substituted or unsubstituted aromatic moiety (such as a substituted or unsubstituted phenylene moiety), and R 8 and R 9 are the same or different and are selected from H, aryl and alkyl.

[0126] According to certain embodiments of the present invention, the polyol compound is or includes 1,4-bis(3-acryloyloxy-2-hydroxypropoxy)butane (wherein in formula (II'a), R 2 and R 4 Each is -CH 2 -OC(=O)-CH=CH 2 , and R 3 -CH 2 -O-(CH 2 ) 4 -O-CH 2 -). This compound can be obtained by reacting 1,4-butanediol diglycidyl ether with acrylic acid.

[0127] According to certain aspects of the present invention, the polyol compound is a triol compound corresponding to formula (II'b):

[0128]

[0129] Among them, R 2 , R 3 , R 4 and R 10 is as described above for formula (IIb).

[0130] According to certain embodiments of the present invention, the polyol compound is or includes trimethylolpropane triglycidyl ether triacrylate, (wherein in formula (II'b), R 2 , R 4 and R 10 Each is -CH 2 -OC(=O)-CH=CH 2 , and R 3 for

[0131]

[0132] This compound can be obtained by reacting trimethylolpropane triglycidyl ether and acrylic acid.

[0133] The polyol compound may, for example, be a reaction product comprising the following reactants: an acid-functional (meth)acrylate and a polyepoxide (eg, a diepoxide or a triepoxide). The acid-functional (meth)acrylate may have a structure corresponding to formula (V):

[0134] H 2 C=C(R)C(=O)O[CH 2 CH 2 C(=O)O] n H (V)

[0135] Where R is H or CH 3 , and n is an integer from 0 to 5. The compounds according to formula (V) include acrylic acid (R=H, n=0), methacrylic acid (R=CH 3 , n=0), and oligomers thereof (wherein n=1, 2, 3, 4 or 5), and mixtures thereof.

[0136] Suitable acid-functional (meth)acrylates also include the so-called "half esters" which are obtained by reacting anhydrides or dibasic acids with hydroxy-functional acrylates or methacrylates.

[0137] Suitable anhydrides and dibasic acids for such purposes include aliphatic, aromatic and araliphatic anhydrides (which contain anhydride groups) and dibasic acids (which contain two carboxylic acid groups). Illustrative anhydrides and dibasic acids include, but are not limited to, phthalic anhydride, isophthalic acid, terephthalic acid, tetrabromophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, itaconic acid, phthalic acid, 5-norbornene-endo-2,3-dicarboxylic anhydride, naphthylic anhydride, maleic anhydride, succinic anhydride, chlorendic anhydride, maleic acid, succinic acid, fumaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, and dimer fatty acids.

[0138] The hydroxyl-functional (meth)acrylate that can be reacted with an anhydride or a dibasic acid to obtain an acid-functional (meth)acrylate can have a structure corresponding to formula (IV'):

[0139] HO-R 7 -[OC(=O)-CR 8 =CH 2 ] n (IV')

[0140] Among them, R 7 is an n+1 valent organic part, R 8 H or CH 3 , and n is an integer from 1 to 3.

[0141] In certain embodiments of the present invention, hydroxyalkyl (meth)acrylates, such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate, are used as the hydroxy-functional (meth)acrylate to be reacted with the diepoxide. Examples of other suitable hydroxyl-functional (meth)acrylates include, without limitation, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, triethylolpropane di(meth)acrylate, hydroxybutyl(meth)acrylate, glycerol di(meth)acrylate, neopentyl glycol mono(meth)acrylate, hexylene glycol mono(meth)acrylate, octanediol mono(meth)acrylate, decanediol mono(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, alkoxylated (e.g., ethoxylated and / or propoxylated) trimethylolpropane di(meth)acrylate, alkoxylated triethylolpropane di(meth)acrylate, alkoxylated glycerol di(meth)acrylate, alkoxylated hexylene glycol mono(meth)acrylate, alkoxylated neopentyl glycol mono(meth)acrylate, alkoxylated hydroxyl-functional (meth)acrylates having the structure H 2 C=CR-C(=O)-O-CH 2 -CH 2 -(OC(=O)-CH2 -CH 2 -CH 2 -CH 2 -CH 2 ) x -OH (where R is H or CH 3 and x is an integer from 1 to 10) (sometimes also referred to as "caprolactone-modified (meth)acrylates"), mono(meth)acrylates of bisphenols and alkoxylated bisphenols, mono(meth)acrylates of bis(hydroxymethyl)cyclohexane and alkoxylated bis(hydroxymethyl)cyclohexane, mono(meth)acrylates of tricyclodecane dimethanol and alkoxylated tricyclodecane dimethanol, and the like, and combinations thereof.

[0142] Suitable diepoxides or triepoxides that can be reacted with the acid-functionalized (meth)acrylates include, but are not limited to, diepoxides selected from diene diepoxides and diglycidyl ethers, and triepoxides selected from triglycidyl ethers. "Diolefin diepoxides" are compounds corresponding to dienes in which both olefinic sites (i.e., both sites of olefinic unsaturation) have been epoxidized. "Diglycidyl ethers" are compounds containing two glycidyl ether functional groups (i.e., having the structure

[0143]

[0144] The diepoxide may be aliphatic, aromatic or araliphatic. "Triglycidyl ether" is a compound containing three glycidyl ether functional groups (i.e., having the structure

[0145]

[0146] The triepoxide may be aliphatic, aromatic or araliphatic.

[0147] Illustrative examples of suitable diepoxides include: diglycidyl ethers of bisphenol compounds (e.g., diglycidyl ethers of bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z), diglycidyl ethers of hydrogenated bisphenol compounds, diglycidyl ethers of aliphatic diols (e.g., diglycidyl ethers of ethylene glycol, propylene glycol, or neopentyl glycol), 1,4-butanediol, diglycidyl ether, 1,3-butadiene diepoxide, diepoxide of vinylcyclohexene, diepoxide of octadiene, dicyclopentadiene dioxide, diglycidyl 1,2-cyclohexanedicarboxylate, diepoxycyclooctane, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, diglycidyl ether of dihydroxynaphthalene, diglycidyl ether, 1,4-dihydroxybenzene diglycidyl ether, catechol diglycidyl ether, and resorcinol diglycidyl ether, and combinations thereof. Illustrative examples of suitable triepoxides include trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil glycidyl ether, glycerol triglycidyl ether, propoxylated glycol triglycidyl ether, polyglycerol-3-polyglycidyl ether, phloroglucinol triglycidyl ether, tris(4-hydroxyphenyl)methane triglycidyl ether, tris(4-hydroxyphenyl)ethane triglycidyl ether, and combinations thereof.

[0148] The terminal end-capping compound may be selected from (meth)acrylates of polyols in which all hydroxyl groups except one have been (meth)acrylated. The polyol may be, for example, a diol, a triol or a tetraol. Suitable terminal end-capping compounds may generally correspond to the hydroxyl functional (meth)acrylates mentioned above and may have a structure corresponding to formula (IV'):

[0149] HO-R 7 -[OC(=O)-CR 8 =CH 2 ] n (IV')

[0150] Where R 7 is an n+1 valent organic part, R 8 H or CH 3 , and n is an integer from 1 to 3.

[0151] In certain embodiments of the present invention, hydroxyalkyl (meth)acrylates, such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate, are used as terminal capping compounds. Examples of other suitable terminal end-capping compounds include, but are not limited to, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, triethylolpropane di(meth)acrylate, hydroxybutyl(meth)acrylate, glycerol di(meth)acrylate, neopentyl glycol mono(meth)acrylate, hexanediol mono(meth)acrylate, octanediol mono(meth)acrylate, decanediol mono(meth)acrylate, tri(2-hydroxyethyl)isocyanurate di(meth)acrylate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, alkoxylated (e.g., ethoxylated and / or propoxylated) trimethylolpropane di(meth)acrylate, alkoxylated triethylolpropane di(meth)acrylate, alkoxylated glycerol di(meth)acrylate, alkoxylated hexanediol mono(meth)acrylate, alkoxylated neopentyl glycol mono(meth)acrylate, alkoxylated esters of the structure H 2 C=CR-C(=O)-O-CH 2 -CH 2 -(OC(=O)-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 ) x -OH (where R is H or CH 3 , and x is an integer from 1 to 10), mono(meth)acrylates of bisphenol and alkoxylated bisphenol, mono(meth)acrylates of bis(hydroxymethyl)cyclohexane and alkoxylated bis(hydroxymethyl)cyclohexane, mono(meth)acrylates of tricyclodecane dimethanol and alkoxylated tricyclodecane dimethanol, and the like, and combinations thereof.

[0152] As mentioned previously, the poly(meth)acrylate functionalized oligomers may optionally be prepared using one or more polymeric diols and / or one or more non-polymeric diols as reactants. Such diols may be considered chain-extending diols because they may function to increase the average spacing between poly(meth)acrylate functionalized segments along the polyurethane backbone of the oligomer, and / or to increase the number average molecular weight of the oligomer. As used herein, the term "polymeric diol" means a polymer having two isocyanate-reactive hydroxyl groups per molecule. As used herein, the term "non-polymeric diol" means a non-polymeric compound having two isocyanate-reactive hydroxyl groups per molecule. In the context of the present invention, the term "polymer" means a compound having five or more repeating units per molecule, and the term "non-polymeric compound" means a compound having up to four repeating units per molecule (and thus both monomeric and oligomeric compounds having 2 to 4 repeating units per molecule). For example, ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol are examples of non-polymeric diols, while polyethylene glycol containing five or more oxyalkylene repeating units is an example of a polymeric diol.

[0153] Preferably, the hydroxyl groups are primary and / or secondary hydroxyl groups. In the case where the chain-extending diol is a polymeric polyol, according to certain embodiments, the hydroxyl groups may be located at the terminal ends of the polymer. However, the hydroxyl groups may also be present along the backbone of the polymer, or on side chains or groups suspended from the polymer backbone. The polymer portion of the polymeric diol may comprise a plurality of repeating units, such as oxyalkylene units, ester units, carbonate units, acrylic units, alkylene units, etc., or combinations thereof.

[0154] According to certain embodiments of the present invention, the polymeric diol may be represented by the following formula (III'):

[0155] HO-R 6 -OH (III')

[0156] Among them, R 6 is a polyether (eg, polyoxyalkylene), polycarbonate, polydiene, polyorganosiloxane or polyester chain.

[0157] Particularly preferred polymeric diols include polyether diols and polyester diols. Suitable polyether diols include, for example, polytetramethylene glycol (a hydroxy-functionalized polymer of tetrahydrofuran) and polyethylene glycol (a hydroxy-functionalized polymer of ethylene oxide). Suitable polyester diols include, for example, poly(caprolactone), poly(lactide), poly(alkylene glycol adipate), and poly(alkylene glycol succinate).

[0158] Other types of polymeric polyols potentially useful in the present invention include polycarbonate polyols, polyorganosiloxane diols (eg, polydimethylsiloxane diols), and polydiene diols (eg, polybutadiene diols, including fully or partially hydrogenated polydiene polyols).

[0159] The molecular weight of the polymeric diol can vary as desired or required to achieve specific properties in: a multi-(meth)acrylate functionalized oligomer prepared from the polymeric diol, and / or a curable composition containing the multi-(meth)acrylate functionalized oligomer, and / or a cured composition obtained by curing the curable composition. For example, the number average molecular weight of the polymeric diol can be at least 300, at least 350, or at least 400 Daltons. In other embodiments, the polymeric diol can have a number average molecular weight of 5000 Daltons or less, 4500 Daltons or less, or 4000 Daltons or less. For example, the polymeric diol can have a number average molecular weight of 250 to 5000 Daltons, 300 to 4500 Daltons, or 350 to 4000 Daltons.

[0160] According to certain embodiments of the present invention, the chain-extending diol may be represented by the following formula (IIIa'):

[0161] HO-R 6a -OH (IIIa')

[0162] Among them, R 6a is a divalent non-polymeric aliphatic moiety optionally further comprising one or more heteroatoms such as O, N, S and / or halogen.

[0163] In certain aspects of the invention, the chain-extending diol is or includes a non-polymeric diol that is a hydrogenated dimer fatty acid (sometimes also referred to as a "dimer diol"), such as a diol obtained by dimerizing one or more unsaturated fatty acids (such as oleic acid or linoleic acid) and subsequently hydrogenating to convert the carboxylic acid groups to hydroxyl groups. 2033 (a product sold by Croda) is an example of a suitable commercially available hydrogenated dimer fatty acid.

[0164] Other types of suitable non-polymeric diols include, but are not limited to: 2 -C 12Aliphatic diols and oligomers thereof (containing up to four oxyalkylene repeating units). The aliphatic diol structure may be linear, branched, or cyclic, wherein the hydroxyl groups are all primary, or all secondary, or one of each type (one primary and one secondary).

[0165] Examples of suitable C2-C12 aliphatic diols include, but are not limited to, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexanediol, diethylene glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,5-pentanediol, and 2-methyl-2-ethyl-1,3-propanediol, and oligomers thereof (containing up to four oxyalkylene repeating units).

[0166] Illustrative Methods for Making Multi-(Meth)acrylate Functionalized Oligomers

[0167] Various exemplary methods for preparing the multi-(meth)acrylate functionalized oligomers according to the present invention can be described as follows.

[0168] Method 1: The multi-(meth)acrylate functionalized oligomer according to the present invention can be synthesized by a process comprising combining and reacting the following to obtain the multi-(meth)acrylate functionalized oligomer: at least one diisocyanate, at least one diol compound (which contains at least two (meth)acrylate functional groups) or at least one triol compound (which contains at least three (meth)acrylate functional groups) or a mixture thereof, at least one terminal capping compound (which contains a single isocyanate-reactive hydroxyl group and at least one (meth)acrylate functional group), and optionally, at least one polymeric diol.

[0169] Method 2: The multi-(meth)acrylate functionalized oligomer according to the present invention can be synthesized by a process comprising: a) combining and reacting at least one diisocyanate, at least one diol compound (which contains at least two (meth)acrylate functional groups) or at least one triol compound (which contains at least three (meth)acrylate functional groups) or a mixture thereof, and optionally, at least one polymeric diol to obtain an isocyanate-terminated intermediate oligomer; and b) combining and reacting at least one terminal capping compound (which contains a single isocyanate-reactive hydroxyl group and at least one (meth)acrylate functional group) and the isocyanate-terminated intermediate oligomer to obtain the multi-(meth)acrylate functionalized oligomer. In order to facilitate the production of the isocyanate-terminated intermediate oligomer in step a), the NCO:OH stoichiometry of the reactants in step a) can be adjusted, and / or the method and / or order of combining and reacting the reactants can be changed.

[0170] Method 3: The multi-(meth)acrylate functionalized oligomer according to the present invention can be synthesized by a process comprising: a) combining and reacting at least one diisocyanate, at least one diol compound (which contains at least two (meth)acrylate functional groups) or at least one triol compound (which contains at least three (meth)acrylate functional groups) or a mixture thereof, and optionally, at least one polymeric diol to obtain a hydroxyl-terminated intermediate oligomer; and b) combining and reacting the hydroxyl-terminated intermediate oligomer, and at least one isocyanate-functional (meth)acrylate (or a combination of a diisocyanate and a terminal end-capping compound, such as a hydroxyl-functional (meth)acrylate, for example, 2-hydroxyethyl acrylate) to obtain the multi-(meth)acrylate functionalized oligomer. In order to facilitate the production of the hydroxyl-terminated intermediate oligomer in step a), the NCO:OH stoichiometry of the reactants in step a) can be adjusted, and / or the method and / or order of combining and reacting the reactants can be changed. The isocyanate functional (meth)acrylate may be provided by reacting a diisocyanate as described herein and a terminal capping compound comprising a single isocyanate-reactive hydroxyl group and at least one (meth)acrylate functional group.

[0171] Method 4: The multi-(meth)acrylate functionalized oligomer according to the present invention can be synthesized by a process comprising: a) combining and reacting the following to obtain an isocyanate-terminated intermediate oligomer: at least one diisocyanate, and at least one diol compound (which contains at least two (meth)acrylate functional groups) or at least one triol compound (which contains at least three (meth)acrylate functional groups) or a mixture thereof; b) combining and reacting the following to obtain a hydroxyl-terminated intermediate oligomer: the isocyanate-terminated intermediate oligomer and a chain-extending polyol (which contains at least two hydroxyl groups and zero or one (meth)acrylate functional group), and, d) combining and reacting the following to obtain the multi-(meth)acrylate functionalized oligomer: the hydroxyl-terminated intermediate oligomer, and at least one isocyanate-functionalized (meth)acrylate (or a combination of a diisocyanate and a terminal blocking compound, the terminal blocking compound such as a hydroxyl-functionalized (meth)acrylate, for example 2-hydroxyethyl acrylate). To facilitate the production of isocyanate-terminated intermediate oligomers in step a), the NCO:OH stoichiometry of the reactants in step a) may be adjusted, and / or the method and / or order of combining and reacting the reactants may be altered. To facilitate the production of hydroxyl-terminated intermediate oligomers in step b), the NCO:OH stoichiometry of the reactants in step b) may be adjusted, and / or the method and / or order of combining and reacting the reactants may be altered. The isocyanate-functional (meth)acrylate may be provided by reacting a diisocyanate as described herein and a terminal capping compound comprising a single isocyanate-reactive hydroxyl group and at least one (meth)acrylate functional group.

[0172] Depending on the application, the amounts of the various components may vary over a wide range. The at least one diol compound (which contains at least two (meth)acrylate functional groups) or the at least one triol compound (which contains at least three (meth)acrylate functional groups), either individually or collectively, may preferably vary from 0.1 wt% (calculated based on all reactants) to 35 wt%, more preferably from 0.2 wt% to 25 wt%, and most preferably from 1 wt% to 10 wt%. The overall NCO:OH stoichiometry may be adjusted so that the free hydroxyl number in the final product is from 0 to 20 mg KOH / gm sample. The free hydroxyl number is determined by hydroxyl titration (ASTM E1899-08).

[0173] To prevent undesirable side reactions, antioxidants (stabilizers) such as butylated hydroxytoluene may be present while the components for preparing the oligomer are reacting, and / or air may be used to sparge the reaction mixture while such a reaction is occurring. Conditions effective for achieving a reaction between an isocyanate compound and an isocyanate-reactive compound of the type described herein (which may be used to prepare the oligomer according to the present invention) are known in the art and may be readily selected and adjusted as required to achieve the desired results for the purposes of this invention. For example, to accelerate the reaction, the reaction mixture may be heated and / or a urethane catalyst (as described below) may be introduced. Further, the stoichiometry between the different components for preparing the oligomer may be adjusted according to conventional practice to achieve a specific desired degree of polyurethane chain extension and / or terminal group functionalization.

[0174] Urethane Catalyst

[0175] According to certain embodiments of the present invention, one or more urethane catalysts are employed in the preparation of the multi-(meth)acrylate functionalized oligomers from the reactants previously described herein. As used herein, "urethane catalyst" means a substance capable of catalyzing the reaction between hydroxyl groups and isocyanate groups to form a urethane linking moiety. Thus, a urethane catalyst can accelerate the rate at which such a reaction occurs at a given temperature, and / or achieve a target degree of completion of such a reaction at a temperature below the temperature at which the target degree of completion is achieved in the absence of any urethane catalyst.

[0176] Any tin-based urethane catalyst known in the art can be used. However, according to certain preferred embodiments, a non-tin urethane catalyst or a combination of non-tin urethane catalysts is used. In certain embodiments, the intermediate reaction mixture and the resulting product (which contains the multi-(meth)acrylate functionalized oligomer) are free of or substantially free of any tin urethane catalyst. For example, the reaction mixtures at each stage and the final reaction product and curable composition may contain less than 500 ppb tin, less than 400 ppb tin, less than 300 ppb tin, less than 200 ppb tin, or less than 100 ppb tin.

[0177] Suitable non-tin urethane catalysts include, for example, one or more non-tin urethane catalysts selected from the following: carboxylate complexes of bismuth (such as bismuth octoate); acetylacetonate complexes of zirconium; acetylacetonate complexes of hafnium; acetylacetonate complexes of titanium; β-diketiminate complexes of zirconium; β-diketiminate complexes of hafnium; β-diketiminate complexes of titanium; amidinate complexes of zirconium; amidinate complexes of hafnium; amidinate complexes of titanium; carboxylate complexes of zinc; tertiary amines; imidazoles; N-heterocyclic carbenes; tetraalkylammonium halides; phosphines; and combinations thereof.

[0178] Typically, urethane catalysts are used in amounts of 0.0001 to 0.1 wt %, based on the total weight of the final (meth)acrylate functionalized oligomer.

[0179] Curable compositions containing multi-(meth)acrylate functionalized oligomers

[0180] While the multi-(meth)acrylate functionalized oligomers of the present invention can be used as curable compositions (i.e., compositions that can be cured to provide a polymerized, cured material) by themselves, in other aspects of the present invention, one or more multi-(meth)acrylate functionalized oligomers according to the present invention can be formulated with one or more additives (i.e., substances other than the multi-(meth)acrylate functionalized oligomers of the present invention) to provide a curable composition. Such additives can include, for example, reactive diluents, oligomers other than the multi-(meth)acrylate functionalized oligomers according to the present invention (especially (meth)acrylate functionalized oligomers), stabilizers, initiators (including photoinitiators), fillers, pigments, etc., and combinations thereof. Any additive known or used in the art of curable (meth)acrylate resins can also be employed with the multi-(meth)acrylate functionalized oligomers of the present invention to formulate curable compositions that can be used in a variety of end-use applications. Certain such additives are discussed in more detail below.

[0181] Additional reactive components

[0182] The curable composition can be formulated to include one or more additional components that are capable of reacting with the multi-(meth)acrylate functionalized oligomer according to the present invention. That is, such additional components become covalently bonded to the polymeric matrix formed when the curable composition is cured. Typically, such additional reactive components contain one or more ethylenically unsaturated functional groups per molecule, particularly one or more (meth)acrylate functional groups per molecule. Suitable ethylenically unsaturated functional groups of other types include, for example, vinyl functional groups and allyl functional groups. The additional reactive component characteristics may be monomeric or oligomeric, as described in more detail below.

[0183] The relative amounts of the multi-(meth)acrylate functionalized oligomer according to the present invention and the additional reactive components (such as other (meth)acrylate functionalized compounds) in the curable composition are not considered critical and may vary widely, depending on the specific components selected for use and the properties sought in the curable composition and the cured composition obtained therefrom. For example, the curable composition may comprise 0.5 to 99.5 wt. % of the (meth)acrylate functionalized oligomer according to the present invention and 0.5 to 99.5 wt. % of the additional reactive components, based on the total weight of the multi-(meth)acrylate functionalized oligomer according to the present invention and the additional reactive components.

[0184] Suitable (meth)acrylate functional compounds include both (meth)acrylate functional monomers and (meth)acrylate functional oligomers.

[0185] According to certain embodiments of the present invention, the curable composition comprises, in addition to at least one multi-(meth)acrylate functionalized oligomer according to the present invention, at least one (meth)acrylate functionalized monomer containing two or more (meth)acrylate functional groups per molecule. Examples of useful (meth)acrylate functionalized monomers containing two or more (meth)acrylate functional groups per molecule include: acrylates and methacrylates of polyhydric alcohols (organic compounds containing two or more, for example, 2 to 6 hydroxyl groups per molecule). Specific examples of suitable polyhydric alcohols include: polyhydric alcohols including C 2-20 Alkylene glycol (preferably having C 2-10diols having an alkylene group, wherein the carbon chain may be branched; for example: ethylene glycol, trimethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, tetramethylene glycol (1,4-butanediol), 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,12-dodecanediol, cyclohexane-1,4-dimethanol, bisphenols, and hydrogenated bisphenols, and alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof, wherein, for example, 1 to 20 mol of alkylene oxides (such as ethylene oxide and / or propylene oxide) have been reacted with 1 mol of diol), diethylene glycol, glycerol, alkoxylated glycerol, triethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane Alkane, alkoxylated trimethylolpropane, ditrimethylolpropane, alkoxylated ditrimethylolpropane, pentaerythritol, alkoxylated pentaerythritol, dipentaerythritol, alkoxylated dipentaerythritol, cyclohexanediol, alkoxylated cyclohexanediol, cyclohexanedimethanol, alkoxylated cyclohexanedimethanol, norbornene dimethanol, alkoxylated norbornene dimethanol, norbornane dimethanol, alkoxylated norbornane dimethanol, polyols containing aromatic rings, cyclohexane-1,4-dimethanol ethylene oxide adduct, bisphenol ethylene oxide adduct, hydrogenated bisphenol ethylene oxide adduct, bisphenol propylene oxide adduct, hydrogenated bisphenol propylene oxide adduct, cyclohexane-1,4-dimethanol propylene oxide adduct, sugar alcohols, and alkoxylated sugar alcohols. Such polyhydric alcohols may be fully or partially esterified (with (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.), provided that they contain at least two (meth)acrylate functional groups per molecule. As used herein, the term "alkoxylated" refers to compounds in which one or more epoxides (such as ethylene oxide and / or propylene oxide) have been reacted with active hydrogen-containing groups (e.g., hydroxyl groups) of a base compound (such as a polyhydric alcohol) to form one or more oxyalkylene moieties. For example, 1 to 25 moles of epoxide may be reacted per mole of base compound. According to certain aspects of the invention, the (meth)acrylate functionalized monomers used may be of relatively low molecular weight (e.g., 100 to 1000 Daltons).

[0186] Any (meth)acrylate functionalized oligomer known in the art may also be used in the curable composition of the present invention, provided that the curable composition contains at least one multi-(meth)acrylate functionalized oligomer according to the present invention. According to certain embodiments, such oligomers contain two or more (meth)acrylate functional groups per molecule. The number average molecular weight of such oligomers can vary widely, for example, from about 500 to about 50,000.

[0187] Suitable (meth)acrylate functionalized oligomers include, for example, polyester (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polyurethane (meth)acrylate oligomers, acrylic (meth)acrylate oligomers, polydiene (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and combinations thereof. Such oligomers may be selected and used in combination with one or more (meth)acrylate functionalized monomers to enhance the flexibility, strength and / or modulus of the cured resin prepared using the multi-component system of the present invention.

[0188] Exemplary polyester (meth)acrylate oligomers include the reaction products of acrylic acid or methacrylic acid or mixtures thereof with hydroxyl-terminated polyester polyols. The reaction process may be carried out such that all or substantially all of the hydroxyl groups of the polyester polyol have been (meth)acrylated, particularly where the polyester polyol is difunctional. The polyester polyol may be made by the polycondensation reaction of polyhydroxy-functional components, particularly diols, and carboxylic acid-functional compounds, particularly dicarboxylic acids and anhydrides. The polyhydroxy-functional and polycarboxylic acid-functional components may each have a linear, branched, alicyclic or aromatic structure, and may be used alone or as a mixture.

[0189] Examples of suitable epoxy (meth)acrylate oligomers include reaction products of acrylic acid or methacrylic acid, or mixtures thereof, with glycidyl ethers or esters.

[0190] Suitable polyether (meth) acrylate oligomers include, but are not limited to, condensation products of acrylic acid or methacrylic acid or mixtures thereof with polyether alcohols such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol as polyether polyols. Suitable polyether alcohols may be linear or branched materials containing ether bonds and terminal hydroxyl groups. Polyether alcohols may be prepared by ring-opening polymerization of cyclic ethers such as tetrahydrofuran or alkylene oxides with starter molecules. Suitable starter molecules include water, polyhydroxyl functional materials, polyester polyols and amines.

[0191] Polyurethane (meth)acrylate oligomers (sometimes also referred to as "urethane (meth)acrylate oligomers") that can be used in the multi-component system of the present invention include urethanes terminated with (meth)acrylate terminal groups based on aliphatic and / or aromatic polyester polyols and polyether polyols and aliphatic and / or aromatic polyester diisocyanates and polyether diisocyanates. Suitable polyurethane (meth)acrylate oligomers include, for example, urethane di- and tetra-acrylate oligomers based on aliphatic polyesters, urethane di- and tetra-acrylate oligomers based on aliphatic polyethers, and urethane di- and tetra-acrylate oligomers based on aliphatic polyesters / polyethers.

[0192] In various embodiments, the polyurethane (meth) acrylate oligomer can be prepared by reacting an aliphatic and / or aromatic diisocyanate with an OH-terminated polyester polyol (including aromatic, aliphatic and mixed aliphatic / aromatic polyester polyols), a polyether polyol, a polycarbonate polyol, a polycaprolactone polyol, a polyorganosiloxane polyol (e.g., a polydimethylsiloxane polyol), or a polydiene polyol (e.g., a polybutadiene polyol), or a combination thereof to form an isocyanate-functionalized oligomer, which is then reacted with a hydroxyl-functionalized (meth) acrylate (such as hydroxyethyl acrylate or hydroxyethyl methacrylate) to provide a terminal (meth) acrylate group. For example, the polyurethane (meth) acrylate oligomer may contain two, three, four or more (meth) acrylate functional groups per molecule.

[0193] Suitable acrylic (meth)acrylate oligomers (sometimes also referred to in the art as "acrylic oligomers") include oligomers that can be described as having an oligomeric acrylic backbone functionalized with one or more (meth)acrylate groups (the (meth)acrylate groups can be located at the ends of the oligomer or pendant to the acrylic backbone). The acrylic backbone can be a homopolymer, a random copolymer, or a block copolymer comprising repeating units of acrylic monomers. The acrylic monomers can be any monomeric (meth)acrylate (such as (meth)acrylate C 1 -C 6 The acrylic (meth)acrylate oligomers can be prepared using any procedure known in the art, such as by oligomerizing monomers at least a portion of which are functionalized with hydroxyl, carboxylic acid and / or epoxy groups (e.g., hydroxyalkyl (meth)acrylates, (meth)acrylic acid, glycidyl (meth)acrylate) to obtain a functionalized oligomer intermediate, which is subsequently reacted with one or more (meth)acrylate-containing reactants to introduce the desired (meth)acrylate functionality.

[0194] Exemplary (meth)acrylate functionalized monomers and oligomers may include: ethoxylated bisphenol A di(meth)acrylate; triethylene glycol di(meth)acrylate; ethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; 1,4-butanediol diacrylate; 1,4-butanediol methacrylate; diethylene glycol diacrylate; diethylene glycol methacrylate, 1,6-hexanediol diacrylate; 1,6-hexanediol methacrylate; neopentyl diol diacrylate; neopentyl glycol di(meth)acrylate; polyethylene glycol (600) methacrylate (where 600 refers to the approximate number average molecular weight of the polyethylene glycol portion); polyethylene glycol (200) diacrylate; 1,12-dodecanediol methacrylate; tetraethylene glycol diacrylate; triethylene glycol diacrylate, 1,3-butanediol methacrylate, tripropylene glycol diacrylate, polybutadiene diacrylate; methylpentanediol diacrylate; polyethylene glycol (400) diacrylate; ethoxylated 2 Bisphenol A methacrylate; ethoxylated 3 Bisphenol A methacrylate; ethoxylated 3 Bisphenol A diacrylate; Cyclohexanedimethanol methacrylate; Cyclohexanedimethanol diacrylate; Ethoxylated 10 Bisphenol A methacrylate (wherein the number following "ethoxylated" is the average number of oxyalkylene moieties per molecule); dipropylene glycol diacrylate; ethoxylated 4 Bisphenol A methacrylate; ethoxylated 6 Bisphenol A methacrylate; ethoxylated 8 Bisphenol A methacrylate; alkoxylated hexanediol diacrylate; alkoxylated cyclohexanedimethanol diacrylate; dodecane diacrylate; ethoxylated 4 Bisphenol A diacrylate; ethoxylated 10 Bisphenol A diacrylate; polyethylene glycol (400) methacrylate; polypropylene glycol (400) methacrylate; mellitic acid (metallic) diacrylate; modified mellitic acid diacrylate; mellitic acid methacrylate; polyethylene glycol (1000) methacrylate; methacrylated polybutadiene; propoxylated 2 Neopentyl glycol diacrylate; ethoxylated 30 Bisphenol A methacrylate; ethoxylated 30 Bisphenol A diacrylate; alkoxylated neopentyl glycol diacrylate; polyethylene glycol methacrylate; 1,3-butylene glycol diacrylate; ethoxylated 2 Bisphenol A methacrylate; dipropylene glycol diacrylate; ethoxylated4 Bisphenol A diacrylate; Polyethylene glycol (600) diacrylate; Polyethylene glycol (1000) dimethacrylate; Tricyclodecane dimethanol diacrylate; Propoxylated 2 Neopentyl glycol diacrylate; alkoxylated aliphatic alcohol diacrylate, trimethylolpropane trimethacrylate; trimethylolpropane triacrylate; tri(2-hydroxyethyl)isocyanurate triacrylate; ethoxylated 20 Trimethylolpropane triacrylate; Pentaerythritol triacrylate; Ethoxylated 3 Trimethylolpropane triacrylate; propoxylated 3 Trimethylolpropane triacrylate; ethoxylated 6 Trimethylolpropane triacrylate; propoxylated 6 Trimethylolpropane triacrylate; ethoxylated 9 Trimethylolpropane triacrylate; alkoxylated trifunctional acrylate; trifunctional methacrylate; trifunctional acrylate; propoxylated 3 Glyceryl triacrylate; propoxylated 5.5 Glyceryl triacrylate; ethoxylated 15 Trimethylolpropane triacrylate; trifunctional phosphoric acid ester; trifunctional acrylic acid ester; pentaerythritol tetraacrylate; ditrimethylolpropane tetraacrylate; ethoxylated 4 Pentaerythritol tetraacrylate; pentaerythritol polyoxyethylene tetraacrylate; dipentaerythritol pentaacrylate; pentaacrylate; epoxy acrylate oligomer; epoxy methacrylate oligomer; urethane acrylate oligomer; urethane methacrylate oligomer; polyester acrylate oligomer; polyester methacrylate oligomer; stearyl methacrylate oligomer; acrylic acrylate oligomer; perfluorinated acrylate oligomer; perfluorinated methacrylate oligomer; amino acrylate oligomer; amine-modified polyether acrylate oligomer; and amino methacrylate oligomer.

[0195] The curable composition of the present invention may optionally contain one or more (meth)acrylate functionalized compounds containing a single acrylate or methacrylate functional group per molecule (referred to herein as "mono (meth)acrylate functionalized compounds"). Any such compound known in the art may be used.

[0196] Examples of suitable mono(meth)acrylate functionalized compounds include, but are not limited to: mono(meth)acrylates of aliphatic alcohols (wherein the aliphatic alcohol may be linear, branched or alicyclic, and may be a monool, diol or polyol, provided that only one hydroxyl group is (meth)acrylated); mono(meth)acrylates of aromatic alcohols (such as phenol, including alkylated phenols); mono(meth)acrylates of alkylaryl alcohols (such as benzyl alcohol); mono(meth)acrylates of oligomeric and polymeric glycols (such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol); mono(meth)acrylates; mono(meth)acrylates of monoalkyl ethers of diols, oligomeric diols, polymeric diols; mono(meth)acrylates of alkoxylated (e.g., ethoxylated and / or propoxylated) aliphatic alcohols (wherein the aliphatic alcohol may be linear, branched or alicyclic, and may be a monool, a diol or a polyol, provided that only one hydroxyl group in the alkoxylated aliphatic alcohol is (meth)acrylated); mono(meth)acrylates of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (such as alkoxylated phenols); caprolactone mono(meth)acrylates; and the like.

[0197] The following compounds are specific examples of mono(meth)acrylate functionalized compounds suitable for use in the curable compositions of the present invention: methyl(meth)acrylate; ethyl(meth)acrylate; n-propyl(meth)acrylate; n-butyl(meth)acrylate; isobutyl(meth)acrylate; n-hexyl(meth)acrylate; 2-ethylhexyl(meth)acrylate; n-octyl(meth)acrylate; isooctyl(meth)acrylate; n-decyl(meth)acrylate; n-dodecyl(meth)acrylate; tridecyl(meth)acrylate; tetradecyl(meth)acrylate; hexadecyl(meth)acrylate; 2-hydroxyethyl(meth)acrylate; 2-hydroxypropyl(meth)acrylate and 3-hydroxypropyl(meth)acrylate; 2-methoxyethyl(meth)acrylate; 2-ethoxyethyl(meth)acrylate; 2-ethoxypropyl(meth)acrylate and 3-ethoxypropyl(meth)acrylate; tetrahydrofurfuryl(meth)acrylate; alkoxy alkoxylated tetrahydrofurfuryl (meth)acrylate; isobornyl (meth)acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; lauryl (meth)acrylate; isobornyl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; alkoxylated phenol phenyl (meth)acrylate; alkoxylated nonylphenol (meth)acrylate; cyclic trimethylolpropane formal (meth)acrylate; trimethylcyclohexanol (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; diethylene glycol monoethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; ethoxylated lauryl (meth)acrylate; methoxy polyethylene glycol (meth)acrylate; and combinations thereof.

[0198] Stabilizer

[0199] In general, it is desirable to include one or more stabilizers in the curable composition of the present invention to provide sufficient storage stability and shelf life. Advantageously, one or more such stabilizers are present in each stage of the method for preparing the curable composition to prevent the undesirable reaction of the components of the curable composition (particularly the components of the curable composition with (meth) acrylate functional groups). As used herein, the term "stabilizer" means the following compound or substance: it delays or prevents the reaction or curing of the (meth) acrylate functional groups present in the composition in the absence of actinic radiation. However, it will be advantageous to select the amount and type of stabilizer so that the composition can still be cured when exposed to actinic radiation (that is, the stabilizer does not prevent the radiation curing of the composition). Typically, effective stabilizers for the purposes of the present invention will be classified as free radical stabilizers (that is, stabilizers that function by inhibiting free radical reactions).

[0200] Any stabilizer known in the art in connection with (meth)acrylate functionalized compounds may be used in the present invention. Quinones represent a particularly preferred type of catalyst that may be employed in the context of the present invention. As used herein, the term "quinone" includes both quinone and hydroquinone and their ethers, such as monoalkyl, monoaryl, monoaralkyl and bis(hydroxyalkyl) ethers of hydroquinone. Hydroquinone monomethyl ether is an example of a suitable stabilizer that may be used.

[0201] The stabilizer concentration in the curable composition will depend on the following changes: the specific stabilizer or the combination of stabilizers selected for use, and the required stabilization degree, and the sensitivity of the components in the curable composition to degradation in the absence of stabilizers. However, typically, the curable composition is formulated to comprise 50 to 5000ppm stabilizer. According to some embodiments of the present invention, during each stage of the method for making the curable composition, the reaction mixture contains at least some stabilizers, for example at least 50ppm stabilizer.

[0202] Photoinitiator

[0203] In certain embodiments of the present invention, the curable compositions described herein include at least one photoinitiator and are curable by radiation energy. A photoinitiator may be considered to be any type of substance that, when exposed to radiation (e.g., actinic radiation), forms a species that initiates the reaction and curing of the polymerizable organic material present in the curable composition. Suitable photoinitiators include both free radical photoinitiators and cationic photoinitiators, and combinations thereof.

[0204] The free radical polymerization initiator is a substance that forms free radicals when irradiated. It is particularly preferred to use a free radical photoinitiator. Non-limiting types of free radical photoinitiators suitable for use in the curable composition of the present invention include, for example, benzoin, benzoin ether, acetophenone, benzyl, benzyl ketal, anthraquinone, phosphine oxide, α-hydroxy ketone, benzoyl formate, α-amino ketone, benzophenone, thioxanthone, xanthone, acridine derivatives, phenazine derivatives, quinoxaline derivatives, and triazine compounds.

[0205] The amount of the photoinitiator may vary appropriately depending on factors such as the photoinitiator selected, the amount and type of polymerizable species present in the curable composition, the radiation source, and the radiation conditions used. However, typically, the amount of the photoinitiator may be 0.05 wt % to 5 wt %, preferably 0.1 wt % to 2 wt %, based on the total weight of the curable composition.

[0206] Other additives

[0207] The curable composition of the present invention may optionally contain one or more additives instead of the above-mentioned ingredients or in addition to the above-mentioned ingredients. Such additives include, but are not limited to, antioxidants / light stabilizers, light retarder / absorbers, polymerization inhibitors, foam inhibitors, leveling or leveling agents, colorants, pigments, dispersants (wetting agents, surfactants), lubricating (slip) additives, fillers, chain transfer agents, thixotropic agents, matting agents, impact modifiers, waxes, or other various additives, including any additives conventionally used in the fields of coatings, sealants, adhesives, molding, 3D printing or inks.

[0208] The curable composition of the present invention may include one or more light retarders (sometimes referred to in the art as absorbers), particularly when the curable composition is used as a resin in a three-dimensional printing method involving photocuring the curable composition. The light blocker may be any such substance known in the field of three-dimensional printing, including, for example, non-reactive pigments and dyes. For example, the light blocker may be a visible light blocker, or a UV light blocker. Examples of suitable light blockers include, but are not limited to, titanium dioxide, carbon black, and organic ultraviolet light absorbers, such as hydroxybenzophenone, hydroxyphenylbenzotriazole, oxalyl dianilide, benzophenone, thioxanthone, hydroxyphenyl triazine, Sudan I, bromothymol blue, 2,2'-(2,5-thiophene diyl) bis(5-tert-butylphenylpropionazole) (sold under the trade name "Benetex OB Plus"), and benzotriazole ultraviolet light absorbers.

[0209] The amount of light retarder can vary as desired or appropriate for a particular application. Generally speaking, if the curable composition contains a light retarder, it is present in a concentration of 0.001 to 10 weight percent, based on the weight of the curable composition.

[0210] Advantageously, the curable composition of the present invention can be formulated to be solvent-free, i.e., to be free of any non-reactive volatile materials (materials having a boiling point of 150° C. or less at atmospheric pressure). For example, the curable composition of the present invention can contain little (contain a small amount) or no non-reactive solvent, such as less than 10%, or less than 5%, or less than 1%, or even 0% non-reactive solvent, based on the total weight of the curable composition.

[0211] Use of multi-(meth)acrylate functionalized oligomers and curable compositions containing multi-(meth)acrylate functionalized oligomers

[0212] As mentioned above, the curable composition prepared according to the present invention may contain one or more photoinitiators and may be photocurable. In some other embodiments of the present invention, the curable composition described herein does not include any initiator and is curable (at least partially) by electron beam energy. In other embodiments, the curable composition described herein includes at least one free radical initiator that decomposes when heated or in the presence of an accelerator and is chemically curable (i.e., without exposing the curable composition to radiation). The at least one free radical initiator that decomposes when heated or in the presence of an accelerator may, for example, include peroxides or azo compounds. Suitable peroxides for this purpose may include any compound containing at least one peroxy (-OO-) part, particularly any organic compound, such as dialkyl, diaryl and aryl / alkyl peroxides, hydroperoxides, percarbonates (salts), peresters, peracids, acyl peroxides, etc. At least one accelerator may include, for example, at least one tertiary amine and / or one or more other reducing agents based on metal-containing salts (e.g., carboxylates of transition metals such as iron, cobalt, manganese, vanadium, etc., and combinations thereof). The accelerator may be selected to promote the decomposition of the free radical initiator at room temperature or ambient temperature to generate active free radical species so that curing of the curable composition is achieved without the need to heat or bake the curable composition. In other embodiments, there is no accelerator, and the curable composition is heated to a temperature effective to cause decomposition of the free radical initiator and generate free radical species that initiate curing of the polymerizable compound present in the curable composition.

[0213] Advantageously, the curable composition of the present invention can be formulated to be solvent-free, i.e., not containing any non-reactive volatile materials (materials having a boiling point of 150° C. or less at atmospheric pressure). For example, the curable composition of the present invention can contain little or no non-reactive solvent, for example, less than 10%, or less than 5%, or less than 1%, or even 0% non-reactive solvent, based on the total weight of the curable composition. If a reactive diluent is used in the curable composition, it can be selected so that the viscosity of the curable composition is low enough (even in the absence of solvent) so that the curable composition can be applied to the surface of the substrate at a suitable application temperature to form a relatively thin, uniform layer.

[0214] In a preferred embodiment of the present invention, the curable composition is a liquid at 25° C. In various embodiments of the present invention, the curable composition described herein is formulated to have a viscosity of less than 10,000 mPa.s (cP), or less than 5000 mPa.s (cP), or less than 4000 mPa.s (cP), or less than 3000 mPa.s (cP), or less than 2500 mPa.s (cP), or less than 2000 mPa.s (cP), or less than 1500 mPa.s (cP), or less than 1000 mPa.s (cP), or even less than 500 mPa.s (cP), as measured at 25° C. using a Brookfield viscometer (Model DV-II) using a 27 spindle (wherein the spindle speed typically varies between 20 and 200 rpm, depending on the viscosity). In an advantageous embodiment of the present invention, the viscosity of the curable composition is 200 to 5000 mPa.s (cP), or 200 to 2000 mPa.s (cP), or 200 to 1500 mPa.s (cP), or 200 to 1000 mPa.s (cP) at 25° C. The relatively high viscosity can provide satisfactory performance in applications where the curable composition is heated above 25° C., such as 3D printing operations, etc., which employ machines with heated resin tanks (vat).

[0215] The curable compositions described herein may be compositions that will be subjected to curing, the curing being by free radical polymerization, cationic polymerization or other types of polymerization. In a particular embodiment, the curable composition is photocured (i.e., cured by exposure to actinic radiation, such as light, particularly visible or UV light). End-use applications of the curable composition include, but are not limited to: inks, coatings, adhesives, resins for additive manufacturing (such as 3D printing resins), molding resins, sealants, composites, antistatic layers, electronic applications, recyclable materials, smart materials (which are capable of detecting and responding to stimuli), and biomedical materials.

[0216] The cured composition prepared from the curable composition as described herein can be used, for example, in the following: a three-dimensional article (wherein the three-dimensional article may be essentially composed of the cured composition, or consist of the cured composition), a coated article (wherein a substrate is coated with one or more layers of the cured composition, including an encapsulated article in which a substrate is completely wrapped by the cured composition), a laminated or adhered article (wherein a first component of the article is laminated or adhered to a second component with the aid of the cured composition), a composite article or a printed article (wherein an image or the like is imprinted on a substrate, such as paper, plastic or a substrate containing M, using the cured composition).

[0217] The curing of the curable composition according to the present invention can be carried out by any suitable method, such as free radical and / or cationic polymerization. One or more initiators may be present in the curable composition, such as free radical initiators (e.g., photoinitiators, peroxide initiators). Before curing, the curable composition can be applied to the substrate surface in any conventional manner, for example, by spraying, blade coating, roller coating, casting, drum coating, dip coating, etc., and combinations thereof. Indirect application using a transfer process can also be used. Substrate can be any commercially available related substrate, such as a high surface energy substrate or a low surface energy substrate, such as a metal substrate or a plastic substrate, respectively. The substrate may include: metal, paper, cardboard, glass, thermoplastics, such as polyolefins, polycarbonates, acrylonitrile butadiene styrene (ABS), and blends thereof, composites, wood, leather, and combinations thereof. When used as an adhesive, the curable composition may be placed between two substrates and subsequently cured, whereby the cured composition bonds substrates together to provide adhered products. The curable composition according to the invention may also be shaped or cured in bulk (eg, the curable composition may be poured into a suitable mold and subsequently cured).

[0218] Curing can be accelerated or promoted by supplying energy to the curable composition, for example by heating the curable composition and / or by exposing the curable composition to a radiation source, such as visible or UV light, infrared radiation, and / or electron beam radiation. Thus, the cured composition can be considered a reaction product of the curable composition formed by curing. The curable composition can be partially cured by exposure to actinic radiation, and further curing is achieved by heating the partially cured article. For example, an article (e.g., a 3D printed article) formed from the curable composition can be heated at a temperature of 40°C to 120°C for a period of 5 minutes to 12 hours.

[0219] Multiple layers of the curable composition according to the invention may be applied to a substrate surface; the multiple layers may be cured simultaneously (eg by exposure to a single dose of radiation), or each layer may be cured sequentially prior to applying an additional layer of the curable composition.

[0220] The curable compositions described herein can be used as resins in three-dimensional printing applications. Three-dimensional (3D) printing (also known as additive manufacturing) is a process in which a 3D digital model is manufactured by the accumulation of building materials. The 3D printed object is produced by the successive construction of two-dimensional (2D) layers or sheets corresponding to the cross-section of the 3D object using computer-aided design (CAD) data of the object. Stereolithography (SL) is a type of additive manufacturing in which a liquid resin is cured by selective exposure to radiation to form each 2D layer. The radiation may be in the form of electromagnetic waves or electron beams. The most commonly used energy sources are ultraviolet, visible or infrared radiation.

[0221] The curable composition of the present invention described herein can be used as a 3D printing resin formulation, that is, a composition intended to be used for manufacturing three-dimensional products using 3D printing technology. Such a three-dimensional product can be free-standing / self-supporting, and can be substantially composed of a composition according to the present invention that has been cured, or composed of it. The three-dimensional product can also be a composite, the composite comprising at least one component substantially composed of or composed of a cured composition as mentioned above, and at least one additional component (e.g., a metal component or a thermoplastic component) comprising one or more materials different from such a cured composition. The curable composition of the present invention is particularly useful in digital light printing (DLP), although other types of three-dimensional (3D) printing methods can also be practiced using the curable composition of the present invention (e.g., SLA, inkjet). The curable composition of the present invention can be used in a three-dimensional printing operation together with another material used as a support or support for an article formed by the curable composition of the present invention.

[0222] Thereby, the curable composition of the present invention can be used for practicing various types of three-dimensional manufacturing or printing technology, including the method of three-dimensional object construction carried out step by step or layer by layer. In such a method, layer shaping can be carried out by solidifying (curing) the curable composition under the effect of exposure to radiation (such as visible, UV or other actinic irradiation). For example, a new layer can be formed at the top surface of the object being grown, or at the bottom surface of the object being grown. The curable composition of the present invention can also be advantageously used in the method for producing three-dimensional objects by additive manufacturing, wherein the method is carried out in a continuous manner. For example, the object can be produced from a liquid interface. The suitable method of this type is sometimes referred to as "continuous liquid interface (interfase) (or interphase (interphase)) production (or printing)" ("CLIP") method in the art. Such methods are described, for example, in WO 2014 / 126830; WO 2014 / 126834; WO 2014 / 126837; and Tumbleston et al., “Continuous Liquid Interface Production of 3D Objects,” Science Vol. 347, Issue 6228, pp. 1349-1352 (March 20, 2015), the entire disclosures of which are incorporated herein in their entirety for all purposes.

[0223] When stereolithography is performed above an oxygen-permeable build window, it is possible to produce articles using the curable composition according to the present invention by creating an oxygen-containing "dead zone" in the CLIP process, the "dead zone" being a thin uncured layer of the curable composition between the window and the surface of the cured article when the cured article is being produced. In such a process, a curable composition is used in which curing (polymerization) is inhibited by the presence of molecular oxygen; typically, such inhibition is observed in curable compositions that can be cured by a free radical mechanism, for example. The desired dead zone thickness can be maintained by selecting various control parameters, such as photon flux and the optical and curing properties of the curable composition. The CLIP process is performed by projecting a continuous sequence of actinic radiation (e.g. UV) images (which can be generated, for example, by a digital light processing imaging unit) through an oxygen-permeable, actinic radiation (e.g. UV) transparent window below a bath of the curable composition maintained in liquid form. The liquid interface below the developing (growing) article is maintained by the dead zone created above the window. The curing article is continuously withdrawn from the bath of curable composition above the dead zone, which is subsequently replenished by feeding an additional amount of curable composition into the bath to compensate for the amount of curable composition being cured and incorporated into the growing article.

[0224] Aspects of the Invention

[0225] Illustrative, non-limiting embodiments of the present invention can be summarized as follows:

[0226] Aspect 1: A multi-(meth)acrylate functionalized oligomer having a polyurethane backbone, a plurality of (meth)acrylate functional groups pendant to the polyurethane backbone, and one or more terminal (meth)acrylate functional groups, wherein the oligomer comprises: a) at least one multi-(meth)acrylate functionalized segment having at least two pendant (meth)acrylate groups, b) a urethane-containing segment, c) at least one terminal end-capping segment having at least one (meth)acrylate group, and optionally, d) at least one chain-extending segment having no (meth)acrylate groups or having no more than one (meth)acrylate group, and wherein the at least one multi-(meth)acrylate functionalized segment is positioned at a position along the polyurethane backbone of the multi-(meth)acrylate functionalized oligomer, and at least one (meth)acrylate functional group is present at one or more terminal positions of the multi-(meth)acrylate functionalized oligomer.

[0227] Aspect 2: The multi-(meth)acrylate functionalized oligomer of Aspect 1, comprising at least one chain extending segment selected from the following: a non-polymeric aliphatic segment, a polyether-containing segment, a polyester-containing segment, a polydiene-containing segment, a polycarbonate-containing segment, and a polyorganosiloxane-containing segment.

[0228] Aspect 3: The multi-(meth)acrylate functionalized oligomer of Aspect 1 or 2, wherein the urethane-containing segment corresponds to formula (I):

[0229] [-OC(=O)-NH-R 1 -NH-C(=O)-O-] (I)

[0230] Among them, R 1 It is a divalent hydrocarbon part.

[0231] Aspect 4: The multi-(meth)acrylate functionalized oligomer of any one of Aspects 1 to 3, wherein the urethane-containing segment comprises a residue of a diisocyanate selected from the group consisting of tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, benzyl diisocyanate, tetramethyl benzyl diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane -2,6-diisocyanate, 1,3-(isocyanate methyl)cyclohexane, isophorone diisocyanate, trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, dianisidine diisocyanate, phenyl diisocyanate, halogenated phenyl diisocyanate, methylene diisocyanate, ethylene diisocyanate, butylene diisocyanate, propylene diisocyanate, octadecylene diisocyanate, 1,5-naphthylene diisocyanate, polymethylene polyphenylene diisocyanate, tolylene diisocyanate polymer, diisocyanate Phenylmethane diisocyanate polymer, hexamethylene diisocyanate polymer, 3-phenyl-2-ethylene diisocyanate, cumene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 2,4'-diisocyanate diphenyl ether, 5,6-dimethyl-1,3-phenylene diisocyanate, 4,4'-diisocyanate diphenyl ether, benzidine diisocyanate, 9,10-anthracene diisocyanate, 4,4'-diisocyanate benzene Methyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 2,6'-dimethyl-4,4'-diisocyanatodiphenyl, 3,3'-dimethoxy-4,4'-diisocyanatodiphenyl, 1,4-anthracene diisocyanate, phenylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 4,4'-methylene-bis(cyclohexyl isocyanate), and combinations thereof.

[0232] Aspect 5: The multi-(meth)acrylate functionalized oligomer of any one of Aspects 1 to 4, wherein the oligomer comprises at least one multi-(meth)acrylate functionalized segment corresponding to formula (IIa):

[0233] [-CHR 2 -R 3 -CHR 4 -](IIa)

[0234] Among them, R 2 and R 4 are the same or different and correspond to -CH 2 -OC(=O)-CR 5 =CH2 , where R 5 H or CH 3 , and R 3 It is a divalent organic part.

[0235] Aspect 6: The multi-(meth)acrylate functionalized oligomer of Aspect 5, wherein R 3 For-R 3’ -or-CH 2 -OR 3’ -O-CH 2 -, and R 3’ It is a divalent hydrocarbon part.

[0236] Aspect 7: The multi-(meth)acrylate functionalized oligomer of Aspects 1 to 6, wherein the oligomer comprises at least one multi-(meth)acrylate functionalized segment corresponding to formula (IIb):

[0237]

[0238] Among them, R 2 and R 4 and R 10 are the same or different and correspond to -CH 2 -OC(=O)-CR 5 =CH 2 , where R 5 H or CH 3 , R 3 is a trivalent organic moiety and the wavy lines represent points of attachment to additional segments of the oligomer, particularly to the urethane-containing segments.

[0239] Aspect 8: The multi-(meth)acrylate functionalized oligomer of Aspect 7, wherein R 3 For-R 3’ -or

[0240]

[0241] And R 3’ It is a trivalent hydrocarbon part.

[0242] Aspect 9: The multi-(meth)acrylate functionalized oligomer of any one of Aspects 1 to 8, wherein the oligomer comprises at least one chain extender segment as a polymer-containing segment.

[0243] Aspect 10: The multi-(meth)acrylate functionalized oligomer of Aspect 9, wherein the polymer-containing segment corresponds to formula (III):

[0244] [-R 6 -](III)

[0245] Among them, R 6 is a divalent polymeric moiety selected from the group consisting of a polyether moiety, a polyester moiety, a polydiene moiety, a polycarbonate moiety, and a polyorganosiloxane moiety.

[0246] Aspect 11: The multi-(meth)acrylate functionalized oligomer of Aspect 10, wherein the divalent polymeric moiety is a divalent polyether moiety selected from the group consisting of a divalent polyoxyethylene moiety, a divalent polyoxypropylene moiety, a divalent polyoxyethylene / oxypropylene moiety, and a divalent polyoxytetramethylene moiety.

[0247] Aspect 12: The multi-(meth)acrylate functionalized oligomer of any of Aspects 1 to 11, wherein the oligomer comprises at least one chain extender segment that is a non-polymeric aliphatic segment.

[0248] Aspect 13: The multi-(meth)acrylate functionalized oligomer of Aspect 12, wherein the non-polymeric aliphatic segment corresponds to formula (IIIa):

[0249] [-R 6a -](IIIa)

[0250] Among them, R 6a is a divalent non-polymeric aliphatic hydrocarbon moiety optionally further comprising one or more heteroatoms.

[0251] Aspect 14: The multi-(meth)acrylate functionalized oligomer of any of Aspects 1 to 13, wherein the at least one terminal capping segment has a structure corresponding to Formula (IV):

[0252] -OR 7 -[OC(=O)-CR 8 =CH 2 ] n (IV)

[0253] Among them, R 7 is an n+1 valent organic part, R 8 H or CH 3 , and n is an integer from 1 to 3.

[0254] Aspect 15: The multi-(meth)acrylate functionalized oligomer of Aspect 14, wherein n=1, and R 7 -CH 2 -CH 2 -or-(CH 2 ) 5 -C(=O)-[O-(CH 2 ) 5 -C(=O)] x -O-CH 2-CH 2 -, wherein x is an integer from 0 to 9.

[0255] Aspect 16: The multi-(meth)acrylate functionalized oligomer of any of Aspects 1 to 15, wherein the oligomer has a number average molecular weight of 3000 to 20,000 g / mol.

[0256] Aspect 17: The multi-(meth)acrylate functionalized oligomer of any of Aspects 1 to 16, wherein the chain extending segment and the multi-(meth)acrylate functionalized segment are present in a molar ratio of 0:1 to 10:1.

[0257] Aspect 18: The multi-(meth)acrylate functionalized oligomer of any of Aspects 1 to 17, wherein the urethane-containing segments are positioned between the multi-(meth)acrylate functionalized segments and connect the multi-(meth)acrylate functionalized segments together.

[0258] Aspect 19: The multi-(meth)acrylate functionalized oligomer of any of Aspects 1 to 18, wherein one or more chain extender segments are present, and the segment containing urethane is positioned between the multi-(meth)acrylate functionalized segment and the chain extender segment and connects the multi-(meth)acrylate functionalized segment and the chain extender segment together.

[0259] Aspect 20: The multi-(meth)acrylate functionalized oligomer of any of Aspects 1 to 19, wherein the segment containing carbamate is positioned between the terminal capping segment and the multi-(meth)acrylate functionalized segment and connects the terminal capping segment and the multi-(meth)acrylate functionalized segment together, and / or, if one or more chain extending segments are present, is positioned between the terminal capping segment and the chain extending segment and connects the terminal capping segment and the chain extending segment together.

[0260] Aspect 21: The multi-(meth)acrylate functionalized oligomer of any of Aspects 1 to 20, wherein one or more chain extender segments are present, and the chain extender segments and multi-(meth)acrylate functionalized segments are randomly arranged along the polyurethane backbone and connected together by segments containing urethane.

[0261] Aspect 22: The multi-(meth)acrylate functionalized oligomer of any of Aspects 1 to 21, wherein the oligomer comprises one or more units having formula (A2):

[0262] [-OC(=O)-NH-R 1 -NH-C(=O)-O-CHR 2 -R 3 -CHR 4 -] (A2)

[0263] Among them, R 1 is a divalent hydrocarbon part, R 2 and R 4 are the same or different and correspond to -CH 2 -OC(=O)-CR 5 =CH 2 , where R 5 H or CH 3 , and R 3 It is a divalent organic part.

[0264] Aspect 23: The multi-(meth)acrylate functionalized oligomer of Aspect 22, wherein the oligomer further comprises one or more units having formula (B):

[0265] [OC(=O)-NH-R 1 -NH-C(=O)-OR 6 -] (B)

[0266] Among them, R 1 is a divalent hydrocarbon moiety, and R 6 The divalent polymeric moiety is selected from the group consisting of a divalent polyether moiety, a divalent polyester moiety, a divalent polydiene moiety, a divalent polycarbonate moiety, and a divalent polyorganosiloxane moiety.

[0267] Aspect 24: The multi-(meth)acrylate functionalized oligomer of Aspect 22 or 23, wherein the oligomer further comprises one or more units of formula (B'):

[0268] [OC(=O)-NH-R 1 -NH-C(=O)-OR 6a -] (B')

[0269] Among them, R 1 is a divalent hydrocarbon moiety, and R 6a is a divalent non-polymeric aliphatic moiety optionally further comprising one or more heteroatoms.

[0270] Aspect 25: The multi-(meth)acrylate functionalized oligomer of Aspects 1 to 24, wherein the oligomer comprises one or more units having formula (A3):

[0271]

[0272] Among them, R 1 is a divalent hydrocarbon part; R 2 , R 4 and R 10 are the same or different and correspond to -CH 2 -OC(=O)-CR 5=CH 2 , where R 5 H or CH 3 ; R 3 is a trivalent organic moiety; and the wavy lines represent points of attachment to additional segments of the oligomer, particularly to urethane-containing segments.

[0273] Aspect 26: The multi-(meth)acrylate functionalized oligomer of Aspect 25, wherein the oligomer further comprises one or more units having formula (B):

[0274] [OC(=O)-NH-R 1 -NH-C(=O)-OR 6 -] (B)

[0275] Among them, R 1 is a divalent hydrocarbon moiety, and R 6 The divalent polymeric moiety is selected from the group consisting of a divalent polyether moiety, a divalent polyester moiety, a divalent polydiene moiety, a divalent polycarbonate moiety, and a divalent polyorganosiloxane moiety.

[0276] Aspect 27: The multi-(meth)acrylate functionalized oligomer of any of Aspects 1 to 6 and 9 to 24, wherein:

[0277] The carbamate-containing segment corresponds to formula (I):

[0278] [-OC(=O)-NH-R 1 -NH-C(=O)-O-] (I)

[0279] Among them, R 1 It is a divalent hydrocarbon part;

[0280] The at least one multi-(meth)acrylate functionalized segment corresponds to formula (IIa):

[0281] [-CHR 2 -R 3 -CHR 4 -] (IIa)

[0282] Among them, R 2 and R 4 are the same or different and correspond to -CH 2 -OC(=O)-CR 5 =CH 2 , where R 5 H or CH 3 , and R 3 is a divalent organic moiety; and

[0283] Any chain extension segment, if present, corresponds to at least one of formula (III) or formula (IIIa):

[0284] [-R 6 -] (III)

[0285] Among them, R 6 is a divalent polymeric moiety selected from the group consisting of a divalent polyether moiety, a divalent polyester moiety, a divalent polydiene moiety, a divalent polycarbonate moiety, and a divalent polyorganosiloxane moiety;

[0286] [-R 6a -] (IIIa)

[0287] Among them, R 6a is a divalent non-polymeric aliphatic moiety optionally further comprising one or more heteroatoms.

[0288] Aspect 28: A multi-(meth)acrylate functionalized oligomer having a polyurethane backbone, multiple (meth)acrylate functional groups pendant to the polyurethane backbone, and one or more terminal (meth)acrylate functional groups, wherein the oligomer is the reaction product of reactants comprising: a) at least one diisocyanate, b) at least one diol compound comprising at least two (meth)acrylate functional groups or at least one triol compound comprising at least three (meth)acrylate functional groups, or mixtures thereof, c) at least one terminal capping compound comprising a single isocyanate-reactive hydroxyl group and at least one (meth)acrylate functional group, and optionally, d) at least one chain-extending polyol comprising at least two hydroxyl groups and zero or one (meth)acrylate functional group.

[0289] Aspect 29: The multi-(meth)acrylate functionalized oligomer of Aspect 28, wherein b) comprises at least one diol compound, and the diol compound is the reaction product of reactants comprising an acid-functional (meth)acrylate and a diepoxide.

[0290] Aspect 30: The multi-(meth)acrylate functionalized oligomer of Aspect 28 or 29, wherein b) comprises at least one triol compound, and the triol compound is the reaction product of reactants comprising an acid-functional (meth)acrylate and a triepoxide.

[0291] Aspect 31: The multi-(meth)acrylate functionalized oligomer of Aspect 29 or 30, wherein the acid-functionalized (meth)acrylate has a structure corresponding to Formula (V):

[0292] H 2 C=C(R)C(=O)O[CH 2CH 2 C(=O)O] n H (V)

[0293] Where R is H or CH 3 , and n is an integer from 0 to 5.

[0294] Aspect 32: The multi-(meth)acrylate functionalized oligomer of Aspect 29, wherein the diepoxide is selected from the group consisting of diene diepoxides and diglycidyl ethers.

[0295] Aspect 33: The multi-(meth)acrylate functionalized oligomer of any of Aspects 28, 29, 31 or 32, wherein the diol compound is 1,4-bis(3-acryloyloxy-2-hydroxypropoxy)butane.

[0296] Aspect 34: The multi-(meth)acrylate functionalized oligomer of any of Aspects 28 to 33, wherein the terminal end-capping compound is selected from (meth)acrylate esters of polyols, wherein all but one hydroxyl group of the polyol has been (meth)acrylated.

[0297] Aspect 35: The multi-(meth)acrylate functionalized oligomer of any of Aspects 28 to 34, wherein the terminal end-capping compound is selected from hydroxyalkyl (meth)acrylates.

[0298] Aspect 36: The multi-(meth)acrylate functionalized oligomer of any of Aspects 28 to 35, wherein the reactants comprise at least one chain-extending polyol selected from the group consisting of non-polymeric aliphatic diols having up to one (meth)acrylate functional group per molecule, polyether polyols, polyester polyols, polydiene polyols, polycarbonate polyols, and polysiloxane polyols.

[0299] Aspect 37: A method for making a multi-(meth)acrylate functionalized oligomer, wherein the multi-(meth)acrylate functionalized oligomer has a polyurethane backbone, multiple (meth)acrylate functional groups pendant to the polyurethane backbone, and one or more terminal (meth)acrylate functional groups, wherein the method comprises reacting the following: a) at least one diisocyanate, b) at least one diol compound (which comprises at least two (meth)acrylate functional groups), c) at least one terminal capping compound (which comprises a single isocyanate-reactive hydroxyl group and at least one (meth)acrylate functional group), and optionally, d) at least one chain extending polyol (which comprises at least two hydroxyl groups and zero or one (meth)acrylate functional group).

[0300] Aspect 38: A curable composition comprising at least one multi-(meth)acrylate functionalized oligomer according to any of Aspects 1 to 36, and at least one of: a) a photoinitiator, or b) a curable compound different from the multi-(meth)acrylate functionalized oligomer according to any of Aspects 1 to 36.

[0301] In this specification, the embodiments have been described in a manner that enables a clear and concise description to be written, but it is intended and will be understood that the embodiments may be combined or separated in various ways without departing from the present invention. For example, it will be understood that all preferred features described herein are applicable to all aspects of the invention described herein.

[0302] In some embodiments, the invention herein can be understood to exclude any element or process step that does not substantially affect the basic and novel characteristics of the compositions and methods described herein. In addition, in some embodiments, the invention can be understood to exclude any element or process step not described herein.

[0303] While the invention is illustrated and described herein with reference to particular embodiments, it is not intended that the invention be limited to the details shown. Rather, various modifications may be made in the details without departing from the invention and within the scope and range of equivalents of the claims.

[0304] Example

[0305] Examples 1-3 show the preparation of acrylate functional urethane oligomers having acrylate functionality pendant to the oligomer type chain location of the oligomer, rather than located at the terminal position of the oligomer type chain. Such acrylate functional urethane oligomers can be used as intermediates in the preparation of multi-(meth)acrylate functionalized oligomers according to the present invention by reacting the terminal groups of such oligomers to end-cap the oligomers with (meth)acrylate functional groups, as described in Example 4.

[0306] Embodiment 1:

[0307] Polypropylene glycol (Carpenter, PGP2000-60 polyol) (724.0 g), 1,4-bis(3-acryloyloxy-2-hydroxypropoxy)butane (Sartomer, CN132) (152.7 g), isophorone diisocyanate (Covestro, I) (121.0 g) and butylated hydroxytoluene (Aldrich) (2.0 g) were added and stirred at room temperature for 5 minutes. Air aeration was applied. Subsequently, dibutyltin dilaurate (Aldrich) (0.3 g) was added to the mixture. The reaction was exothermic. When the pot temperature stopped rising, the mixture was carefully heated to 80° C. with stirring and air aeration, and then kept at 80° C. for 4 hours or until the residual NCO was <0.06%. The yield was 1000 grams. Example 4 describes how this polymer can be converted into a multi-(meth)acrylate functionalized oligomer according to the present invention.

[0308] Embodiment 2:

[0309] To the reactor were added poly(neopentyl glycol adipate) polyol (Coim, Diexter-G 5500-56) (739.9 g) having a number average molecular weight of approximately 2000 g / mol, 1,4-bis(3-acryloyloxy-2-hydroxypropoxy)butane (Sartomer, CN132) (133.1 g), isophorone diisocyanate (Covestro, Desmodur I) (123.4 g) and 1035 (BASF) (3.0 g) and heated to 60° C. with stirring. Air aeration was applied. Subsequently, bismuth neodecanoate (Reaxis, C716) (0.6 g) was added to the mixture when the pot temperature reached 60° C. The reaction was exothermic. When the pot temperature stopped rising, the mixture was carefully heated to 105° C. with stirring and air aeration, and then maintained at 105° C. for two hours or until residual NCO <0.06%. The yield was 1000 grams.

[0310] Example 3

[0311] Trimethylolpropane triglycidyl ether triacrylate (Sartomer, CN133) (866.1 g), bismuth (3+) neodecanoate (Reaxis, C716) (0.6 g) and butylated hydroxytoluene (Aldrich) (2.0 g) were added to the reactor. The mixture was carefully heated to 65° C. with stirring and air aeration. Over a period of 2 hours, isophorone diisocyanate (Covestro, I) (131.3 g). The reaction was exothermic. The pot temperature was allowed to reach 95°C and then held at 95°C for 1 hour or until residual NCO < 0.06%. The yield was 1000 grams.

[0312] Examples 4-9 illustrate the synthesis of acrylate functional urethane oligomers according to the present invention wherein the acrylate functionality is positioned both pendant to the oligomeric chain and at the terminal end of the oligomeric chain.

[0313] Embodiment 4:

[0314] The final product from Example 1 (888.7 g), 2-hydroxyethyl acrylate (Nippon Shokubai) (38.2 g) and isophorone diisocyanate (Covestro, I) (73.1 g). Air aeration was applied. The reaction was exothermic. When the pot temperature stopped rising, the mixture was carefully heated to 95° C. with stirring and air aeration and then maintained at 95° C. for four hours or until residual NCO <0.06%. The yield was 1000 g.

[0315] Embodiment 5:

[0316] To the reactor were added 2-hydroxyethyl acrylate (Nippon Sukubai) (38.2 g), 1,4-bis(3-acryloyloxy-2-hydroxypropoxy)butane (Sartomer, CN132) (118.0 g), polypropylene glycol having a number average molecular weight of about 2000 g / mol (Carpenter, PGP2000-60 polyol) (657.3 g), isophorone diisocyanate (Covestro, I) (182.6 g) and butylated hydroxytoluene (Aldrich) (3 g) were added and stirred at room temperature for 5 minutes. Air aeration was applied. Dibutyltin dilaurate (Aldrich) (0.9 g) was then added to the mixture. The reaction was exothermic. When the pot temperature stopped rising, the mixture was carefully heated to 95° C. with stirring and air aeration and then maintained at 95° C. for four hours or until residual NCO <0.06%. The yield was 1000 grams.

[0317] Embodiment 6:

[0318] To the reactor were added caprolactone-modified 2-hydroxyethyl acrylate (Sartomer, SR495B) (493.6 g), 1,4-bis(3-acryloyloxy-2-hydroxypropoxy)butane (Sartomer, CN132) (257.5 g), hexamethylene diisocyanate (Covestro, H) (245.2 g) and butylated hydroxytoluene (Aldrich) (3.0 g) were added and stirred at room temperature for 5 minutes. Air aeration was applied. Dibutyltin dilaurate (Aldrich) (0.7 g) was then added to the mixture. The reaction was exothermic. When the pot temperature stopped rising, the mixture was carefully heated to 90° C. with stirring and air aeration and then maintained at 90° C. for nine hours or until residual NCO <0.06%. The yield was 1000 grams.

[0319] Embodiment 7:

[0320] To the reactor were added caprolactone-modified 2-hydroxyethyl acrylate (Sartomer, SR495B) (109.4 g), 1,4-bis(3-acryloyloxy-2-hydroxypropoxy)butane (Sartomer, CN132) (114.0 g), polypropylene glycol having a number average molecular weight of about 2000 g / mol (Carpenter, PGP2000-60 polyol) (635.0 g), hexamethylene diisocyanate (Covestro, H) (137.9 g) and butylated hydroxytoluene (Aldrich) (3.0 g) were added and stirred at room temperature for 5 minutes. Air aeration was applied. Subsequently, dibutyltin dilaurate (Aldrich) (0.7 g) was added to the mixture. The reaction was exothermic. When the pot temperature stopped rising, the mixture was carefully heated to 90° C. with stirring and air aeration and then maintained at 90° C. for nine hours or until residual NCO <0.06%. The yield was 1000 grams.

[0321] Embodiment 8:

[0322] The reactor was charged with 2-hydroxyethyl acrylate (Nippon Sukubai) (37.7 g), 1,4-bis(3-acryloyloxy-2-hydroxypropoxy)butane (Sartomer, CN132) (118.2 g), poly(neopentyl glycol adipate) polyol having a number average molecular weight of about 2000 g / mol (Coim, Diexter-G 5500-56) (659.0 g), isophorone diisocyanate (Covestro, I) (181.5 g) and 1035 (BASF) (3.0 g) and heated to 60° C. with stirring. Air aeration was applied. When the pot temperature reached 60° C., bismuth neodecanoate (Reaxis, C716) (0.6 g) was added to the mixture. The reaction was exothermic. When the pot temperature stopped rising, the mixture was carefully heated to 105° C. with stirring and air aeration, and then maintained at 105° C. for two hours or until residual NCO <0.06%. The yield was 1000 grams.

[0323] Embodiment 9:

[0324] Isophorone diisocyanate (Covestro, I) (177.2 g), 1035 (BASF) (3.0 g) and dibutyltin dilaurate (Aldrich) (0.9 g) were added and stirred at room temperature for 5 minutes. Air aeration was applied. Over a period of half an hour, 1,4-bis(3-acryloyloxy-2-hydroxypropoxy)butane (Sartomer, CN132) (143.0 g) was metered into the mixture. The reaction was exothermic. The pot temperature was allowed to reach 60°C and then maintained at 60°C with stirring and air aeration for half an hour or until the NCO reached a range of 10.1-10.4%. This mixture was transferred to a 16 oz brown bottle with a cap and labeled A. In a 60°C oven, a polycarbonate polyol (UBE, UH-50) (406.5 g) was pre-melted and added to another clean reactor, which was then heated to 60°C with stirring. When the pot temperature reached 60°C, air aeration was applied, and the pre-made isocyanate-terminated prepolymer A was added to the reactor in 10 increments over 1 hour. The pot temperature was allowed to reach 90°C, then maintained at 90°C with stirring and air aeration for half an hour or until NCO=0. Then, over half an hour, a semi-adduct of isophorone diisocyanate and 2-hydroxyethyl acrylate (Evonik, VESTANAT EP-DC 1241) (269.4 g) was added to the mixture with stirring and air aeration. The pot temperature was allowed to reach 105°C, then maintained at 105°C with stirring and air aeration for two hours or until NCO<0.06%. The yield was 1000 grams.

[0325] Table 1 lists the properties of certain oligomers described in the above examples, and the properties of the UV-cured products obtained therefrom. CO-1, included for comparative purposes, is a low Tg conventional terminally functional ("telechelic") acrylated urethane oligomer (i.e., an oligomer having terminal group acrylate functionality, but no acrylate functionality pendant to the backbone of the oligomer). The molecular weight values ​​reported in Table 1 were obtained as follows: using an Agilent 1260 GPC with a refractive index detector, and using polystyrene standards for calibration.

[0326] Table 1

[0327]

[0328] Although the molecular weight of the oligomer of Example 1 is similar to that of CO-1, its viscosity at 60°C is significantly lower than that of CO-1. ​​The oligomer of Example 5 has a similar molecular weight to CO-1, and the glass transition temperatures (Tg) of these oligomers when cured are also similar. However, the Example 5 oligomer yields a cured product having a significantly higher Young's modulus and tensile stress than the cured product obtained from the CO-1 oligomer. Without wishing to be bound by theory, it is believed that the significant enhancement in mechanical properties observed in the case of the Example 5 oligomer can be attributed to the presence of both pendant and terminal group acrylate functional groups.

[0329] Embodiment 10:

[0330] Dicyclohexylmethane-4,4'-diisocyanate (Covestro, W) (319.2 g), butylated hydroxytoluene (Aldrich) (1.0 g), 1,4-bis(3-acryloyloxy-2-hydroxypropoxy)butane (Sartomer, CN132) (100.0 g), trimethylolpropane triglycidyl ether triacrylate (Sartomer, CN133) (100.0 g) and caprolactone-modified 2-hydroxyethyl acrylate (Sartomer, SR495B) (100.0 g) were added and stirred at room temperature for 5 minutes. Air aeration was applied. Dibutyltin dilaurate (Aldrich) (0.9 g) was then added to the mixture. The reaction was exothermic. When the pot temperature stopped rising, the mixture was maintained at 65 to 70° C. with agitation and air aeration for half an hour or until the NCO reached the range of 10.6–11.2%. Then, over the course of one hour, more caprolactone-modified 2-hydroxyethyl acrylate (Sartomer, SR495B) (378.9 g) was metered into the mixture. The pot temperature was allowed to reach 90° C. and then maintained at 90° C. with stirring and air aeration for four hours or until NCO <0.06%. The yield was 1000 g.

[0331] Embodiment 11

[0332] Dicyclohexylmethane-4,4'-diisocyanate (Covestro, W) (323.7 g), butylated hydroxytoluene (Aldrich) (1.0 g), trimethylolpropane triglycidyl ether triacrylate (Sartomer, CN133) (247.5 g) and caprolactone-modified 2-hydroxyethyl acrylate (Sartomer, SR495B) (426.9 g) were added and stirred at room temperature for 5 minutes. Air aeration was applied. Dibutyltin dilaurate (Aldrich) (0.9 g) was then added to the mixture. The reaction was exothermic. When the pot temperature stopped rising, the mixture was carefully heated to 90° C. with stirring and air aeration, and then maintained at 90° C. for four hours or until residual NCO <0.06%. The yield was 1000 grams.

[0333] Embodiment 12:

[0334] Isophorone diisocyanate (Covestro, I) (237.3 g), 1035 (BASF) (2.0 g) and dibutyltin dilaurate (Aldrich) (0.6 g) were added and stirred at room temperature for 5 minutes. Air aeration was applied. 2-Hydroxyethyl acrylate (Nippon Sukubai) (62.0 g) was metered into the mixture over half an hour. The reaction was exothermic. The pot temperature was allowed to reach 50°C and then maintained at 50°C with stirring and air aeration for half an hour or until the NCO reached the range of 22.0–23.0%. Polycarbonate polyol (UBE, UH-50) (272.1 g) was then added to the mixture over a period of 1 hour. The pot temperature was allowed to reach 70°C and then maintained at 70°C with agitation and air aeration for 1 hour or until the NCO reached the range of 4.0-4.5%. Acetone (VWR) (319.1) was added to the mixture to prevent the viscosity from being too high. Trimethylolpropane triglycidyl ether triacrylate (Sartomer, CN133) (106.9 g) was added to the mixture. The pot temperature was maintained at 65°C with agitation and air aeration for 8 hours or until the NCO was <0.06%. The yield was 1000 grams (680.9 grams of dried resin).

Claims

1. A curable composition comprising (i) a multi-(meth)acrylate functionalized oligomer having a polyurethane backbone, a plurality of (meth)acrylate functional groups pendant to the polyurethane backbone, and one or more terminal (meth)acrylate functional groups, wherein: The oligomer comprises a) at least one multi-(meth)acrylate functional segment having at least two pendant (meth)acrylate groups, b) a urethane-containing segment, c) at least one terminal end-capping segment having at least one (meth)acrylate group, and optionally, d) at least one chain-extending segment having no (meth)acrylate groups or having no more than one (meth)acrylate group, and wherein at least one multi-(meth)acrylate functional segment is positioned at a position along the polyurethane backbone of the multi-(meth)acrylate functional oligomer and at least one (meth)acrylate functional group is present at one or more terminal positions of the multi-(meth)acrylate functional oligomer; and (ii) at least one of: a) a photoinitiator, or b) a curable compound different from the multi-(meth)acrylate functional oligomer, The curable composition contains less than 10% of a non-reactive solvent, based on the total weight of the curable composition.

2. The curable composition of claim 1, wherein the multi-(meth)acrylate functionalized oligomer comprises at least one chain extending segment selected from the group consisting of a non-polymeric aliphatic segment, a polyether-containing segment, a polyester-containing segment, a polydiene-containing segment, a polycarbonate-containing segment, and a polyorganosiloxane-containing segment.

3. The curable composition according to claim 1 or 2, wherein The carbamate-containing segment corresponds to formula (I): [-O-C(=O)-NH-R 1 -NH-C(=O)-O-](I) Among them, R 1 It is a divalent hydrocarbon part.

4. The curable composition according to claim 1 or 2, wherein The urethane-containing segments comprise residues of diisocyanates selected from the group consisting of tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3-(isocyanatemethyl)cyclohexane Alkane, isophorone diisocyanate, trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, dianisidine diisocyanate, phenyl diisocyanate, halogenated phenyl diisocyanate, methylene diisocyanate, ethylene diisocyanate, butylene diisocyanate, propylene diisocyanate, octadecylene diisocyanate, 1,5-naphthylene diisocyanate, polymethylene polyphenylene diisocyanate, tolylene diisocyanate polymer, diphenylmethane diisocyanate polymer, hexamethylene diisocyanate polymer, 3-phenyl-2-ethylene diisocyanate, cumene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 2,4'-diisocyanate diphenyl ether, 5,6-dimethyl-1,3-phenylene diisocyanate, 4,4'-diisocyanate diphenyl ether, benzidine diisocyanate, 9,10-anthracene diisocyanate, 4,4'-diisocyanate benzyl, 3,3'- Dimethyl-4,4'-diisocyanatodiphenylmethane, 2,6'-dimethyl-4,4'-diisocyanatodiphenyl, 3,3'-dimethoxy-4,4'-diisocyanatodiphenyl, 1,4-anthracene diisocyanate, phenylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 4,4'-methylene-bis(cyclohexyl isocyanate), and combinations thereof.

5. The curable composition of claim 1 or 2, wherein the oligomer comprises at least one multi-(meth)acrylate functionalized segment corresponding to formula (IIa): [-CHR 2 -R 3 -CHR 4 -](IIa) in, R 2 and R 4 are the same or different and correspond to -CH2-OC(=O)-CR 5 =CH2, where R 5 is H or CH3, and R 3 It is a divalent organic part.

6. The curable composition of claim 5, wherein R 3 For-R 3’ -OR-CH2-OR 3’ -O-CH2-, and R 3’ It is a divalent hydrocarbon part.

7. The curable composition of claim 1 or 2, wherein The oligomer comprises at least one multi-(meth)acrylate-functional segment corresponding to formula (IIb): Among them, R 2 and R 4 and R 10 are the same or different and correspond to -CH2-OC(=O)-CR 5 =CH2, where R 5 is H or CH3, R 3 is a trivalent organic moiety and the wavy lines represent points of attachment to additional segments of the oligomer.

8. The curable composition of claim 7, wherein The wavy lines represent the attachment points to the urethane-containing segments.

9. The curable composition of claim 7, wherein R 3 For-R 3’ - or R 3 Corresponding to formula (IIb') And R 3’ It is a trivalent hydrocarbon part.

10. The curable composition of claim 1 or 2, wherein The oligomer includes at least one chain extender segment as a polymer-containing segment.

11. The curable composition of claim 10, wherein the polymer-containing segment corresponds to formula (III): [−R 6 -](III) in, R 6 is a divalent polymeric moiety selected from the group consisting of a polyether moiety, a polyester moiety, a polydiene moiety, a polycarbonate moiety, and a polyorganosiloxane moiety.

12. The curable composition of claim 11, wherein the divalent polymeric moiety is a divalent polyether moiety selected from the group consisting of a divalent polyoxyethylene moiety, a divalent polyoxypropylene moiety, a divalent polyoxyethylene / oxypropylene moiety, and a divalent polyoxytetramethylene moiety.

13. The curable composition of claim 1 or 2, wherein The oligomer comprises at least one chain extender segment as a non-polymeric aliphatic segment.

14. The curable composition of claim 13, wherein The non-polymeric aliphatic segment corresponds to formula (IIIa): [-R 6a -](IIIa) Among them, R 6a is a divalent non-polymeric aliphatic hydrocarbon moiety optionally further comprising one or more heteroatoms.

15. The curable composition of claim 1 or 2, wherein The oligomer comprises at least one terminal capping segment having a structure corresponding to formula (IV): -O-R 7 -[O-C(=O)-CR 8 =CH2] n (IV) Among them, R 7 is an n+1 valent organic part, R 8 is H or CH3, and n is an integer from 1 to 3.

16. The curable composition of claim 15, wherein n=1,and R 7 -CH2-CH2- or -(CH2)5-C(=O)-[O-(CH2)5-C(=O)] x -O-CH2-CH2-, wherein x is an integer from 0 to 9.

17. The curable composition of claim 1 or 2, wherein The multi-(meth)acrylate functionalized oligomer has a number average molecular weight of 3000 to 20,000 g / mol.

18. The curable composition of claim 1 or 2, wherein The chain extending segments and the multi-(meth)acrylate functionalized segments are present in a molar ratio of 0:1 to 10:

1.

19. The curable composition of claim 1 or 2, wherein The urethane containing segments are positioned between the multi-(meth)acrylate functional segments and link the multi-(meth)acrylate functional segments together.

20. The curable composition of claim 1 or 2, wherein One or more chain extender segments are present, and the urethane containing segment is positioned between the multi (meth)acrylate functional segment and the chain extender segment and connects the multi (meth)acrylate functional segment and the chain extender segment together.

21. The curable composition of claim 1 or 2, wherein The urethane-containing segment is positioned between the terminal end-capping segment and the multi-(meth)acrylate functionalized segment and connects the terminal end-capping segment and the multi-(meth)acrylate functionalized segment together, and / or, if one or more chain extender segments are present, is positioned between the terminal end-capping segment and the chain extender segment and connects the terminal end-capping segment and the chain extender segment together.

22. The curable composition of claim 1 or 2, wherein One or more chain extender segments are present, and the chain extender segments and multi-(meth)acrylate functional segments are randomly arranged along the polyurethane backbone and are linked together by urethane containing segments.

23. The curable composition of claim 1 or 2, wherein The oligomer comprises one or more units having formula (A2): [-O-C(=O)-NH-R 1 -NH-C(=O)-O-CHR 2 -R 3 -CHR 4 -](A2) Among them, R 1 is a divalent hydrocarbon part, R 2 and R 4 are the same or different and correspond to -CH2-OC(=O)-CR5=CH2, wherein R5 is H or CH3, and R3 is a divalent organic moiety.

24. The curable composition of claim 23, wherein The oligomer further comprises one or more units of formula (B): [O-C(=O)-NH-R 1 -NH-C(=O)-O-R 6 -](B) Among them, R 1 is a divalent hydrocarbon moiety, and R 6 The divalent polymeric moiety is selected from the group consisting of a divalent polyether moiety, a divalent polyester moiety, a divalent polydiene moiety, a divalent polycarbonate moiety, and a divalent polyorganosiloxane moiety.

25. The curable composition of claim 23, wherein The oligomer further comprises one or more units of formula (B'): [O-C(=O)-NH-R 1 -NH-C(=O)-O-R 6a -](B’) Among them, R 1 is a divalent hydrocarbon moiety, and R 6a is a divalent non-polymeric aliphatic moiety optionally further comprising one or more heteroatoms.

26. The curable composition of claim 1 or 2, wherein The oligomer comprises one or more units having formula (A3): [-O-C(=O)-NH-R 1 -NH-C(=O)-O-CHR 2 -R 3 (-CHR 4 -)-CHR 10 ](A3) Among them, R 1 is a divalent hydrocarbon part, R 2 and R 4 and R 10 are the same or different and correspond to -CH2-OC(=O)-CR 5 =CH2, where R 5 is H or CH3; R 3 It is a trivalent organic part.

27. The curable composition of claim 26, wherein The oligomer further comprises one or more units of formula (B): [O-C(=O)-NH-R 1 -NH-C(=O)-O-R 6 -](B) Among them, R 1 is a divalent hydrocarbon moiety, and R 6 The divalent polymeric moiety is selected from the group consisting of a divalent polyether moiety, a divalent polyester moiety, a divalent polydiene moiety, a divalent polycarbonate moiety, and a divalent polyorganosiloxane moiety.

28. The curable composition of claim 1 or 2, wherein: The carbamate-containing segment corresponds to formula (I): [-O-C(=O)-NH-R 1 -NH-C(=O)-O-](I) Among them, R 1 It is a divalent hydrocarbon part; The at least one multi-(meth)acrylate functionalized segment corresponds to formula (II): [-CHR 2 -R 3 -CHR 4 -](IIa) Among them, R 2 and R 4 are the same or different and correspond to -CH2-OC(=O)-CR 5 =CH2, where R 5 is H or CH3, and R 3 is a divalent organic moiety; and Any chain extension segment, if present, corresponds to at least one of formula (III) or formula (IIIa): [−R 6 -](III) Among them, R 6 is a divalent polymeric moiety selected from the group consisting of a divalent polyether moiety, a divalent polyester moiety, a divalent polydiene moiety, a divalent polycarbonate moiety, and a divalent polyorganosiloxane moiety; [-R 6a -](IIIa) Among them, R 6a is a divalent non-polymeric aliphatic moiety optionally further comprising one or more heteroatoms.

29. A multi-(meth)acrylate functionalized oligomer having a polyurethane backbone, a plurality of (meth)acrylate functional groups pendant to the polyurethane backbone, and one or more terminal (meth)acrylate functional groups, wherein: The oligomer is the reaction product of reactants consisting of: a) at least one diisocyanate or higher functionality polyisocyanate, b) at least one diol compound comprising at least two (meth)acrylate functional groups, or at least one triol compound comprising at least three (meth)acrylate functional groups, or a mixture thereof, c) at least one terminal capping compound comprising a single isocyanate-reactive hydroxyl group and at least one (meth)acrylate functional group, and optionally, d) at least one chain-extending polyol comprising at least two hydroxyl groups and zero or one (meth)acrylate functional group.

30. The multi-(meth)acrylate functionalized oligomer of claim 29, wherein: b) comprises at least one diol compound, and the diol compound is the reaction product of reactants comprising an acid-functional (meth)acrylate and a diepoxide.

31. The multi-(meth)acrylate functionalized oligomer of claim 29 or 30, wherein: b) comprises at least one triol compound, and the triol compound is the reaction product of reactants comprising an acid-functional (meth)acrylate and a triepoxide.

32. The multi-(meth)acrylate functionalized oligomer of claim 30, wherein: The acid-functional (meth)acrylate has a structure corresponding to formula (V): H2C=C(R)C(=O)O[CH2CH2C(=O)O] n H(V) wherein R is H or CH3, and n is an integer from 0 to 5.

33. The multi-(meth)acrylate functionalized oligomer of claim 30, wherein: The diepoxide is selected from the group consisting of diene diepoxides and diglycidyl ethers.

34. The multi-(meth)acrylate functionalized oligomer of claim 29 or 30, wherein: The diol compound is 1,4-bis(3-acryloyloxy-2-hydroxypropoxy)butane.

35. The multi-(meth)acrylate functionalized oligomer of claim 29 or 30, wherein: The terminal capping compound is selected from (meth)acrylates of polyols, wherein all hydroxyl groups except one hydroxyl group of the polyol have been (meth)acrylated.

36. The multi-(meth)acrylate functionalized oligomer of claim 29 or 30, wherein: The terminal capping compound is selected from hydroxyalkyl (meth)acrylate and caprolactone-modified hydroxyalkyl (meth)acrylate.

37. The multi-(meth)acrylate functionalized oligomer of claim 29 or 30, wherein: The at least one chain-extending polyol is selected from the group consisting of non-polymeric aliphatic diols having up to one (meth)acrylate functional group per molecule, polyether polyols, polyester polyols, polydiene polyols, polycarbonate polyols, and polyorganosiloxane polyols.

38. A method of making a multi-(meth)acrylate functionalized oligomer as defined in any one of claims 29 to 37, the multi-(meth)acrylate functionalized oligomer having a polyurethane backbone, a plurality of (meth)acrylate functional groups pendant to the polyurethane backbone, and one or more terminal (meth)acrylate functional groups, wherein: The method comprises reacting a) at least one diisocyanate, b) at least one diol compound comprising at least two (meth)acrylate functional groups, or at least one triol compound comprising at least three (meth)acrylate functional groups, or a mixture thereof, c) at least one terminal capping compound comprising a single isocyanate-reactive hydroxyl group and at least one (meth)acrylate functional group, and optionally, d) at least one chain-extending polyol comprising at least two hydroxyl groups and zero or one (meth)acrylate functional group.

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