Ethylene-based unsaturated compounds, methods for manufacturing the same, and uses of the same in coating compositions

Abstract

Compounds containing ethylene-based unsaturated groups, silane groups, and aspartate and / or hydantoin groups are described. Additionally, methods for preparing and using such compounds are disclosed, such as their use in coating compositions suitable for application to optical glass fiber substrates.

Description

Technology Field

[0001] This specification relates to compounds containing ethylene-based unsaturated groups and silane groups. This specification also relates to methods for preparing such compounds, as well as the use of such compounds in, for example, coating compositions suitable for application to optical glass fiber substrates. Background Technology

[0002] Radiation-curable, e.g. ultraviolet ("UV") radiation-curable coating compositions are used in many applications due to their ability to produce cured coatings that cure particularly rapidly and exhibit many desirable properties. As used herein, "radiation-curable" coating compositions refer to coating compositions that require radiation to initiate crosslinking to convert a liquid (non-curable) composition into a solid (cured) coating. One specific use of radiation-curable coating compositions is the manufacture of coated optical fibers.

[0003] Optical fibers are composed of glass fibers obtained by hot melt spinning of glass, wherein one or more coating layers are placed on the glass fibers for enhanced protection. Typically, a radiation-curable optical fiber coating is a cured product of a composition containing a mixture of one or more components having one or more ethylene-based unsaturated bonds that undergo crosslinking by free-radical polymerization under the influence of irradiation.

[0004] In many cases, optical fibers are coated with a multilayer coating system comprising an inner "primary coating" in direct contact with the optical fiber and a "secondary coating" covering the primary coating. The inner primary coating is typically formulated to have a significantly lower modulus than the secondary coating.

[0005] The relatively soft inner primary coating provides resistance to microbending that can be induced by thermal stress and / or mechanical lateral forces. Microbending is a microscopic curvature in an optical fiber involving local axial displacement of several micrometers and spatial wavelengths of several millimeters. These are undesirable as they result in additional attenuation (i.e., signal loss) in signal transmission in the coated optical fiber. The harder secondary coating provides resistance to handling forces, such as those typically faced when the coated optical fiber is ribbonized and / or cabled.

[0006] Often, at least the inner "primary coating" is combined with one or more urethane-based reactive oligomers, commonly referred to as "reactive urethane oligomers," comprising a backbone, urethane groups, and polymerizable groups. In many cases, the reactive urethane oligomer comprises a urethane acrylate oligomer that is a reaction product of a polyol, a diisocyanate, and a hydroxyl-group containing acrylate.

[0007] In addition, radiation-curable coating compositions, such as those used for coating optical fibers, often contain silane adhesion promoters. This can be particularly common when the radiation-curable coating composition is intended to be applied to a glass substrate, such as in the case of optical fiber coatings, especially for the inner primary coating. In the primary coating, for example, the adhesion promoter provides a connection between the polymer primary coating and the surface of the optical glass fiber.

[0008] In some cases, the adhesion promoter compound is simply an additive in the coating composition. Alternatively, the adhesion promoter may contain a reactive group that causes it to be covalently bonded to the polymer matrix of the coating. In optical fiber primary coating formulations, for example, the reactive urethane oligomer may itself contain a hydrolyzable silane group. Typically, such reactive urethane oligomers are prepared by including an active-hydrogen-containing silane, such as a mercapto or amino-functional silane, among the reactants used to prepare the reactive urethane oligomer.

[0009] Ethylene-based unsaturated compounds containing silane groups, such as commercially available 3-(trimethoxysilyl)propyl acrylate, also react with reactive urethane oligomers typically used in optical fiber coating formulations to provide covalent bonding of adhesion promoters to the polymer matrix. These compounds can also theoretically be prepared by reacting ethylene-based unsaturated isocyanate-functional compounds, such as isocyanatoethyl acrylate, with amino-functional silanes, such as gamma-aminopropyltriethoxysilane, or thiol-functional silanes, such as gamma-mercaptopropyltriethoxysilane. The synthesis of these compounds is not without significant drawbacks. In the case of amino-functional silanes, the reaction with isocyanates is very fast and difficult to control, whereas in the case of thiol-functional silanes, the reaction is slow and requires sufficient catalysis. Such catalysis has typically been provided through the use of tin catalysts, which is undesirable from a regulatory and environmental perspective. Although commercially available organic bismuth catalysts such as bismuth trineodecanoate are more compliant with regulations and the environment, using them in the reaction of thiol-functional silanes with isocyanates can result in slow reactions as well as significant color changes.

[0010] In light of the above, it would be highly desirable to provide an adhesion-promoting compound that can be synthesized easily and efficiently and exhibits significantly improved adhesion performance compared to other adhesion promoters. Furthermore, it would be desirable to provide such an adhesion-promoting compound that may be particularly suitable for use in optical fiber coating applications, especially in primary coating applications.

[0011] In some aspects, this specification relates to ethylene-based unsaturated compounds. Ethylene-based unsaturated compounds include the following:

[0012] (a) Moiety of the following structure (1):

[0013] ; and

[0014] (b1) Moiety of the following structure (2):

[0015] ; or

[0016] (b2) Moiety of the following structure (3):

[0017] ; or

[0018] (b3) A combination of the moiety of structure (2) and the moiety of structure (3),

[0019] Here, (i) Y represents a linear or branched linker comprising one or more carbon atoms, (ii) each X, which may be the same or different, represents an alkoxy group or an organic group inert to isocyanate groups at a temperature of 100°C or lower, provided that at least one X represents an alkoxy group, and (iii) R, which may be the same or different 1 and R 2 Each represents an organic group that is inert to isocyanate groups at temperatures of 100°C or lower; (iv) R which may be the same or different 3 and R 4 Each represents an organic group that is inert to hydrogen or an isocyanate group at a temperature of 100°C or lower; (v) each " " indicates a connection to another part of the ethylene-based unsaturated compound.

[0020] The present specification also relates to a method for preparing such an ethylene-based unsaturated compound, a composition such as a coating composition comprising such an ethylene-based unsaturated compound, and a substrate such as a glass substrate comprising an optical fiber that is at least partially coated with a coating such as a primary coating deposited from such a coating composition. Specific details for implementing the invention

[0021] Various embodiments are described and illustrated in this specification to provide an overall understanding of the structure, function, characteristics, and uses of the disclosed invention. The various embodiments described and illustrated in this specification are understood to be non-limiting and non-inclusive. Accordingly, the invention is not limited by the description of the various non-limiting and non-inclusive embodiments disclosed in this specification. Features and characteristics described in relation to various embodiments may be combined with features and characteristics of other embodiments. Such variations and modifications are intended to be included within the scope of this specification. Accordingly, the claims may be amended to describe any features or characteristics explicitly or implicitly described in this specification, or otherwise explicitly or implicitly supported by this specification. Additionally, the applicant(s) reserve the right to amend the claims to actively exclude features or characteristics that may exist in the prior art. Accordingly, any such amendment complies with the requirements of 35 USC § 112 and 35 USC § 132(a). Various embodiments disclosed and described in this specification may include, be composed of, or essentially be composed of features and characteristics as variously described herein.

[0022] Any patent, publication, or other disclosure identified herein is incorporated herein by reference in its entirety, unless otherwise indicated, only to the extent that the incorporated material does not conflict with any existing definitions, statements, or other disclosures expressly set forth in this specification. Accordingly, and to the extent necessary, the express disclosures as set forth in this specification shall prevail over any conflicting material incorporated herein by reference. Any material or part thereof that is referred to as incorporated herein by reference but conflicts with any existing definitions, statements, or other disclosures described herein is incorporated only to the extent that no conflict arises between the incorporated material and the existing disclosures. The applicant(s) reserve the right to amend this specification to expressly describe any subject or part thereof incorporated herein by reference.

[0023] In this specification, unless otherwise indicated, all numeric parameters are to be understood as being preceded and modified by the term “about” in all cases, wherein the numeric parameters possess the inherent variability characteristics of the underlying measurement technology used to determine the numeric value of the parameter. At a minimum, and without attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numeric parameter described in this specification should be interpreted by taking into account at least the reported number of significant figures and applying ordinary rounding techniques.

[0024] Additionally, any numerical range mentioned herein is intended to include all sub-ranges of the same numerical precision contained within the mentioned range. For example, the range “1.0 to 10.0” is intended to include all sub-ranges having a minimum value of 1.0 and a maximum value of 10.0 (and including therein), that is, a minimum value greater than or equal to 1.0 and a maximum value less than or equal to 10.0, e.g., 2.4 to 7.6. Any maximum numerical limit mentioned herein is intended to include all lower numerical limits contained therein, and any minimum numerical limit mentioned herein is intended to include all higher numerical limits contained therein. Accordingly, the applicant(s) reserve the right to amend the specification, including the claims, to explicitly enumerate any sub-ranges contained within the scope explicitly enumerated herein. Since all such scopes are intended to be implicitly described in this specification, any correction to explicitly describe any such sub-scopes will comply with the requirements of 35 USC § 112 and 35 USC § 132(a).

[0025] The grammatical articles "one," "a," "an," and "the" as used herein are intended to include "at least one" or "more than one" unless explicitly indicated otherwise. Accordingly, articles are used herein to refer to one or more than one (i.e., "at least one") of the grammatical objects of the article.

[0026] Throughout this specification, "Si" refers to silicon, "H" refers to hydrogen, "N" refers to nitrogen, "O" refers to oxygen, and "S" refers to sulfur.

[0027] As indicated, certain embodiments of this specification relate to ethylene-based unsaturated compounds. In some embodiments, the ethylene-based unsaturated compounds of this specification have a molecular weight calculated from the molecular formula of the ethylene-based unsaturated compounds that is 400 to less than 2000 g / mol, e.g., 400 to 1000 g / mol. As used herein, the term "ethylene-based unsaturated compound" means a compound containing a polymerizable carbon-carbon double bond, that is, a carbon-carbon double bond capable of reacting with another carbon-carbon double bond in a polymerization reaction. The reaction rate of polymerization is determined by the position of the carbon-carbon double bond within the oligomer structure and the substituent structure. For a faster polymerization reaction, it is preferable that at least one carbon-carbon double bond of the ethylene-based unsaturated oligomer is present as a =CH2 terminal group and that there are no additional substituents on its carbon. As is recognized, polymerizable carbon-carbon double bonds are generally contained in acryloyl (-C(=O)-CH=CH2), methacryloyl (-C(=O)-C(CH3)=CH2), or vinyl (-CH=CH2) groups. In some embodiments, the ethylene unsaturated compound comprises at least one acrylate group, methacrylate group, acrylamide group, methacrylamide group, vinyloxy group, N-vinylamide group, or any combination thereof. In some embodiments, the ethylene unsaturated compound comprises only one of the aforementioned ethylene unsaturated groups. In some embodiments, the ethylene unsaturated compound comprises one to four, e.g., one to two, or in some cases, one ethylene unsaturated group. Thus, as is recognized, in some embodiments, the ethylene unsaturated compound of this specification comprises the terminal group of structure (1) and the terminal group of structure (1a):

[0028]

[0029] Here, E represents any of the aforementioned groups containing a polymerizable carbon-carbon double bond, such as an acryloyl, methacryloyl, or vinyl group, and

[0030] represents a connection to another part of the ethylene-based unsaturated compound. For example, in some embodiments, the terminal group of structure (1a) has structure (1b):

[0031]

[0032] Here, R 3 It is H or CH3, and represents a connection to another part of the ethylene-based unsaturated oligomer. In some cases, the first terminal group and the second terminal group are placed at opposite ends of the ethylene-based unsaturated compound. In some cases, the terminal group of structure (1) and the terminal group of structure (1a) are placed at opposite ends of the ethylene-based unsaturated compound. Furthermore, as is recognized, in some cases, the moiety of structure (2) and / or the moiety of structure (3) is placed between the terminal group of structure (1) and the terminal group of structure (1a).

[0033] More specifically, the ethylene-based unsaturated compounds of this specification include the following:

[0034] (a) Moiety of the following structure (1):

[0035] ; and

[0036] (b1) Moiety of the following structure (2):

[0037] ; or

[0038] (b2) Moiety of the following structure (3):

[0039] ; or

[0040] (b3) A combination of the moiety of structure (2) and the moiety of structure (3),

[0041] Here, (i) Y represents a linear or branched linker comprising one or more carbon atoms, (ii) each X, which may be the same or different, represents an alkoxy group or an organic group inert to isocyanate groups at a temperature of 100°C or lower, provided that at least one X represents an alkoxy group, and (iii) R, which may be the same or different 1 and R 2 Each represents an organic group that is inert to isocyanate groups at temperatures of 100°C or lower; (iv) R which may be the same or different 3 and R 4 Each represents an organic group that is inert to hydrogen or an isocyanate group at a temperature of 100°C or lower; (v) each " " indicates a link to another part of the ethylene-based unsaturated compound. In some embodiments, at least one carbon-carbon double bond of the ethylene-based unsaturated compound exists as a =CH2 terminal group, and there are no additional substituents on its carbon.

[0042] As indicated, each X, which may be the same or different, represents an alkoxy group or an organic group inactive to an isocyanate group at temperatures below 100°C, provided that at least one X represents an alkoxy group. As used herein, the phrase "inactive to an isocyanate group at temperatures below 100°C" means that the group is inactive to an isocyanate group at these temperatures when the group is covalently attached to another atom within the structure being discussed, as illustrated in the various structures exemplified herein. The group is covalently attached to another atom within the structure being discussed. As is recognized, Zerevitinov-active hydrogen is not inactive to an isocyanate group at these temperatures, and therefore, any organic group described herein as inactive to an isocyanate group at these temperatures does not include Zerevitinov-active hydrogen (Zerevitinov-active hydrogen is [Rompp's Chemical Dictionary (Rompp Chemie Lexikon), 10 th (Defined in [ed., Georg Thieme Verlag Stuttgart, 1996]). Generally, Zerevitinov-active hydrogen-containing groups are hydroxyl (OH), amino (NH x It is understood in the relevant technical field to mean ) and thiol (SH) groups.

[0043] In some implementations, each R may be the same or different in structures (2) and (3). 1 and R 2 represents an alkyl group, for example, an alkyl group having 1 to 9 or 1 to 4 carbon atoms, for example, each R which may be the same or different in structures (2) and (3). 1 and R 2represents a methyl group, an ethyl group, a propyl group, or a butyl group. Additionally, in some embodiments, each X in structure (1) represents the same or different alkyl, acyloxy, or alkoxy group, for example, having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X represents an alkoxy group, for example, where at least two Xs represent an alkoxy, for example, a methoxy, ethoxy, or propyloxy group, or where each X represents an alkoxy, for example, a methoxy, ethoxy, or propyloxy group. Additionally, in some embodiments, Y in structure (1) comprises a linear or branched alkylene radical having 1 to 8 carbon atoms, for example, a linear alkylene radical having 2 to 4, or in some cases 3, carbon atoms, or a branched alkylene radical having 5 to 6 carbon atoms.

[0044] Additionally, in some embodiments, the ethylene-based unsaturated compound further comprises (c) a segment of the following structure:

[0045]

[0046] Here, G is O, S, or NR, where R represents hydrogen or an organic group inert to isocyanate groups at temperatures below 100°C, and each " " indicates a connection to another part of the ethylene-based unsaturated compound. In some embodiments, the ethylene-based unsaturated compound has 1 to 4 such segments.

[0047] In some embodiments, any ethylene-based unsaturated compound described herein (e.g., any ethylene-based unsaturated compound comprising a moiety of structure (3)) comprises a moiety of structure 3A:

[0048]

[0049] Here, X, Y, R 1 , R2 and " " is as described above for each of structures (1)-(3). In some embodiments, the ethylene-based unsaturated compound has 1 to 4 of these moiety of structure 3A.

[0050] In some embodiments, any ethylene-based unsaturated compound described herein (e.g., any ethylene-based unsaturated compound comprising a moiety of structure (3)) comprises the condition that the ethylene-based unsaturated compound has at least one moiety of structure 3B, in some cases only one:

[0051]

[0052] Here, X, Y, R 1 , R 2 and " " is as described above for each structure (1)-(3).

[0053] In some embodiments, any ethylene-based unsaturated compound described herein (e.g., any ethylene-based unsaturated compound comprising a moiety of structure (2)) comprises the condition that the ethylene-based unsaturated compound has at least one moiety of structure 2A, in some cases only one:

[0054]

[0055] Here, X, Y, R 1 , R 2 and " " is as described above for each structure (1)-(3).

[0056] In some embodiments, any ethylene-based unsaturated compound described herein (e.g., any ethylene-based unsaturated compound comprising a moiety of structure (2)) comprises the condition that the ethylene-based unsaturated compound has 0 or 2 to 4 or 2 moietyes of structure 2B:

[0057]

[0058] Here, X, Y, R 1 , R 2 and " " is as described above for each structure (1)-(3).

[0059] In some embodiments, the ethylene-based unsaturated compound of this specification has the following structure (4A) or structure (4B):

[0060]

[0061] Here (i) R 5 represents H or CH3, and (ii) R 6 represents a group comprising a branched or straight-chain alkylene radical, for example, wherein the branched or straight-chain alkylene radical has at least 2, 2 to 8, or 2 to 4 carbon atoms, and (iii) Y 1 represents a linear or branched linker containing one or more carbon atoms, and (iv) R which may be the same or different 7 and R 8 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, and (v) R which may be the same or different 9 and R 10 Each represents an organic group that is inert to hydrogen or an isocyanate group at a temperature of 100°C or lower, and (vi) each X which may be the same or different. 1 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 1 represents an alkoxy group, and (vii) each q, which may be the same or different, is an integer having a value from 1 to 6, e.g. 1 to 3, e.g. 1.

[0062] In some embodiment of the ethylene-based unsaturated compound represented by structure (4A) or structure (4B), R 6represents a group comprising a carbamate segment in addition to a branched or straight-chain alkylene radical, for example, where R 6... represents a group further comprising a unit derived from polyisocyanate, e.g., where polyisocyanate is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, (hydrogenated) xylylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, 2,4- and / or 4,4'-methylene dicyclohexyl diisocyanate, methylene diphenyl diisocyanate, tetramethylxylene diisocyanate, 1,5-pentane diisocyanate, bis(2-isocyanato-ethyl)fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, lysine isocyanate, hexamethylene diisocyanate trimer (e.g., Desmodur® from Covestro) (commercially available as N3300A), triphenylmethane-4,4',4"-triisocyanate (e.g., commercially available as Desmodur® RE from Covestro), hexamethylene diisocyanate trimer (e.g., commercially available as Desmodur® N3200 from Covestro), toluene diisocyanate-based aromatic polyisocyanate (e.g., commercially available as Desmodur® IL BA from Covestro),It comprises polyisocyanurates of toluene diisocyanate (e.g., commercially available as Desmodur® RC from Covestro), or any combination of two or more of these. As used herein, the term "polyisocyanate" encompasses diisocyanates and isocyanates having an isocyanate functional value greater than 2.0.

[0063] In some embodiment of the ethylene-based unsaturated compound represented by structure (4A) or structure (4B), R 6 It does not contain a carbamate segment.

[0064] In some embodiment of the ethylene-based unsaturated compound represented by structure (4A) or structure (4B), R 6 silver

[0065] Linear or branched alkylene radicals composed of carbon and hydrogen, for example

[0066] ;

[0067]

[0068]

[0069]

[0070] Any combination of two or more of these, wherein each " " indicates a connection to another part of the ethylene-based unsaturated compound, and each " shown to the left of the oxygen "is within structure (4A) or structure (4B) Represents the connection to the segment.

[0071] Additionally, in some embodiments of the ethylene-based unsaturated compound represented by structure (4A) or structure (4B), R, which may be the same or different in structure (4A) and structure (4B). 7 and R 8represents an alkyl group, for example, an alkyl group having 1 to 9 or 1 to 4 carbon atoms, and R, for example, which may be the same or different here. 7 and R 8 represents a methyl group, an ethyl group, a propyl group, or a butyl group. Additionally, in some embodiments, each X in structure (4A) and structure (4B) 1 represents the same or different alkyl, acyloxy, or alkoxy group, for example, the same or different alkyl, acyloxy, or alkoxyl group having 1 to 9 or 1 to 4 carbon atoms, provided that at least 1 X 1 represents an alkoxy group, for example, here at least two X 1 represents an alkoxy, e.g., methoxy, ethoxy, or propyloxy group, or where each X 1 represents an alkoxy group, such as a methoxy, ethoxy, or propyloxy group. Additionally, in some embodiments, Y in structures (4A) and (4B) 1 It includes linear or branched alkylene radicals having 1 to 8 carbon atoms, for example, linear alkylene radicals having 2 to 4, or in some cases 3, carbon atoms (e.g., propylene radicals), or branched alkylene radicals having 5 to 6 carbon atoms.

[0072] In another embodiment, the ethylene-based unsaturated compound of this specification has the following structure (5):

[0073]

[0074] Here, q, R 5 , R 6 , R 7 , R 9 , R 10 , Y 1 and X 1 The structures (4A) and (4B) are as described above.

[0075] In another embodiment, the ethylene-based unsaturated compound of this specification has the following structure (6):

[0076]

[0077] Here, q, R 5 , R 6 , R 7 , R 9 , R 10 , Y 1 and X 1 ... are as described above with respect to structures (4A) and (4B), respectively, where q1 is 0 or 1, and Z represents an organic group inert to isocyanate groups at temperatures of 100°C or lower, in some cases a divalent organic group, optionally containing, for example, isocyanate-inert oxygen, nitrogen, sulfur or a combination thereof, and C1 to C 18 It represents a hydrocarbon group containing an alkylene group or a C5-C6 cycloalkylene group.

[0078] In some embodiment of the ethylene-based unsaturated compound represented by structure (6), Z is

[0079] (Here, x takes a value from 3 to 19);

[0080]

[0081] and, here, each " " indicates a connection to another part of the ethylene-based unsaturated compound.

[0082] In another embodiment, the ethylene-based unsaturated compound of this specification has the following structure (7):

[0083]

[0084] Here, q, q1, R 5 , R 6 , R 8 , R 9 , R 10 , Z, Y 1 , and X 1Each is as described above in relation to the structure (6).

[0085] In a further embodiment, the ethylene-based unsaturated compound of this specification has the following structure (8):

[0086]

[0087] Here, q, R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , Y 1 and X 1 Each is as described above in relation to structure (6), and Z 1 It exhibits an organic group that is inert to isocyanate groups at temperatures below 100°C, and in some cases, a divalent organic group, optionally containing, for example, isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof, and C1 to C 18 Representing a hydrocarbon group comprising an alkylene group or a C5-C6 cycloalkylene group, (vii) m and n, which may be the same or different, are integers each having a value from 1 to 4. In some embodiments, m+n is 4 or less, e.g., where m is 1 or 2, e.g. 1, and n is 1 or 2, e.g. 1. In some embodiments, Z in structure (8) 1 silver

[0088] (Here, x takes a value from 3 to 19);

[0089] (Here, each X1, X2, X3, and X4, which may be identical or different, has a value of 1 to 10, except that the structure has a molecular weight of 200 to 1500);

[0090]

[0091]

[0092] and, here, each " " indicates a connection to another part of the ethylene-based unsaturated compound.

[0093] In another additional embodiment, the ethylene-based unsaturated compound of this specification has the following structure (9):

[0094]

[0095] Here, q, R 5 , R 6 , R 7 , R 9 , R 10 , Y 1 , Z 1 , X 1 , m and n are as described above in relation to the structure (8), respectively.

[0096] In some embodiments, any ethylene-based unsaturated compound of this specification has a silane content of more than 50 mmol, e.g., more than 160 mmol, more than 180 mmol, or more than 200 mmol per 100 grams of the ethylene-based unsaturated compound (determined as described in the Examples section of this specification). Also, in some embodiments, any ethylene-based unsaturated compound of this specification has a silane content (determined to be 50 to 300 mmol or 60 to 250 mmol per 100 grams of the ethylene-based unsaturated compound). In some embodiments, any ethylene-based unsaturated compound of this specification has a silane content of more than 160 mmol, more than 180 mmol, or more than 200 mmol per 100 grams of the ethylene-based unsaturated compound.

[0097] Some embodiments of the ethylene-based unsaturated compound of this specification are reaction products comprising (a) an isocyanate-functional ethylene-based unsaturated compound; and (b) an aspartate silane. In some of these embodiments, the aspartate silane has the following structure:

[0098]

[0099] Here, each R which may be the same or different 15 and each X 4 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, provided that at least one X 4 represents an alkoxy group, and Y 4 represents a linear or branched linker containing one or more carbon atoms, and each R may be the same or different. 15b It represents an organic group that is inert to hydrogen or isocyanate groups at temperatures below 100°C.

[0100] The above aspartate silane is (i) chemical formula (ii) an aminoalkyl alkoxysilane, and chemical formula It may include the reaction product of a reactant comprising a maleic acid or fumaric acid ester, wherein R 16 and R 17 represents the same or different organic group that is isocyanate-inactive below 100°C, for example, where R 16 and R 17 represents the same or different alkyl group having 1 to 4 carbon atoms, and each R which may be the same or different. 18 represents hydrogen, or an organic group that is isocyanate-inert below 100°C, and each X 5 represents the same or different organic group that is isocyanate-inactive below 100°C, provided that at least one X 5 is an alkoxy group, and for example, here each X 5 represents the same or different alkyl or alkoxy group having 1 to 4 carbon atoms, provided that at least 1 X 5 is an alkoxy group, and n is an integer with a value from 2 to 4, e.g., 3.

[0101] Specific examples of suitable aminoalkyl alkoxysilanes include, but are not limited to, 2-aminoethyl-dimethylmethoxysilane, 3-aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropyl-methyl-diethoxysilane, or a mixture of any two or more of these. Specific examples of suitable maleic acid or fumaric acid esters include, but are not limited to, dimethyl maleic acid ester, diethyl maleic acid ester, di-n-butyl maleic acid ester, dimethyl fumaric acid ester, diethyl fumaric acid ester, di-n-butyl fumaric acid ester, or a mixture of any two or more of these.

[0102] The reaction of maleic acid or fumaric acid esters with aminoalkyl alkoxysilanes can be carried out, for example, within a temperature range of 0°C to 100°C. The amounts of acid esters and aminoalkyl alkoxysilanes can be selected so that the starting compounds are used in a molar ratio of acid ester to aminoalkyl alkoxysilane of 0.8 to 1.2:1, e.g. 1.0 to 1.2:1, or in some cases 1.01 to 1.2:1. The reaction can be carried out in the presence or absence of a solvent, e.g., dioxane. Of course, the reaction can be carried out using a mixture of different 3-aminoalkyl alkoxysilanes and a mixture of fumaric acid and / or maleic acid esters.

[0103] In some cases, isocyanate-functional ethylene unsaturated compounds that react with aspartate silanes to produce ethylene unsaturated compounds have the following structure:

[0104]

[0105] Here, R 19 represents H or CH3, and X 6 represents O, S, NH or NR', where R' is an alkyl radical, e.g., an alkyl radical having 1 to 6 carbon atoms, and n is an integer having a value of 2 to 8, e.g., 2 to 4.

[0106] Specific examples of suitable isocyanate-functional ethylene-based unsaturated compounds include, but are not limited to, isocyanatoethyl methacrylate, isocyanatopropyl methacrylate, isocyanatobutyl methacrylate, isocyanatoethyl acrylate, isocyanatopropyl acrylate, isocyanatobutyl acrylate, or a mixture of any two or more of these.

[0107] Other suitable isocyanate-functional ethylene-unsaturated compounds that can be used in combination with any one or more of the previously mentioned isocyanate-functional ethylene-unsaturated compounds are reaction products of reactants comprising (i) monohydroxy-substituted monofunctional or polyfunctional (meth)acrylates, and (ii) polyisocyanates. Specific examples of suitable monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylates are, but are not limited to, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl 2-chloroacrylate, 2-hydroxyethyl 2-ethylacrylate, 2-hydroxyethyl 2-propylacrylate, 2-hydroxyethyl 2-butylacrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl-2-propylacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl 2-butylacrylate, 3-hydroxypropyl 2-bromoacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and 3-hydroxybutyl It includes 2-ethyl acrylate, 4-hydroxybutyl 2-butyl acrylate, 2-hydroxybutyl 2-propyl acrylate, 4-hydroxybutyl 2-chloro acrylate, hydroxyethyl caprolactone (meth)acrylate, caprolactone (meth)acrylate, polypropylene glycol monoacrylate, polyethylene glycol monoacrylate, bis(methacryloyloxy)propanol, bis(acryloyloxy)propanol, pentaerythritol triacrylate, or any combination of two or more of these.Specific examples of polyisocyanates suitable for use in reacting with monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylates to form isocyanate-functional ethylene-based unsaturated compounds are, but are not limited to, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate. Isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, bis(2-isocyanato-ethyl)fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, lysine isocyanate, hexamethylene diisocyanate trimer (commercially available, e.g., from Covestro as Desmodur® N3300A), triphenylmethane-4,4',4"-triisocyanate (e.g. from Covestro It includes a hexamethylene diisocyanate trimer (commercially available as Desmodur® RE from Covestro, e.g., commercially available as Desmodur® N3200 from Covestro), an aromatic polyisocyanate based on toluene diisocyanate (commercially available as Desmodur® IL BA from Covestro), a polyisocyanurate of toluene diisocyanate (commercially available as Desmodur® RC from Covestro), or any combination of two or more of these.

[0108] The reaction of a monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylate with a polyisocyanate may be carried out, for example, within a temperature range of 25°C to 100°C. The reaction may be carried out, if desired, in the presence of a catalyst. Suitable catalysts include, but are not limited to, organometallic catalysts, amine catalysts, or combinations thereof, for example, wherein the catalyst comprises a copper compound, e.g., copper naphthenate; a cobalt compound, e.g., cobalt naphthenate; a zinc compound, e.g., zinc naphthenate; a bismuth compound, e.g., bismuth neodecanoate; a tin compound, e.g., di-n-butyltin dilaurate; triethylamine; triethylenediamine; 1,4-diazacyclo[2.2.2]octane (DABCO); dimethylethanolamine (DMEA); or any combination of two or more of the above. The amounts of monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylates and polyisocyanates are generally selected so that the starting compounds are used in a molar ratio of monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylates to polyisocyanates of 0.1:1 to 2:1, e.g. 0.5:1 to 1.5:1, or in some cases 1:1. The reaction may be carried out without a solvent or in the presence of a suitable solvent, such as propanolmethylene chloride, chloroform, tetrahydrofuran (THF), toluene, xylene, ethyl acetate, tetrachloroethane, dioxane, and any mixture of two or more of these. Of course, the reaction may be carried out using a mixture of different monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylates and different polyisocyanates.

[0109] The reaction of an isocyanate-functional ethylene-unsaturated compound and an aspartate silane to produce an ethylene-unsaturated compound of a specific embodiment of this specification may be carried out in the presence of a catalyst, if desired. Suitable catalysts include, but are not limited to, organometallic catalysts, amine catalysts, or combinations thereof, for example, wherein the catalyst comprises a copper compound, e.g., copper naphthenate; a cobalt compound, e.g., cobalt naphthenate; a zinc compound, e.g., zinc naphthenate; a bismuth compound, e.g., bismuth neodecanoate; a tin compound, e.g., di-n-butyl tin dilaurate; triethylamine; triethylenediamine; DABCO; DMEA; or any combination of two or more of the above. In some embodiments, the reaction is carried out at a temperature of 10 to 120°C or 25 to 100°C. Additionally, in some embodiments, the reactants are used in relative amounts providing at least 1:1, for example, a molar ratio of isocyanate-reactive group to isocyanate group of greater than 1 and less than 1.5. The resulting ethylene-based unsaturated compound comprises an aspartate group from an aspartate silane, for example, as illustrated by the structures (4A) and (4B) described above.

[0110] In some embodiments, the resulting aspartate group-containing ethylene-based unsaturated compound is subjected to further processing to convert the aspartate group into a hydantoin group, wherein this conversion is optionally carried out at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, or 80 to 100°C in the presence of a catalyst, e.g., Brønsted acid, carboxylic acid, sulfonic acid, phenol, or any mixture of two or more of these. The resulting ethylene-based unsaturated compound contains a hydantoin group, for example, as illustrated by the structure (5) described above.

[0111] As a result, the present specification also relates to a method for producing an ethylene-based unsaturated compound. The method comprises reacting an isocyanate-functionalized ethylene-based unsaturated compound with an aspartate silane in the presence of optionally a catalyst to produce an ethylene-based unsaturated compound containing an aspartate group. In this method, the aspartate silane has the following structure:

[0112]

[0113] Here, each R which may be the same or different 20 ...exhibits an organic group that is inert to isocyanate groups at temperatures below 100°C, and each R, which may be the same or different. 20b represents an organic group that is inert to hydrogen or isocyanate groups at temperatures below 100°C, and each X 6 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 6 represents an alkoxy group, and Y 5 represents an organic group that is inert to isocyanate groups at temperatures of 100°C or lower. In some embodiments, the method further comprises converting aspartate groups to hydantoin groups, wherein this conversion is optionally carried out in the presence of a catalyst to produce an ethylene-based unsaturated compound containing hydantoin groups.

[0114] Another embodiment of the ethylene-based unsaturated compound of the present specification is a reaction product comprising (a) a polyisocyanate; (b) a hydroxyl-functional ethylene-based unsaturated compound; and (b) an aspartate silane of the type described above.In these embodiments, suitable polyisocyanates are, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4 Trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, bis(2-isocyanato-ethyl)fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, lysine isocyanate, hexamethylene diisocyanate trimer (commercially available, e.g., from Covestro as Desmodur® N3300A), triphenylmethane-4,4',4"-triisocyanate (commercially available, e.g., from Covestro as Desmodur® RE), hexamethylene diisocyanate trimer (commercially available, e.g., from Covestro as Desmodur® N3200 It includes an aromatic polyisocyanate based on toluene diisocyanate (commercially available, e.g., Desmodur® IL BA from Covestro), a polyisocyanurate of toluene diisocyanate (commercially available, e.g., Desmodur® RC from Covestro), or any combination of two or more of these.In addition, in these embodiments, suitable hydroxyl-functional ethylene-based unsaturated compounds include, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, hydroxyhexyl (meth)acrylate, or any combination of two or more of these.

[0115] Accordingly, the present specification also relates to a method for preparing an ethylene-based unsaturated compound, comprising reacting a diisocyanate, a hydroxyl-functional ethylene-based unsaturated compound, and an aspartate silane in the presence of optionally a catalyst to produce an ethylene-based unsaturated compound containing an aspartate group. In such a method, the aspartate silane has the following structure:

[0116]

[0117] Here, each R which may be the same or different 20 ...exhibits an organic group that is inert to isocyanate groups at temperatures below 100°C, and each R, which may be the same or different. 20b represents an organic group that is inert to hydrogen or isocyanate groups at temperatures below 100°C, and each X 6 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 6 represents an alkoxy group, and Y 5 represents an organic group that is inert to isocyanate groups at temperatures of 100°C or lower. In some embodiments, the method further comprises converting aspartate groups to hydantoin groups, wherein this conversion is optionally carried out in the presence of a catalyst to produce an ethylene-based unsaturated compound containing hydantoin groups.

[0118] In another embodiment, the ethylene-based unsaturated compound of this specification comprises (a) a primary amine-containing aspartate and / or polyaspartate amine; (b) an isocyanate-functional ethylene-based unsaturated compound; and (c) a reaction product of a reactant comprising an isocyanate-functional silane.

[0119] Primary amine-containing aspartates suitable for use in preparing such ethylene-based unsaturated compounds include, but are not limited to, those having the following structures:

[0120]

[0121] Here, Z 2 ...represents an organic group that is inert to isocyanate groups at temperatures below 100°C, or in some cases, a divalent organic group, and optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof, and C1 to C 18 Representing a hydrocarbon group comprising an alkylene group or a C5-C6 cycloalkylene group, each R which may be the same or different. 21 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, for example, where each R 21 represents the same or different alkyl groups, for example, alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, where each R 21 is a methyl group, ethyl group, propyl group, or butyl group, and each R may be the same or different. 21a represents an organic group that is inert to hydrogen or an isocyanate group at a temperature of 100°C or lower, and m and n, which may be the same or different, are integers having values ​​from 1 to 4, for example, where m+n is 4 or less, for example, where m is 1 or 2, for example 1, and n is 1 or 2, for example 1.

[0122] Polyaspartate amines suitable for use in preparing such ethylene-based unsaturated compounds include, but are not limited to, those having the following structures:

[0123]

[0124] Here, Z 3 ...exhibits an organic group that is inert to isocyanate groups at temperatures below 100°C, and in some cases, a divalent organic group, and optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof, and C1 to C 18 Representing a hydrocarbon group comprising an alkylene group or a C5-C6 cycloalkylene group, each R which may be the same or different. 22a represents an organic group inert to hydrogen or isocyanate groups at temperatures below 100°C, and each R may be the same or different. 22 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, for example, where each R 22 represents the same or different alkyl groups, for example, alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, where each R 22 m and n, which may be the same or different, are integers having values ​​from 1 to 4, for example, where m+n is 4 or less, for example, where m is 1 or 2, for example 1, and n is 1 or 2, for example 1.

[0125] These primary amine-containing aspartates and polyaspartate amines have the chemical formula: (NH2) m Z 3 (NH2) n (Here Z 3is optionally an isocyanate-hydrocarbon group containing inert oxygen, nitrogen, sulfur, or a combination thereof, and m+n is an integer having a value of at least 2, e.g., 2 to 4) and a primary polyamine corresponding to and a maleic acid or fumaric acid ester of the following chemical formula (isomers of both are as indicated by wavy bonding):

[0126] (Here, each R which may be the same or different) 23 ...exhibits an organic group that is inert to isocyanate groups at temperatures below 100°C, and each R, which may be the same or different. 24 It can be prepared by reacting with hydrogen, or an organic group that is inert to isocyanate groups at a temperature of 100°C or lower.

[0127] Specific examples of suitable primary polyamines include, but are not limited to, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, bis-(3-aminopropyl)ether, 1,2-bis-(3-aminopropyloxy)ethane, and 1,3-bis-(3-aminopropyloxy)-2,2'-dimethylpropane. 1,2-Bisaminocyclohexane, 1,3-Bisaminocyclohexane, 1,4-Bisaminocyclohexane, 1,3-Bisaminomethylcyclohexane, 1,4-Bisaminomethylcyclohexane, 1,3-Bisaminoethylcyclohexane, 1,4-Bisaminoethylcyclohexane, 1,3-Bisaminopropylcyclohexane, 1,4-Bisaminopropylcyclohexane, hydrogenated 4,4'-Diaminodiphenylmethane, 1-Amino-3,3,5-Trimethyl-5-Aminomethyl-cyclohexane, 2,4- and / or 2,6-Hexahydrotoluylenediamine, 2,4'- and / or 4,4'-Diamino-Dicyclohexylmethane, 3,3'-Dimethyl-4,4'-Diamino-Dicyclohexylmethane, Propane-1,2,3-Triamine, Pentane-1,3,5-triamine, benzene-1,3,5-triamine, isophoronediamine, menthandiamine, 1,4-bis-aminopropylpiperazine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, 2,4-toluenediamine, 2,4'- and / or 4,4'-diaminodiphenylmethane, m-aminobenzylamine, 4-chloro-o-phenylenediamine, tetrachloro-p-xylylenediamine, 4-methoxy-6-methyl-m-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, benzidine, 4,4'-bis(o-toluidine), dianisidine, 4,4'-Diaminodiphenylmethane, 2,2-(4,4'-Diaminodiphenyl)propane, 4,4'-Diaminodiphenyl ether, 4,4'-Thiodianiline, 4,4'-diaminodiphenylsulfone, 4,4'-diaminoditolylsulfone, methylenebis(o-chloroaniline), 3,9-bis(3-aminopropyl) 2,4,8,10-tetraoxaspiro[5,5]undecane, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,4-bis(aminoethylpiperazine), 1,4-bis(aminopropylpiperazine), 2,6-diaminopyridine, and bis(3,4-diaminophenyl)sulfone, relatively high molecular weight polyether polyamines containing aliphatic-bonded primary amino groups (e.g., JEFFAMINE® products commercially available from Huntsman Corp.), and any combination of two or more of the above Includes.

[0128] Specific examples of suitable maleic acid or fumaric acid esters include, but are not limited to, dimethyl, diethyl, and di-n-butyl esters of maleic acid and fumaric acid, and corresponding maleic acid or fumaric acid esters substituted by methyl at the 2- and / or 3-positions.

[0129] The preparation of primary amine-containing aspartate from the above-mentioned starting material can be carried out, for example, at a temperature of -20°C to 100°C using the starting material in a ratio such that 0.8+m / n to 1.2+m / n, e.g. 1+m / n primary amino groups are present for each olefinic double bond, where m and n are as defined above for the chemical formula of the primary polyamine. The reaction can be carried out without a solvent or in the presence of a suitable solvent, such as methanol, ethanol, propanol, dioxane, and a mixture of these solvents. The reaction may optionally be carried out in the presence of a catalyst such as an organometallic catalyst, wherein the catalyst comprises a copper compound, e.g., copper naphthenate; a cobalt compound, e.g., cobalt naphthenate; a zinc compound, e.g., zinc naphthenate; a bismuth compound, e.g., bismuth neodecanoate; a tin compound, e.g., di-n-butyl tin dilaurate; or any combination of two or more of the above.

[0130] As indicated, according to some embodiments, the ethylene-based unsaturated compound of this specification comprises, in addition to the primary amine-containing aspartate and / or polyaspartate amine described above, also (b) an isocyanate-functionalized ethylene-based unsaturated compound; and (c) a reaction product of a reactant comprising an isocyanate-functionalized silane. Isocyanate-functionalized ethylene-based unsaturated compounds suitable for this purpose include, but are not limited to, those having the following structures:

[0131]

[0132] Here, R 25 represents H or CH3, and X 7 represents O, S, NH or NR', where R' is an alkyl radical, e.g., an alkyl radical having 1 to 6 carbon atoms, and n is an integer having a value of 2 to 8, e.g., 2 to 4.

[0133] Specific examples of suitable isocyanate-functional ethylene-based unsaturated compounds include, but are not limited to, isocyanatoethyl methacrylate, isocyanatopropyl methacrylate, isocyanatobutyl methacrylate, isocyanatoethyl acrylate, isocyanatopropyl acrylate, isocyanatobutyl acrylate, or a mixture of any two or more of these.

[0134] Other suitable isocyanate-functional ethylene-unsaturated compounds that can be used in combination with any one or more of the previously mentioned isocyanate-functional ethylene-unsaturated compounds are reaction products comprising (i) monohydroxy-substituted monofunctional or polyfunctional (meth)acrylates, and (ii) diisocyanates. Specific examples of suitable monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylates are, but are not limited to, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl 2-chloroacrylate, 2-hydroxyethyl 2-ethylacrylate, 2-hydroxyethyl 2-propylacrylate, 2-hydroxyethyl 2-butylacrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl-2-propylacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl 2-butylacrylate, 3-hydroxypropyl 2-bromoacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and 3-hydroxybutyl It includes 2-ethyl acrylate, 4-hydroxybutyl 2-butyl acrylate, 2-hydroxybutyl 2-propyl acrylate, 4-hydroxybutyl 2-chloro acrylate, hydroxyethyl caprolactone (meth)acrylate, caprolactone (meth)acrylate, polypropylene glycol monoacrylate, polyethylene glycol monoacrylate, bis(methacryloyloxy)propanol, bis(acryloyloxy)propanol, pentaerythritol triacrylate, or any combination of two or more of these.Specific examples of polyisocyanates suitable for use in reacting with monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylates to form isocyanate-functional ethylene-based unsaturated compounds are, but are not limited to, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate. Isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, bis(2-isocyanato-ethyl)fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, lysine isocyanate, hexamethylene diisocyanate trimer (commercially available, e.g., from Covestro as Desmodur® N3300A), triphenylmethane-4,4',4"-triisocyanate (e.g. from Covestro It includes a hexamethylene diisocyanate trimer (commercially available as Desmodur® RE from Covestro, e.g., commercially available as Desmodur® N3200 from Covestro), an aromatic polyisocyanate based on toluene diisocyanate (commercially available as Desmodur® IL BA from Covestro), a polyisocyanurate of toluene diisocyanate (commercially available as Desmodur® RC from Covestro), or any combination of two or more of these.

[0135] The reaction of a monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylate with a polyisocyanate may be carried out, for example, within a temperature range of 25°C to 100°C. The reaction may be carried out, if desired, in the presence of a catalyst. Suitable catalysts include, but are not limited to, organometallic catalysts, amine catalysts, or combinations thereof, for example, wherein the catalyst comprises a copper compound, e.g., copper naphthenate; a cobalt compound, e.g., cobalt naphthenate; a zinc compound, e.g., zinc naphthenate; a bismuth compound, e.g., bismuth neodecanoate; a tin compound, e.g., di-n-butyltin dilaurate; triethylamine; triethylenediamine; DABCO; DMEA; or any combination of two or more of the above. The amounts of monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylates and polyisocyanates are generally selected so that the starting compounds are used in a molar ratio of monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylates to polyisocyanates of 0.1:1 to 2:1, e.g. 0.5:1 to 1.5:1, or in some cases 1:1. The reaction may be carried out without a solvent or in the presence of a suitable solvent, e.g., methylene chloride, chloroform, THF, toluene, xylene, ethyl acetate, tetrachloroethane, dioxane, and any mixture of two or more of these. Of course, the reaction may be carried out using a mixture of different monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylates and different polyisocyanates.

[0136] Suitable isocyanate-functional silanes are, without limitation, structure: OCN-Y 6 -Si(X 8 Includes the things of )3, where Y 6 represents a linear or branched linker containing one or more carbon atoms, for example, where Y 6... comprises linear or branched alkylene radicals having 1 to 8 carbon atoms, for example, linear alkylene radicals having 2 to 4 or, in some cases, 3 carbon atoms, or branched alkylene radicals having 5 to 6 carbon atoms, and each X 8 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 8 represents an alkoxy group, for example, where each X 8 represents the same or different alkyl, acyloxy, or alkoxy group, for example, the same or different alkyl, acyloxy, or alkoxyl group having 1 to 9 or 1 to 4 carbon atoms, provided that at least 1 X 8 represents an alkoxy group, for example, here at least two X 8 represents an alkoxy, e.g., methoxy, ethoxy, or propyloxy group, or where each X 8 It represents an alkoxy group, such as methoxy, ethoxy, or propyloxy.

[0137] Specific examples of suitable isocyanate-functional silanes include, but are not limited to, 3-isocyanatopropyl-methyldimethoxysilane, 3-isocyanatopropyl-trimethoxysilane, 3-isocyanatopropyl-triethoxysilane, as well as mixtures of any two or more of these.

[0138] The reaction of a primary amine-containing aspartate and / or polyaspartate amine, an isocyanate-functionalized ethylene-unsaturated compound, and an isocyanate-functionalized silane isocyanate-functional group to produce an ethylene-based unsaturated compound of a specific embodiment of this specification may be carried out in the presence of a catalyst, if desired. Suitable catalysts include, but are not limited to, organometallic catalysts, amine catalysts, or combinations thereof, for example, wherein the catalyst comprises a copper compound, e.g., copper naphthenate; a cobalt compound, e.g., cobalt naphthenate; a zinc compound, e.g., zinc naphthenate; a bismuth compound, e.g., bismuth neodecanoate; a tin compound, e.g., di-n-butyltin dilaurate; triethylamine; triethylenediamine; DABCO; DMEA; or any combination of two or more of the above. In some embodiments, the reaction is carried out at a temperature of 10 to 120°C or 25 to 100°C. Also, in some embodiments, the reactants are used in relative amounts providing at least 1:1, for example, a molar ratio of isocyanate-reactive group to isocyanate group of greater than 1 and less than 1.5. The resulting ethylene-based unsaturated compound contains aspartate groups, for example, as illustrated by the structures (6) and / or (8) described above.

[0139] In some embodiments, the resulting aspartate group-containing ethylene-based unsaturated compound is subjected to further processing to convert at least a portion of the aspartate groups into hydantoin groups, wherein this conversion is carried out at reaction temperatures of 0 to 200°C, 70 to 130°C, 75 to 105°C, 80 to 100°C, 90 to 120°C, or 100 to 120°C, optionally in the presence of a catalyst, such as Brønsted acid, carboxylic acid, sulfonic acid, phenol, or any mixture of two or more of these. The resulting ethylene-based unsaturated compound contains hydantoin groups, for example, as illustrated by the structures (7) and / or (9) described above.

[0140] As a result, the present specification also relates to a method for producing an ethylene-unsaturated compound comprising reacting (a) a primary amine-containing aspartate and / or polyaspartate amine as described above; (b) an isocyanate-functional ethylene-unsaturated compound as described above; and (c) an isocyanate-functional silane as described above, optionally in the presence of a catalyst to produce an ethylene-unsaturated compound containing aspartate groups. In some embodiments, the method further comprises converting at least some aspartate groups to hydantoin groups, wherein such conversion is optionally carried out in the presence of a catalyst to produce an ethylene-unsaturated compound containing hydantoin groups.

[0141] This specification also relates to the use of the various ethylene-based unsaturated compounds described above. More particularly, in some aspects, this specification relates to the use of these compounds in coating compositions, such as radiation-curable coating compositions, comprising such compositions suitable for application, for example, to optical glass fiber substrates. In particular, the ethylene-based unsaturated compounds described in this specification are currently considered to serve a particularly beneficial function as adhesion-promoting compounds in such compositions. In fact, surprisingly, it has been observed that at least some embodiments of these ethylene-based unsaturated compounds can produce cured coatings that exhibit significantly improved adhesion performance compared to similar coatings using other adhesion promoters, including adhesion promoters commonly used in radiation-curable coating compositions suitable for application to optical glass fiber substrates, while being easily and efficiently synthesized.

[0142] Accordingly, some aspects of this specification relate to a radiation-curable coating composition comprising an ethylene-based unsaturated compound as described above. In some embodiments, such an ethylene-based unsaturated compound is present in an amount of 0.01 to 99 wt%, 0.1 to 20 wt%, 1 to 50 wt%, 5 to 30 wt%, 40 to 70 wt%, 60 to 80 wt%, 65 to 99 wt%, or 0.01 to 20 wt% based on the total weight of the solid in the radiation-curable coating composition.

[0143] In these embodiments, the radiation-curable coating composition may comprise other compounds having radiation-curable groups, and such other radiation-curable compositions may be used in an amount of, for example, 99 wt%, 90 wt%, 75 wt%, or 70 wt% or less, based on the total weight of the solid in the radiation-curable coating composition. Examples of such other radiation-curable compounds are, but not limited to, polyether (meth)acrylates, polyester (meth)acrylates, urethane (meth)acrylates, epoxy (meth)acrylates, and oligomers and polymers including known reactive diluents from radiation curing (Reference [Rompp Lexikon Chemie, p. 491, 10 th [See Ed. 1998, Georg-Thieme-Verlag, Stuttgart]).

[0144] Additionally, in some embodiments, the radiation-curable coating composition comprises an ethylene-based unsaturated oligomer. As used herein, "oligomer" means a molecule of intermediate relative molecular mass, the structure of which comprises a plurality of units derived actually or conceptually from a molecule of lower relative molecular mass. In some embodiments, the reactive oligomer described herein has a number average molecular weight (Mn) of 1,000 g / mol to 35,000 g / mol, 1,000 g / mol to 30,000 g / mol, 1,000 g / mol to 25,000 g / mol, 1,000 g / mol to 20,000 g / mol, 2,200 to 10,000 g / mol, or 2,200 to 5,500 g / mol when measured by size exclusion chromatography (SEC). Ethylene-based unsaturated oligomers contain at least one ethylene-based unsaturated group per molecule, and in some cases, two or more ethylene-based unsaturated groups. As used herein, molecular weight values ​​measured by size exclusion chromatography (SEC) are measured using a Waters GPC (gel permeation chromatography) system equipped with a refractive index (RI) detector and a photodiode array detector, wherein: (a) for chromatographic separation, a chromatographic size exclusion column: 3 x 7.8 mm x 300 mm TSK-GEL MULTIPORE HXL-M, 5 m, TosoHaas, or an equivalent is used; (b) the detector and column are operated at 40°C; and (c) a calibration curve is established using a polystyrene molecular weight standard; (d) Before performing SEC, each oligomer and polystyrene molecular weight standard is dissolved in a high-purity grade tetrahydrofuran (THF)-containing BHT stabilizer at a concentration ranging from 0.5 to 10 mg / ml, wherein this THF solution is also used as the eluent in the SEC analysis.(e) after the completion of dissolution, determine the relative molar mass and molar mass distribution using the detection method described above with respect to the refractive index and absorbance; (f) generate a calibration curve with a series of polystyrene standards from which molecular weights can be assigned to each data slice and relative molar masses and distributions can be obtained; and (g) determine the calibration curve, molecular mass average, and molar mass distribution by integrating the entire refractive index chromatogram. Any polydispersity index (PDI) value reported herein refers to Mw / Mn.

[0145] In some embodiments, the ethylene-based unsaturated oligomer comprises a urethane (meth)acrylate oligomer comprising a (meth)acrylate group, a urethane group, and a backbone, for example, wherein the backbone is derived from a polyol reacted with an isocyanate, such as a polyisocyanate (e.g., diisocyanate), and a hydroxyl group-containing (meth)acrylate. As used herein, "(meth)acrylate" includes acrylates and methacrylates.

[0146] Examples of suitable polyols are, without limitation, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, acrylic polyols, and mixtures of any two or more of these. In some embodiments, the backbone of the urethane acrylate oligomer comprises a compound derived from polypropylene glycol (PPG). The compounds derived from polypropylene glycol used herein include end-capped PPG, e.g., EO-end-capped PPG. There are no specific restrictions on the polymerization method of the structural units in these polyols. Random polymerization, block polymerization, or graft polymerization are permitted.

[0147] As used herein, a block copolymer refers to a portion of an oligomer or polymer comprising a plurality of constituent units, wherein at least one constituent unit comprises a feature not present in an adjacent portion. As used herein, mono-, di-, and tri-block copolymers refer to the average amount of a particular block present in an oligomer. In some embodiments, a particular block refers to a polyether block derived from one or more polyols, such as polyether polyols described elsewhere in this invention. In some embodiments, the block referred to by the mono-, di-, and / or tri-block copolymer is a polyether block derived from one or more polyols described elsewhere in this invention. In one embodiment, a monoblock copolymer is a copolymer having only an average of about 1, or about 0.9 to less than 1.5 particular blocks, such as polyether blocks. In another embodiment, the diblock copolymer may be described as a copolymer having an average of about 2, or at least 1.5 to fewer than 2.5 specific blocks, such as polyether blocks, and in another embodiment, the triblock copolymer may be described as a copolymer having an average of about 3, or at least 2.5 to fewer than 3.5 specific blocks, such as polyether blocks. The number of polyether units in the oligomer may be determined by the number of polyether polyol molecules used in the synthesis of a single oligomer.

[0148] Suitable polyether polyols include, but are not limited to, polyethylene glycol, polypropylene glycol, polypropylene glycol-ethylene glycol copolymer, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, and two or more ion-polymerizable cyclic compounds, such as cyclic ethers, such as, but are not limited to, polyether diols obtained by ring-opening copolymerization of ethylene oxide, isobutene oxide, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, isoprene monooxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate. Specific examples of combinations of two or more ion-polymerizable cyclic compounds include, but are not limited to, combinations for preparing binary copolymers, e.g., tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, and tetrahydrofuran and ethylene oxide; and combinations for preparing ternary copolymers, e.g., combinations of tetrahydrofuran, 2-methyltetrahydrofuran and ethylene oxide, combinations of tetrahydrofuran, butene-1-oxide and ethylene oxide, etc. The ring-opening copolymers of these ion-polymerizable cyclic compounds may be random or block copolymers.

[0149] Suitable polyester diols include, but are not limited to, those obtained by reacting a polyhydric alcohol with a polybasic acid. Suitable polyhydric alcohols include, but are not limited to, ethylene glycol, polyethylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, and mixtures of any two or more of these. Suitable polybasic acids include, but are not limited to, phthalic acid, dimeric acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, and mixtures of any two or more of these.

[0150] Suitable polycarbonate polyols include, but are not limited to, polytetrahydrofuran polycarbonates, poly(hexanediol carbonates), poly(nonanediol carbonates), poly(3-methyl-1,5-pentamethylene carbonates), and mixtures of any two or more of these.

[0151] Suitable polycaprolactone diols include, but are not limited to, those having a melting point of 0°C or higher obtained by reacting e-caprolactone and a diol compound. Suitable diol compounds include, but are not limited to, ethylene glycol, polyethylene glycol, polypropylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-butanediol, and mixtures of any two or more of these.

[0152] Other suitable polyols include ethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, polyoxyethylene bisphenol A ether, polyoxypropylene bisphenol A ether, polyoxyethylene bisphenol F ether, polyoxypropylene bisphenol F ether, and mixtures of any two or more of these, with the exception of limitation. In some embodiments, these other polyols have an alkylene oxide structure within their molecules and include, for example, polyols containing polytetramethylene glycol and copolymer glycols of butylene oxide and ethylene oxide.

[0153] In some embodiments, the number average molecular weight derived from the hydroxyl group of the polyol is 50 to 15,000 g / mol, e.g. 1,000 to 8,000 g / mol.

[0154] Polyisocyanates suitable for manufacturing urethane (meth)acrylate oligomers are, but are not limited to, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), and 2,2,4-trimethylhexamethylene Aromatic compounds based on diisocyanates, bis(2-isocyanato-ethyl)fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, lysine isocyanate, hexamethylene diisocyanate trimer (commercially available, e.g., from Covestro as Desmodur® N3300A), triphenylmethane-4,4',4"-triisocyanate (commercially available, e.g., from Covestro as Desmodur® RE), hexamethylene diisocyanate trimer (commercially available, e.g., from Covestro as Desmodur® N3200), and toluene diisocyanate Polyisocyanates (commercially available, e.g., from Covestro as Desmodur® IL BA), polyisocyanurates of toluene diisocyanates (commercially available, e.g., from Covestro as Desmodur® RC), as well as any combination of two or more of these.

[0155] Hydroxyl group-containing (meth)acrylates suitable for use in preparing urethane (meth)acrylate oligomers include, but are not limited to, (meth)acrylates derived from (meth)acrylic acid and epoxy, and (meth)acrylates comprising alkylene oxides, such as, in particular, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl acrylate, and 2-hydroxy-3-oxyphenyl (meth)acrylate.

[0156] To prepare a urethane (meth)acrylate oligomer, the ratio of polyol, polyisocyanate, and hydroxyl group-containing (meth)acrylate is determined such that, in some embodiments, 0.1 to 0.9 equivalents of hydroxyl groups contained in the hydroxyl group-containing (meth)acrylate and 1.0 to 1.5 equivalents of total hydroxyl groups present from the polyol and the hydroxyl group-containing (meth)acrylate are used for every 1 equivalent of isocyanate groups contained in the polyisocyanate.

[0157] In some embodiments, a urethane catalyst is present during the reaction of the three components. Suitable such catalysts include, but are not limited to, copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin dilaurate, bismuth neodecanoate, triethylamine, triethylenediamine-2-methyltriethyleneamine, as well as mixtures of any two or more of these. In some cases, the urethane catalyst is used in an amount of 0.01 to 1 weight percent based on the total weight of the reactants. In some cases, the reaction is carried out at a temperature of 10 to 90°C, for example, 30 to 80°C.

[0158] Other ethylene-based unsaturated oligomers that may be used in embodiments of the radiation-curable compositions of this specification in addition to or instead of the urethane (meth)acrylates described above include polyester (meth)acrylates, epoxy (meth)acrylates, polyamide (meth)acrylates, siloxane polymers having (meth)acryloyloxy) groups, reactive polymers obtained by reacting (meth)acrylic acid with a copolymer of glycidyl methacrylate and other polymerizable compounds, as well as mixtures of any two or more of these. In some embodiments, the oligomers include bisphenol A-based acrylate oligomers, such as alkoxylated bisphenol-A-diaacrylate and diglycidyl-bisphenol-A-diaacrylate.

[0159] In some embodiments, the oligomer may comprise an unsaturated urethane-free oligomer, such as an unsaturated urethane-free polyester acrylate oligomer and / or an unsaturated urethane-free alkyd acrylate oligomer. Examples of such oligomeric unsaturated compounds are acrylated epoxy resins, acrylated polyethers, and acrylated polyesters. Further examples of unsaturated oligomers are unsaturated polyester resins, such as those prepared from maleic acid, phthalic acid, and one or more diols, having a molecular weight greater than about 500. Unsaturated oligomers of this type are also known as prepolymers. Typical examples of unsaturated compounds are esters of ethylene-based unsaturated carboxylic acids and polyols or polyepoxides, and polymers containing ethylene-based unsaturated groups in their chains or side groups, such as unsaturated polyesters, polyamides and copolymers thereof, polybutadiene-butadiene copolymers, polyisoprene-isoprene copolymers, polymers and copolymers containing (meth)acrylic groups in their side chains, as well as mixtures of one or more of these polymers. Exemplary examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, and unsaturated fatty acids, such as linolenic acid or oleic acid. Suitable polyols are aromatic, aliphatic, and cycloaliphatic polyols. Aromatic polyols are typically hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane, as well as novolac and cresol. Polyepoxides include those based on the mentioned polyols, for example, aromatic polyols and epichlorohydrin.

[0160] One or more of the above-mentioned ethylene-based unsaturated oligomers may be used in any suitable amount in the composition according to the present invention, and may be selected alone or in a combination of one or more of the types listed herein. In some embodiments, the ethylene-based unsaturated oligomers are present in an amount of 1 to 99 weight%, 5 to 95 weight%, 10 to 90 weight%, 10 to 80 weight%, or 30 to 90 weight%, or 50 to 80 weight%, based on the total weight of the solid in the radiation-curable composition.

[0161] In addition, in some embodiments, the radiation-curable coating composition comprises a reactive diluent compound comprising one or more ethylene-based unsaturated groups. Examples of such compounds include those containing one double bond, such as alkyl or hydroxyalkyl (meth)acrylates, suitable examples thereof, but are not limited to methyl, ethyl, butyl, 2-ethylhexyl and 2-hydroxyethyl acrylates, isobornyl acrylates, methyl and ethyl methacrylates, lauryl acrylates, ethoxylated nonyl-phenol acrylates, phenoxyethyl (meth)acrylates, diethylene-glycol-ethyl-hexyl acrylates (DEGEHA), acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamides, vinyl esters such as vinyl acetate, styrene, alkylstyrene, halostyrene, N-vinylpyrrolidone, N-vinyl caprolactam, vinyl chloride, vinylidene chloride, and mixtures of any two or more of these. Examples of such reactive diluent compounds containing more than one double bond are ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate, bisphenol A diacrylate, 4,4'-bis(2-acryloyloxyethoxy)diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate and tetraacrylate, vinyl acrylate, divinyl benzene, divinyl succinate, diallyl phthalate, trialyl phosphate, trialyl isocyanurate, tris(2-acryloylethyl) isocyanurate, and any mixture of two or more of these.

[0162] In some embodiments, the reactive diluent compound is present in an amount of 1 to 99 weight%, 5 to 90 weight%, 10 to 90 weight%, 10 to 80 weight%, 10 to 60 weight%, 10 to 40 weight%, or 10 to 30 weight% based on the total weight of the solid in the radiation-curable composition.

[0163] In some embodiments, the radiation-curable composition of this specification comprises a free-radical photoinitiator. More specifically, in some cases, the free-radical photoinitiator comprises an acylphosphine oxide, such as bis-acylphosphine oxide (BAPO) and / or mono-acylphosphine oxide (MAPO), an α-hydroxy ketone, or a mixture of any two or more of these.

[0164] In some cases, the photoinitiator comprises a bisylphosphine oxide having the following structure:

[0165]

[0166] Here, R 50 C1-C 12 It is alkyl, cyclohexyl, or phenyl, which is unsubstituted or substituted by 1 to 4 halogen atoms, or C1-C8 alkyl; R 51 and R 52 are each independently a C1-C8 alkyl or a C1-C8 alkoxy; R 53 is hydrogen or C1-C8 alkyl; R 54 is hydrogen or methyl. For example, in some embodiments, R 50 C2-C 10 It is alkyl, cyclohexyl, or phenyl, which is unsubstituted or substituted by 1 to 4 C1-C4 alkyl, Cl, or Br. In another embodiment, R 50 is a C3-C8 alkyl, cyclohexyl, or phenyl, which is unsubstituted or substituted by a C1-C4 alkyl at the 2-, 3-, 4-, or 2,5-position. In some cases, R 50 C4-C 12 It is alkyl or cyclohexyl, and R 51 and R 52 are each independently a C1-C8 alkyl or C1-C8 alkoxy, and R 53 is hydrogen or a C1-C8 alkyl. In some embodiments, R 51 and R 52 is a C1-C4 alkyl or C1-C4 alkoxy, and R 53It is hydrogen or a C1-C4 alkyl. Another embodiment is R 51 and R 52 ga is methyl or methoxy, and R 53 This is the case where it is hydrogen or methyl, for example, R 51 , R 52 and R 53 This is the case where it is methyl. In another embodiment, R 51 , R 52 and R 53 is methyl, and R 54 is hydrogen. In another embodiment, R 50 is a C3-C8 alkyl, for example, where R 51 and R 52 is methoxy, and R 53 and R 54 is hydrogen, and R 50 It is isooctyl. In some cases, R 50 It is isobutyl or phenyl. Specific examples of suitable bis-acylphosphine oxides include, but are not limited to, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-(2,4-bis-pentyloxyphenyl)phosphine oxide, or mixtures thereof.

[0167] Specific examples of suitable photoinitiator blends include, but are not limited to, those disclosed in U.S. Patent Nos. 6,020,528 and 7,169,826. In some embodiments, the photoinitiator blend comprises a mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (CAS #162881-26-7) and 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide (CAS #84434-11-7) in, for example, a weight ratio of 1:11 to 1:7. In another embodiment, the photoinitiator blend comprises a mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, and 2-hydroxy-2-methyl-1-phenyl-1-propanone (CAS #7473-98-5) in, for example, a weight ratio of 3:1:15 to 4:1:16. In yet another embodiment, the photoinitiator blend comprises a mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-1-propanone in, for example, a weight ratio of 1:3 to 1:5.

[0168] Other suitable photoinitiators are, but not limited to, other mono- or bis-acylphosphine oxides, e.g., diphenyl-2,4,6-trimethylbenzoylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; α-hydroxyketones, e.g., 1-hydroxycyclohexylphenylketone and 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone; α-aminoketones, e.g., 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-(4-methylbenzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and 2-benzyl-2-(dimethylamino)-1-[3,4-dimethoxyphenyl]-1-butanone; benzophenones, e.g., benzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 2-methylbenzophenone, 2-methoxycarbonylbenzophenone, 4,4'-bis(chloromethyl)-benzophenone, 4-chlorobenzophenone, It comprises 4-phenylbenzophenone, 4,4'-bis(dimethylamino)-benzophenone, 4,4'-bis(diethylamino)benzophenone, methyl 2-benzoylbenzoate, 3,3'-dimethyl-4-methoxybenzophenone, 4-(4-methylphenylthio)benzophenone, 2,4,6-trimethyl-4'-phenyl-benzophenone and 3-methyl-4'-phenyl-benzophenone; ketal compounds, e.g., 2,2-dimethoxy-1,2-diphenyl-ethanone; and compound or dimeric phenylglyoxylic acid esters, e.g., methylphenylglyoxylic acid ester, 5,5'-oxo-di(ethyleneoxydicarbonylphenyl) and 1,2-(benzoylcarboxy)ethane, or any mixture of two or more of these.

[0169] Other suitable photoinitiators include, but are not limited to, oxime esters as disclosed in U.S. Patent No. 6,596,445. Phenyl glyoxalate as disclosed in U.S. Patent No. 6,048,660 and germanium-based photoinitiators as disclosed in the document [Dalton Trans. 2021, 50, 12392-12398] are also suitable.

[0170] In some embodiments, the free-radical photoinitiator is present in an amount of 0.1 to 10 weight%, e.g. 0.1 to 5 weight%, or in some cases 1 to 5 weight%, based on the total weight of the radiation-curable composition.

[0171] A photoinitiator suitable for use in the radiation-curable compositions of this specification is also described in

[0080] -

[0128] of U.S. Patent Application Publication No. US2021 / 0088720 A1, the cited portion of which is incorporated herein by reference.

[0172] As is recognized, the radiation-curable compositions of this specification may include any various additional components, including any various additives, which can enable the composition to achieve certain desirable features such as improved shelf life, improved coating oxidation and hydrolysis stability, improved curing rate, and additional coating functional performance. For example, in some embodiments, the radiation-curable compositions of this specification may include, in particular, photosensitizers, radiation-curable amine synergists, UV absorbers, antioxidants, UV stabilizers, light stabilizers, fillers, chain transfer thiol compounds, surface-active compounds, viscosity modifiers, additional additive promoters, water scavengers, such as tetraethyl orthosilicate (TEOS) and orthoformate, oxygen quenchers, or one or more functional materials including pigments, dyes, photochromic dyes, laser dyes, liquid crystals, luminescent materials, nanomaterials, quantum dots, fluorescent materials, dichroic dyes, antistatic materials, refractive index modifiers, and bioactive materials. Some suitable additives are described in

[0122] -

[0134] of U.S. Patent Application Publication No. US2021 / 0088720 A1, the cited portions of which are incorporated herein by reference.

[0173] In some embodiments, the radiation-curable composition of this specification comprises an adhesion promoter different from the ethylene-based unsaturated compound previously described herein. Suitable adhesion promoters include silane coupling agents (different from the ethylene-based unsaturated compound previously described), such as hydrolyzable silane compounds containing mercapto groups and / or a plurality of alkoxy groups, such as those described in U.S. Patent Application Publication No. US 2002 / 0013383 A1, the relevant portion of which is incorporated herein by reference. Specific examples of such adhesion promoters are gamma-mercaptopropyltrimethoxysilane, trimethoxysilylpropyl acrylate, 3-trimethoxysilylpropane-1-thiol, and mixtures of any two or more of these. In some embodiments, the radiation-curable composition may comprise a polysilane, such as a polysilane comprising the following:

[0174] (a) At least two, in some cases two, moiety of the following structure (1):

[0175] ; and

[0176] (b1) Moiety of the following structure (2):

[0177] ;

[0178] (b2) Moiety of the following structure (3):

[0179] ; or

[0180] (b3) A combination of the moiety of structure (2) and the moiety of structure (3),

[0181] Here (i) Y 7 represents a linear or branched linker containing one or more carbon atoms, and (ii) each X 9 represents an alkoxy group or an organic group inert to isocyanate groups at temperatures of 100°C or lower, provided that at least one X 9 represents an alkoxy group, and (iii) R, which may be the same or different. 26 and R27 Each represents an organic group that is inert to isocyanate groups at temperatures below 100°C; (iv) R which may be the same or different 28 and R 29 Each represents an organic group that is inert to hydrogen or an isocyanate group at a temperature of 100°C or lower; (v) each " " indicates a connection to another part of the polysilane. Such polysilane, as well as its preparation, is described in U.S. Provisional Patent Application No. 63 / 616,868, filed concurrently with and incorporated herein by reference, titled Polysilane, Method of Preparing the Same, and Use of the Same in Coating Compositions.

[0182] In some embodiments, the radiation-curable composition of this specification has a total silane content of 10 mmol or less per 100 grams of radiation-curable composition, e.g., 1 to 10 mmol, 1 to 8 mmol, or in some cases 2 to 6 mmol (determined as described in the Examples section of this specification). Additionally, in some embodiments, the radiation-curable composition of this specification has a total urea+urethane content of 20 to 200 mmol per 100 grams of radiation-curable composition, e.g., 30 to 150 mmol, or in some cases 40 to 100 mmol (determined as described in the Examples section of this specification).

[0183] Additionally, in some embodiments, the cured coating deposited from the coating composition exhibits a peel strength of at least 40 gram-force / inch ("gf / in") or at least 55 gf / in when measured after at least 7 days, as described in the Examples section of this specification. Also, in some embodiments, the cured coating deposited from the coating composition exhibits an elongation at break of at least 35%, e.g., at least 50%, when measured, as described in the Examples section of this specification.

[0184] Additionally, in some embodiments, the coating composition of this specification is configured to have a viscosity of at least >0.1 Pascal-second (Pa·s), at least 0.2, at least 0.5, at least 1 Pa·s, and / or less than 15 Pa·s, less than 12 Pa·s, or less than 10 Pa·s, or 1 to 15 Pa·s, 2 to 12 Pa·s, or 3 to 10 Pa·s, wherein the viscosity is measured at 25°C and a shear rate of 50 s-1.

[0185] In some aspects, the present specification relates to a method for coating an optical fiber. The method comprises the steps of: providing a glass optical fiber, for example, by drawing the glass optical fiber through a draw tower; applying a primary coating composition onto the surface of the glass optical fiber; optionally applying a dose of UV light sufficient to at least partially cure the primary coating composition; applying a secondary coating composition to the primary coating composition; and exposing the secondary coating composition to at least one radiation source capable of emitting ultraviolet radiation to induce curing of the secondary coating composition and optionally the primary coating composition. In this method, the primary coating composition and / or the secondary coating composition are compositions of the type described herein.

[0186] As is also recognized, the present specification also relates to a coated optical fiber, wherein the coated optical fiber comprises a glass core and a cladding layer in contact with and surrounding the glass core; and a coating portion, wherein the coating portion further comprises a primary coating layer in contact with the cladding layer; and a secondary coating layer in contact with and surrounding the primary coating layer. According to this aspect, the primary coating layer and / or the secondary coating layer are cured products of a coating composition of the type described herein. In some cases, the optical fiber comprises a core, a cladding, a primary coating in contact with and surrounding an outer annular cladding region, and a secondary coating. According to some of these embodiments, the core comprises silica glass having one or more dopants that increase the refractive index of the glass core compared to pure silica glass (SiO2) or pure undoped silica glass. Suitable such dopants include, but are not limited to, GeO2, Al2O3, P2O5, TiO2, ZrO2, Nb2O5, Ta2O5, and / or combinations thereof. The cladding layer may comprise pure silica glass (SiO2), silica glass having one or more dopants that increase the refractive index (e.g., GeO2, Al2O3, P2O5, TiO2, ZrO2, Nb2O5, and / or Ta2O5), provided that the maximum relative refractive index of the core [Δ1MAX] is greater than the maximum relative refractive index of the cladding [Δ4MAX], silica glass having one or more dopants that increase the refractive index (e.g., GeO2, Al2O3, P2O5, TiO2, ZrO2, Nb2O5, and / or Ta2O5), or silica glass having a dopant that decreases the refractive index (e.g., fluorine), provided that the inner cladding is "down-doped." According to one embodiment, the cladding is pure silica glass. According to some of these embodiments, the primary coating has an in-situ (or fibrous) tensile modulus of less than 5 MPa, less than 2 MPa, less than 1.5 MPa, or less than 1.0 MPa.Methods for describing in-situ modulus are widely known in the art, particularly described in US7,171,103 and US6,961,508, which are incorporated herein by reference. In one embodiment, the cured primary coating has an in-situ glass transition temperature of less than -10°C, less than -35°C, less than -40°C, less than -45°C, and in another embodiment, less than -50°C. A primary coating having a low in-situ modulus reduces microbending, which is a coupling mechanism between modes propagating within the fiber. A low in-situ glass transition temperature ensures that the in-situ modulus of the primary coating remains low even when the fiber is placed in a very low temperature environment.

[0187] The primary coating typically has a thickness in the range of 20 to 50 μm (e.g., about 25 or 32.5 μm), and for 200 μm fibers, has a thinner thickness in the range of 15 to 25 μm. In other cases, the primary coating has a thickness of 40 μm or less, e.g., 20 to about 40 μm, or 20 to 30 μm.

[0188] The secondary coating contacts and surrounds the primary coating. The secondary coating is, for example, a polymerization product of a coating composition in which molecules are highly crosslinked during polymerization. According to one embodiment, the secondary coating may have an in-situ tensile modulus greater than 800 MPa, greater than 1110 MPa, greater than 1300 MPa, greater than 1400 MPa, or in some cases greater than 1500 MPa. In some embodiments, the secondary coating has a high in-situ modulus (e.g., greater than about 800 MPa at 25°C) and a high Tg (e.g., greater than about 50°C). In some cases, the in-situ secondary modulus is 1000 MPa to 8000 MPa, e.g., 1200 MPa to 5000 MPa or 1500 MPa to 3000 MPa. The in-situ Tg of the secondary coating is, in some embodiments, 50°C to 120°C, or in some cases, 50°C to 100°C. Furthermore, in some embodiments, the secondary coating has a thickness of 40 μm or less, e.g., 20 to 40 μm, or in some cases, 20 to 30 μm.

[0189] Suitable outer (or secondary) coating materials, as well as considerations regarding the selection of such materials, are also described, for example, in U.S. Patent Nos. 4,962,992 and 5,104,433, each incorporated herein by reference. As an alternative, high modulus coatings have also been obtained using low oligomer content coating systems, as described in U.S. Patent No. 6,775,451 and U.S. Patent No. 6,689,463 (each incorporated herein by reference). High modulus coatings prepared using non-reactive oligomer components, as described in U.S. Patent Application Publication No. US 2007 / 0100039 A1 (incorporated herein by reference), are also suitable. The secondary coating may also include inks as widely known in the art, in which case it may be referred to as a "colored secondary coating."

[0190] The coated optical fiber may, if desired, include one or more additional layers disposed on the secondary layer, such as an independent “ink” layer that is applied and cured separately from the secondary coating.

[0191] Methods for formulating typical optical fiber coatings for primary and secondary coatings for fibers as described above, as well as inks and matrix materials for curing using broadband UV lamps, are known in the art. An excellent discussion of these techniques and related chemistry and test methods can be found in paragraphs 4.6 through the end of Chapter 4 of the literature published by Elsevier ["Specialty Optical Fibers Handbook" by A. Mendez and TF Morse, © Elsevier Inc. 2007].

[0192] Any type of optical fiber may be used in the embodiments of the invention described herein. However, in some embodiments, the coated optical fiber has a mode-field diameter of 8 to 10 μm at a wavelength of 1310 nm, a mode-field diameter of 9 to 13 μm at a wavelength of 1550 nm, and / or 20 to 200 μm 2 These fibers have an effective area. These fibers may be single-mode and / or large-effective-area fibers, as there is expected demand for coating processes utilizing higher line or processing speeds for these fibers. However, other fiber types, such as multimode fibers, may also be used.

[0193] Also, as is recognized, this specification also relates to an optical fiber cable, wherein the optical fiber comprises at least one optical fiber as described herein and / or the optical fiber is a cured product of a coating composition as described herein.

[0194] Various aspects of the subject matter described herein are presented in the following numbered clauses:

[0195] Clause 1. Ethylene-based unsaturated compounds including the following:

[0196] (a) Moiety of the following structure (1):

[0197] ; and

[0198] (b1) Moiety of the following structure (2):

[0199] ; or

[0200] (b2) Moiety of the following structure (3):

[0201] ; or

[0202] (b3) A combination of the moiety of structure (2) and the moiety of structure (3),

[0203] Here, (i) Y represents a linear or branched linker comprising one or more carbon atoms, (ii) each X, which may be the same or different, represents an alkoxy group or an organic group inert to isocyanate groups at a temperature of 100°C or lower, provided that at least one X represents an alkoxy group, and (iii) R, which may be the same or different 1 and R 2 Each represents an organic group that is inert to isocyanate groups at temperatures of 100°C or lower; (iv) R which may be the same or different 3 and R 4 Each represents an organic group that is inert to hydrogen or an isocyanate group at a temperature of 100°C or lower; (v) each " " indicates a connection to another part of the ethylene-based unsaturated compound.

[0204] Clause 2. An ethylene-based unsaturated compound according to Clause 1, wherein at least one carbon-carbon double bond of the ethylene-based unsaturated oligomer exists as a =CH2 terminal group and there are no additional substituents on its carbon.

[0205] Clause 3. An ethylene-based unsaturated compound comprising the terminal group of structure (1) and the terminal group of structure (1a) in Clause 1 or Clause 2:

[0206]

[0207] Here, E represents a group containing a polymerizable carbon-carbon double bond, such as an acryloyl, methacryloyl, or vinyl group, and represents a connection to another part of an ethylene-based unsaturated compound, for example, the terminal group of structure (1a) has structure (1b).

[0208]

[0209] Here, R 3 It is H or CH3, and represents a link to another part of the ethylene-based unsaturated compound.

[0210] Clause 4. An ethylene-based unsaturated compound in which, in any one of Clauses 1 to 3, the terminal group of structure (1) and the terminal group of structure (1a) are disposed at opposite ends of the ethylene-based unsaturated compound.

[0211] Clause 5. Each R that may be the same or different in structure (2) and (3) in any one of Clauses 1 through 4. 1 and R 2 α represents an alkyl group, for example, an alkyl group having 1 to 9 or 1 to 4 carbon atoms, and each R, for example, which may be the same or different in structures (2) and (3). 1 and R 2 An ethylene-based unsaturated compound that represents a methyl group, an ethyl group, a propyl group, or a butyl group.

[0212] Article 6. An ethylene-based unsaturated compound in which, in any one of Articles 1 to 5, each X in the structure (1) represents the same or different alkyl, acyloxy or alkoxy group, for example, the same or different alkyl, acyloxy or alkoxyl group having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X represents an alkoxy group, for example, where at least two X represent an alkoxy, for example, a methoxy, ethoxy or propyloxy group, or where each X represents an alkoxy, for example, a methoxy, ethoxy or propyloxy group.

[0213] Clause 7. An ethylene-based unsaturated compound in which, in any one of Clauses 1 to 6, Y in the structure (1) comprises a linear or branched alkylene radical having 1 to 8 carbon atoms, e.g., a linear alkylene radical having 2 to 4, or in some cases 3, carbon atoms, or a branched alkylene radical having 5 to 6 carbon atoms.

[0214] Clause 8. An ethylene-based unsaturated compound comprising, in any one of Clauses 1 through 7, a segment having the following structure:

[0215]

[0216] Here, G is O, S, or NR, where R represents hydrogen or an organic group inert to isocyanate groups at temperatures below 100°C, and each " " indicates a connection to another part of the ethylene-based unsaturated compound. In some embodiments, the ethylene-based unsaturated compound has 1 to 4 such segments.

[0217] Clause 9. An ethylene-based unsaturated compound having a molecular weight calculated from the molecular formula of any one of Clauses 1 to 8 of which is less than 400 to 2000 g / mol, e.g., 400 to 1000 g / mol.

[0218] Clause 10. An ethylene-based unsaturated compound in which, in any one of Clauses 1 to 9, for example, the ethylene-based unsaturated compound comprises a moiety of structure (3) and the ethylene-based unsaturated compound comprises a moiety of structure 3A:

[0219]

[0220] Here, X, Y, R 1 , R 2 and " " is as described in Clause 1 with respect to each of the structures (1)-(3), for example, the ethylene-based unsaturated compound here has 1 to 4 such moiety of structure 3A.

[0221] Clause 11. An ethylene unsaturated compound, for example, in any one of Clauses 1 to 10, wherein the ethylene unsaturated compound comprises a moiety of structure (3), provided that the ethylene unsaturated compound has at least one moiety of structure 3B, and in some cases only one:

[0222]

[0223] Here, X, Y, R 1 , R 2 and " " is as described in paragraph 1 for each structure (1)-(3).

[0224] Clause 12. An ethylene-based unsaturated compound, wherein, in any one of Clauses 1 to 11, the ethylene-based unsaturated compound comprises, for example, a moiety of structure (2), provided that the ethylene-based unsaturated compound has at least one moiety of structure 2A, and in some cases only one:

[0225]

[0226] Here, X, Y, R 1 , R 2 and " " is as described in paragraph 1 for each structure (1)-(3).

[0227] Clause 13. An ethylene unsaturated compound, wherein, in any one of Clauses 1 to 12, for example, the ethylene unsaturated compound comprises a moiety of structure (2), provided that the ethylene unsaturated compound has 0 or 2 to 4 or 2 moietyes of structure 2B:

[0228]

[0229] Here, X, Y, R 1 , R 2 and " " is as described in paragraph 1 for each structure (1)-(3).

[0230] Clause 14. An ethylene-based unsaturated compound having the following structure (4A) or structure (4B) (or an ethylene-based unsaturated compound of any one of Clauses 1 to 13):

[0231]

[0232] Here (i) R 5 represents H or CH3, and (ii) R 6 represents a group comprising a branched or straight-chain alkylene radical, for example, wherein the branched or straight-chain alkylene radical has at least 2, 2 to 8, or 2 to 4 carbon atoms, and (iii) Y 1 represents a linear or branched linker containing one or more carbon atoms, and (iv) R which may be the same or different 7 and R 8 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, and (v) R which may be the same or different 9 and R 10Each represents an organic group that is inert to hydrogen or an isocyanate group at a temperature of 100°C or lower, and (vi) each X which may be the same or different. 1 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 1 (vii) each q, which may be the same or different, is an integer having a value of 1 to 6, e.g. 1 to 3, e.g. 1, e.g., where the molecular weight of the ethylene-based unsaturated compound calculated from the molecular formula of the ethylene-based unsaturated compound is less than 400 to 2000 g / mol, e.g., 400 to 1000 g / mol.

[0233] Clause 15. In Clause 14, R 6 In addition to this branched or straight-chain alkylene radical, it represents a group further comprising a carbamate segment, e.g., where R 6It represents a group further comprising a unit derived from this polyisocyanate, for example, wherein the polyisocyanate is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, (hydrogenated) xylylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), 2,2,4-Trimethylhexamethylene diisocyanate, 2,4,4-Trimethylhexamethylene diisocyanate, Hexamethylene diisocyanate, 2,4- and / or 4,4'-methylene dicyclohexyl diisocyanate, Methylene diphenyl diisocyanate, Tetramethylxylene diisocyanate, 1,5-Pentane diisocyanate, Bis(2-isocyanato-ethyl)fumarate, 6-Isopropyl-1,3-phenyl diisocyanate, 4-Diphenylpropane diisocyanate, Hydrogenated diphenylmethane diisocyanate, Hydrogenated xylylene diisocyanate, Tetramethylxylylene diisocyanate, Lysine isocyanate, Hexamethylene diisocyanate trimer, Triphenylmethane-4,4',4"-Triisocyanate, Hexamethylene An ethylene-based unsaturated compound comprising a diisocyanate trimer, an aromatic polyisocyanate based on toluene diisocyanate, a polyisocyanurate of toluene diisocyanate, or any combination of two or more of these.

[0234] Clause 16. In Clause 14, R 6 An ethylene-based unsaturated compound that does not contain this carbamate segment.

[0235] Clause 17. In any one of Clauses 14 through 16, R 6 this

[0236] Linear or branched alkylene radicals composed of carbon and hydrogen, for example

[0237] ;

[0238]

[0239]

[0240] ; or

[0241] Any combination of two or more of these, wherein each " " indicates a connection to another part of the ethylene-based unsaturated compound, and each " shown to the left of the oxygen " is within structures (4A) and (4B) An ethylene-based unsaturated compound that represents a connection to a segment.

[0242] Clause 18. In any one of Clauses 14 through 17, R which may be the same or different 7 and R 8 This represents an alkyl group, for example, an alkyl group having 1 to 9 or 1 to 4 carbon atoms, for example, each R which may be the same or different here. 7 and R 8 An ethylene-based unsaturated compound that represents a methyl group, ethyl group, propyl group, or butyl group.

[0243] Clause 19. In any one of Clauses 14 through 18, each X 1 This represents the same or different alkyl, acyloxy, or alkoxy groups, for example, the same or different alkyl, acyloxy, or alkoxyl groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 This represents an alkoxy group, for example, here at least two X 1 This represents an alkoxy, such as a methoxy, ethoxy, or propyloxy group, or each X1 An ethylene-based unsaturated compound that represents an alkoxy group, such as a methoxy, ethoxy, or propyloxy group.

[0244] Clause 20. In any one of Clauses 14 through 19, Y 1 An ethylene-based unsaturated compound comprising a linear or branched alkylene radical having 1 to 8 carbon atoms, for example, a linear alkylene radical having 2 to 4, or in some cases 3, carbon atoms, or a branched alkylene radical having 5 to 6 carbon atoms.

[0245] Clause 21. An ethylene-based unsaturated compound having the following structure (5) (or an ethylene-based unsaturated compound of any one of Clauses 1 to 13):

[0246]

[0247] Here (i) R 5 represents H or CH3, and (ii) R 6 represents a group comprising a branched or straight-chain alkylene radical, for example, wherein the branched or straight-chain alkylene radical has at least 2, 2 to 8, or 2 to 4 carbon atoms, and (iii) Y 1 represents a linear or branched linker containing one or more carbon atoms, and (iv) R 7 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, and (v) R which may be the same or different 9 and R 10 Each represents an organic group that is inert to hydrogen or an isocyanate group at a temperature of 100°C or lower, and (vi) each X which may be the same or different. 1 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 1(vii) each q, which may be the same or different, is an integer having a value of 1 to 6, 1 to 3, or 1, for example, where the molecular weight of the ethylene-based unsaturated compound calculated from the molecular formula of the ethylene-based unsaturated compound is less than 400 to 2000 g / mol, for example, 400 to 1000 g / mol.

[0248] Clause 22. In Clause 21, R 6 In addition to this branched or straight-chain alkylene radical, it represents a group further comprising a carbamate segment, e.g., where R 6 ...represents a group further comprising a unit derived from a polyisocyanate, e.g., wherein the polyisocyanate comprises any of the polyisocyanates listed in Clause 15, an ethylene-based unsaturated compound.

[0249] Clause 23. In Clause 21, R 6 An ethylene-based unsaturated compound that does not contain this carbamate segment.

[0250] Clause 24. In any one of Clauses 21 through 23, R 6 this

[0251] Linear or branched alkylene radicals composed of carbon and hydrogen, for example

[0252] ;

[0253]

[0254]

[0255] ; or

[0256] Any combination of two or more of these, wherein each " " indicates a connection to another part of the ethylene-based unsaturated compound, and each " shown to the left of the oxygen "is within the structure (5) An ethylene-based unsaturated compound that represents a connection to a segment.

[0257] Clause 25. In any one of Clauses 21 through 24, R 7 This represents an alkyl group, for example, an alkyl group having 1 to 9 or 1 to 4 carbon atoms, for example, where R 7 An ethylene-based unsaturated compound that represents a methyl group, ethyl group, propyl group, or butyl group.

[0258] Clause 26. In any one of Clauses 21 through 25, each X 1 This represents the same or different alkyl, acyloxy, or alkoxy groups, for example, the same or different alkyl, acyloxy, or alkoxyl groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 This represents an alkoxy group, for example, here at least two X 1 This represents an alkoxy, such as a methoxy, ethoxy, or propyloxy group, or each X 1 An ethylene-based unsaturated compound that represents an alkoxy group, such as a methoxy, ethoxy, or propyloxy group.

[0259] Article 27. In any one of Articles 21 through 26, Y 1 An ethylene-based unsaturated compound comprising a linear or branched alkylene radical having 1 to 8 carbon atoms, for example, a linear alkylene radical having 2 to 4, or in some cases 3, carbon atoms, or a branched alkylene radical having 5 to 6 carbon atoms.

[0260] Clause 28. An ethylene-based unsaturated compound having the following structure (6) (or an ethylene-based unsaturated compound of any one of Clauses 1 to 13):

[0261]

[0262] Here (i) R5 represents H or CH3, and (ii) R 6 represents a group comprising a branched or straight-chain alkylene radical, for example, wherein the branched or straight-chain alkylene radical has at least 2, 2 to 8, or 2 to 4 carbon atoms, and (iii) R which may be the same or different 7 and R 8 ☐ exhibits an organic group that is inert to isocyanate groups at temperatures below 100°C, and (iv) R which may be the same or different 9 and R 10 Each represents hydrogen or an organic group inert to isocyanate groups at temperatures below 100°C, and (v) Z represents an organic group inert to isocyanate groups at temperatures below 100°C, or in some cases a divalent organic group, optionally containing isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof, and C1 to C 18 Representing a hydrocarbon group comprising an alkylene group or a C5-C6 cycloalkylene group, and (vii) each X which may be the same or different. 1 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 1 (viii) each q, which may be the same or different, is an integer having a value of 1 to 6, e.g. 1 to 3, e.g. 1, and (ix) q1 is 0 or 1, e.g. where the molecular weight of the ethylene-based unsaturated compound calculated from the molecular formula of the ethylene-based unsaturated compound is less than 400 to 2000 g / mol, e.g. 400 to 1000 g / mol.

[0263] Clause 29. In Clause 28, R 6 In addition to this branched or straight-chain alkylene radical, it represents a group further comprising a carbamate segment, e.g., where R 6...represents a group further comprising a unit derived from a polyisocyanate, e.g., wherein the polyisocyanate comprises any of the polyisocyanates listed in Clause 15, an ethylene-based unsaturated compound.

[0264] Clause 30. In Clause 28, R 6 An ethylene-based unsaturated compound that does not contain this carbamate segment.

[0265] Clause 31. In any one of Clauses 28 through 30, R 6 this

[0266] Linear or branched alkylene radicals composed of carbon and hydrogen, for example

[0267] ;

[0268]

[0269]

[0270]

[0271] or any combination of two or more of these, wherein each " " indicates a connection to another part of the ethylene-based unsaturated compound, and each " shown to the left of the oxygen "is within the structure (6) An ethylene-based unsaturated compound that represents a connection to a segment.

[0272] Clause 32. In any one of Clauses 28 through 31, R which may be the same or different 7 and R 8 This represents an alkyl group, for example, an alkyl group having 1 to 9 or 1 to 4 carbon atoms, and R, for example, which may be the same or different here. 7 and R 8 An ethylene-based unsaturated compound that represents a methyl group, ethyl group, propyl group, or butyl group.

[0273] Clause 33. In any one of Clauses 28 through 32, each X 1 This represents the same or different alkyl, acyloxy, or alkoxy groups, for example, the same or different alkyl, acyloxy, or alkoxyl groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 This represents an alkoxy group, for example, here at least two X 1 This represents an alkoxy, such as a methoxy, ethoxy, or propyloxy group, or each X 1 An ethylene-based unsaturated compound that represents an alkoxy group, such as a methoxy, ethoxy, or propyloxy group.

[0274] Clause 34. Each Y that may be identical or different in any one of Clauses 28 through 33 1 An ethylene-based unsaturated compound comprising a linear or branched alkylene radical having 1 to 8 carbon atoms, for example, a linear alkylene radical having 2 to 4, or in some cases 3, carbon atoms, or a branched alkylene radical having 5 to 6 carbon atoms.

[0275] Clause 35. In any one of Clauses 28 through 34, Z

[0276] (Here, x takes a value from 3 to 19);

[0277]

[0278] and, here, each " " is an ethylene unsaturated compound that represents a link to another part of the ethylene unsaturated compound.

[0279] Clause 36. An ethylene-based unsaturated compound having the following structure (7) (or an ethylene-based unsaturated compound of any one of Clauses 1 to 13):

[0280]

[0281] Here (i) R 5 represents H or CH3, and (ii) R 6 represents a group comprising a branched or straight-chain alkylene radical, for example, wherein the branched or straight-chain alkylene radical has at least 2, 2 to 8, or 2 to 4 carbon atoms, and (iii) R which may be the same or different 7 and R 8 ☐ exhibits an organic group that is inert to isocyanate groups at temperatures below 100°C, and (iv) R which may be the same or different 9 and R 10 Each represents hydrogen or an organic group inert to isocyanate groups at temperatures below 100°C, and (v) Z represents an organic group inert to isocyanate groups at temperatures below 100°C, or in some cases a divalent organic group, optionally containing isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof, and C1 to C 18 Representing a hydrocarbon group comprising an alkylene group or a C5-C6 cycloalkylene group, and (vi) each Y which may be the same or different. 1 represents a linear or branched linker containing one or more carbon atoms, and (vii) each X, which may be the same or different. 1 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 1 (viii) each q may be the same or different and is an integer having a value of 1 to 6, e.g. 1 to 3, e.g. 1, and (ix) q1 is 0 or 1, e.g. where the molecular weight calculated from the molecular formula of the ethylene-based unsaturated compound is less than 400 to 2000 g / mol, e.g. 400 to 1000 g / mol.

[0282] Clause 37. In Clause 36, R6 In addition to this branched or straight-chain alkylene radical, it represents a group further comprising a carbamate segment, e.g., where R 6 ...represents a group further comprising a unit derived from a polyisocyanate, e.g., wherein the polyisocyanate comprises any of the polyisocyanates listed in Clause 15, an ethylene-based unsaturated compound.

[0283] Clause 38. In Clause 36, R 6 An ethylene-based unsaturated compound that does not contain this carbamate segment.

[0284] Clause 39. In any one of Clauses 36 through 38, R 6 this

[0285] Linear or branched alkylene radicals composed of carbon and hydrogen, for example

[0286] ;

[0287]

[0288]

[0289]

[0290] or any combination of two or more of these, wherein each " " indicates a connection to another part of the ethylene-based unsaturated compound, and each " shown to the left of the oxygen "is within the structure (7) An ethylene-based unsaturated compound that represents a connection to a segment.

[0291] Clause 40. In any one of Clauses 36 through 39, R 8 This represents an alkyl group, for example, an alkyl group having 1 to 9 or 1 to 4 carbon atoms, for example, where R 8An ethylene-based unsaturated compound that represents a methyl group, ethyl group, propyl group, or butyl group.

[0292] Clause 41. In any one of Clauses 36 through 40, each X 1 This represents the same or different alkyl, acyloxy, or alkoxy groups, for example, the same or different alkyl, acyloxy, or alkoxyl groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 This represents an alkoxy group, for example, here at least two X 1 This represents an alkoxy, such as a methoxy, ethoxy, or propyloxy group, or each X 1 An ethylene-based unsaturated compound that represents an alkoxy group, such as a methoxy, ethoxy, or propyloxy group.

[0293] Clause 42. Each Y that may be identical or different in any one of Clauses 36 through 41 1 An ethylene-based unsaturated compound comprising a linear or branched alkylene radical having 1 to 8 carbon atoms, for example, a linear alkylene radical having 2 to 4, or in some cases 3, carbon atoms, or a branched alkylene radical having 5 to 6 carbon atoms.

[0294] Clause 43. In any one of Clauses 36 through 42, Z

[0295] (Here, x takes a value from 3 to 19);

[0296]

[0297]

[0298] and, here, each " " is an ethylene unsaturated compound that represents a link to another part of the ethylene unsaturated compound.

[0299] Clause 44. An ethylene-based unsaturated compound having the following structure (8) (or an ethylene-based unsaturated compound of any one of Clauses 1 to 13):

[0300]

[0301] Here, (i) each R which may be the same or different 5 represents H or CH3, and (ii) each R, which may be the same or different. 6 represents a group comprising a branched or straight-chain alkylene radical, for example, wherein the branched or straight-chain alkylene radical has at least 2, 2 to 8, or 2 to 4 carbon atoms, and (iii) Z 1 It exhibits an organic group that is inert to isocyanate groups at temperatures below 100°C, and in some cases, a divalent organic group, optionally containing, for example, isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof, and C1 to C 18 Representing a hydrocarbon group comprising an alkylene group or a C5-C6 cycloalkylene group, and (iv) each Y which may be the same or different. 1 represents a linear or branched linker containing one or more carbon atoms, and (v) each R which may be the same or different. 7 and R 8 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, and (vi) each R which may be the same or different 9 and R 10 represents an organic group that is inert to hydrogen or isocyanate groups at temperatures below 100°C, and (vii) each X which may be the same or different. 1 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 1(viii) m and n, which may be the same or different, are integers having a value of 1 to 4 each, and (ix) each q, which may be the same or different, is an integer having a value of 1 to 6, e.g. 1 to 3, e.g. 1, e.g., where the molecular weight of the ethylene-based unsaturated compound calculated from the molecular formula of the ethylene-based unsaturated compound is less than 400 to 2000 g / mol, e.g. 400 to 1000 g / mol.

[0302] Clause 45. In Clause 44, R 6 In addition to this branched or straight-chain alkylene radical, it represents a group further comprising a carbamate segment, e.g., where R 6 ...represents a group further comprising a unit derived from a polyisocyanate, e.g., where the diisocyanate comprises any of the polyisocyanates listed in Clause 15, an ethylene-based unsaturated compound.

[0303] Clause 46. In Clause 44, R 6 An ethylene-based unsaturated compound that does not contain this carbamate segment.

[0304] Clause 47. In Clause 44 or Clause 46, R 6 this

[0305] Linear or branched alkylene radicals composed of carbon and hydrogen, for example

[0306] ;

[0307]

[0308]

[0309]

[0310] or any combination of two or more of these, wherein each " " indicates a connection to another part of the ethylene-based unsaturated compound, and each " shown to the left of the oxygen "is within the structure (8) An ethylene-based unsaturated compound that represents a connection to a segment.

[0311] Clause 48. Each R that may be the same or different in any one of Clauses 44 through 47 7 and R 8 This represents an alkyl group, for example, an alkyl group having 1 to 9 or 1 to 4 carbon atoms, for example, each R which may be the same or different here. 11 and R 12 An ethylene-based unsaturated compound that represents a methyl group, ethyl group, propyl group, or butyl group.

[0312] Clause 49. In any one of Clauses 44 through 48, each X 1 This represents the same or different alkyl, acyloxy, or alkoxy groups, for example, the same or different alkyl, acyloxy, or alkoxyl groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 This represents an alkoxy group, for example, here at least two X 1 This represents an alkoxy, such as a methoxy, ethoxy, or propyloxy group, or each X 1 An ethylene-based unsaturated compound that represents an alkoxy group, such as a methoxy, ethoxy, or propyloxy group.

[0313] Clause 50. Each Y that may be identical or different in any one of Clauses 44 through 49 1 An ethylene-based unsaturated compound comprising a linear or branched alkylene radical having 1 to 8 carbon atoms, for example, a linear alkylene radical having 2 to 4, or in some cases 3, carbon atoms, or a branched alkylene radical having 5 to 6 carbon atoms.

[0314] Article 51. In any one of Articles 44 through 50, Z 1 this

[0315] (Here, x takes a value from 3 to 19);

[0316] (Here, each X1, X2, X3, and X4, which may be identical or different, has a value of 1 to 10, except that the structure has a molecular weight of 200 to 1500);

[0317]

[0318]

[0319] and, here, each " " is an ethylene unsaturated compound that represents a link to another part of the ethylene unsaturated compound.

[0320] Article 52. An ethylene-based unsaturated compound in any one of Articles 44 to 51, wherein m+n is 4 or less, e.g., where m is 1 or 2, e.g., 1, and n is 1 or 2, e.g., 1.

[0321] Clause 53. An ethylene-based unsaturated compound having the following structure (9) (or an ethylene-based unsaturated compound of any one of Clauses 1 to 13):

[0322]

[0323] Here, (i) each R which may be the same or different 5 represents H or CH3, and (ii) each R, which may be the same or different. 6 represents a group comprising a branched or straight-chain alkylene radical, for example, wherein the branched or straight-chain alkylene radical has at least 2, 2 to 8, or 2 to 4 carbon atoms, and (iii) Z 1It exhibits an organic group that is inert to isocyanate groups at temperatures below 100°C, and in some cases, a divalent organic group, optionally containing, for example, isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof, and C1 to C 18 Representing a hydrocarbon group comprising an alkylene group or a C5-C6 cycloalkylene group, and (iv) each Y which may be the same or different. 1 represents a linear or branched linker containing one or more carbon atoms, and (v) each R which may be the same or different. 7 and R 8 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, and (vi) each R which may be the same or different 9 and R 10 represents an organic group that is inert to hydrogen or isocyanate groups at temperatures below 100°C, and (vii) each X which may be the same or different. 1 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 1 (viii) m and n, which may be the same or different, are integers having a value of 1 to 4 each, and (ix) each q, which may be the same or different, is an integer having a value of 1 to 6, e.g. 1 to 3, e.g. 1, e.g., where the molecular weight of the ethylene-based unsaturated compound calculated from the molecular formula of the ethylene-based unsaturated compound is less than 400 to 2000 g / mol, e.g. 400 to 1000 g / mol.

[0324] Clause 54. In Clause 53, R 6 In addition to this branched or straight-chain alkylene radical, it represents a group further comprising a carbamate segment, e.g., where R 6...represents a group further comprising a unit derived from a polyisocyanate, e.g., wherein the polyisocyanate comprises any of the polyisocyanates listed in Clause 15, an ethylene-based unsaturated compound.

[0325] Clause 55. In Clause 53, R 6 An ethylene-based unsaturated compound that does not contain this carbamate segment.

[0326] Clause 56. In any one of Clauses 53 through 55, R 6 this

[0327] Linear or branched alkylene radicals composed of carbon and hydrogen, for example

[0328] ;

[0329]

[0330]

[0331]

[0332]

[0333] or any combination of two or more of these, wherein each " " indicates a connection to another part of the ethylene-based unsaturated compound, and each " shown to the left of the oxygen "is within the structure (9) An ethylene-based unsaturated compound that represents a connection to a segment.

[0334] Clause 57. Each R that may be the same or different in any one of Clauses 53 through 56 7 This represents an alkyl group, for example, an alkyl group having 1 to 9 or 1 to 4 carbon atoms, for example, each R which may be the same or different here. 11 An ethylene-based unsaturated compound that represents a methyl group, ethyl group, propyl group, or butyl group.

[0335] Clause 58. In any one of Clauses 53 through 57, each X 1 This represents the same or different alkyl, acyloxy, or alkoxy groups, for example, the same or different alkyl, acyloxy, or alkoxyl groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 This represents an alkoxy group, for example, here at least two X 1 This represents an alkoxy, such as a methoxy, ethoxy, or propyloxy group, or each X 1 An ethylene-based unsaturated compound that represents an alkoxy group, such as a methoxy, ethoxy, or propyloxy group.

[0336] Clause 59. Each Y that may be identical or different in any one of Clauses 53 through 58 1 An ethylene-based unsaturated compound comprising a linear or branched alkylene radical having 1 to 8 carbon atoms, for example, a linear alkylene radical having 2 to 4, or in some cases 3, carbon atoms, or a branched alkylene radical having 5 to 6 carbon atoms.

[0337] Clause 60. In any one of Clauses 53 through 59, Z 1 this

[0338] (Here, x takes a value from 3 to 19);

[0339] (Here, each X1, X2, X3, and X4, which may be identical or different, has a value of 1 to 10, except that the structure has a molecular weight of 200 to 1500);

[0340]

[0341]

[0342] and, here, each " " is an ethylene unsaturated compound that represents a link to another part of the ethylene unsaturated compound.

[0343] Article 61. An ethylene-based unsaturated compound in any one of Articles 53 to 60, wherein m+n is 4 or less, e.g., where m is 1 or 2, e.g., 1, and n is 1 or 2, e.g., 1.

[0344] Clause 62. (a) an isocyanate-functional ethylene-based unsaturated compound; and (b) an ethylene-based unsaturated compound comprising a reaction product of a reactant comprising an aspartate silane having the following structure (or an ethylene-based unsaturated compound of any one of Clauses 1 to 27):

[0345]

[0346] Here, each R which may be the same or different 15 and each X 4 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, provided that at least one X 4 represents an alkoxy group, and Y 4 represents a linear or branched linker containing one or more carbon atoms, and each R may be the same or different. 15b represents an organic group that is inert to hydrogen or isocyanate groups at a temperature of 100°C or lower, for example, where the molecular weight of the ethylene-based unsaturated compound calculated from the molecular formula of the ethylene-based unsaturated compound is less than 400 to 2000 g / mol, for example, 400 to 1000 g / mol.

[0347] Clause 63. In Clause 62, the aspartate silane is (i) chemical formula aminoalkyl alkoxysilane of and (ii) chemical formula It may include the reaction product of a reactant comprising a maleic acid or fumaric acid ester, wherein R 16 and R17 represents the same or different organic group that is isocyanate-inactive below 100°C, for example, where R 16 and R 17 represents the same or different alkyl group having 1 to 4 carbon atoms, and each R which may be the same or different. 18 represents hydrogen, or an organic group that is isocyanate-inert below 100°C, and each X 5 represents the same or different organic group that is isocyanate-inactive below 100°C, provided that at least one X 5 is an alkoxy group, and for example, here each X 5 represents the same or different alkyl or alkoxy group having 1 to 4 carbon atoms, provided that at least 1 X 5 is an alkoxy group, and n is an integer having a value of 2 to 4, e.g. 3, an ethylene-based unsaturated compound.

[0348] Article 64. An ethylene-based unsaturated compound according to Article 63, wherein the aminoalkyl alkoxysilane comprises 2-aminoethyl-dimethylmethoxysilane, 3-aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropyl-methyl-diethoxysilane, or a mixture of any two or more of these.

[0349] Article 65. An ethylene-based unsaturated compound according to Article 63 or Article 64, wherein the maleic acid or fumaric acid ester comprises dimethyl maleic acid ester, diethyl maleic acid ester, di-n-butyl maleic acid ester, dimethyl fumaric acid ester, diethyl fumaric acid ester, di-n-butyl fumaric acid ester, or a mixture of any two or more of these.

[0350] Article 66. An ethylene-based unsaturated compound in which, in any one of Articles 63 to 65, the maleic acid or fumaric acid ester and the aminoalkyl alkoxysilane are present in a molar ratio of acid ester to aminoalkyl alkoxysilane of 0.8 to 1.2:1, 1.0 to 1.2:1, or 1.01 to 1.2:1.

[0351] Clause 67. An ethylene unsaturated compound in which, in any one of Clauses 62 through 66, the isocyanate-functional ethylene unsaturated compound has the following structure:

[0352]

[0353] Here, R 19 represents H or CH3, and X 6 represents O, S, NH or NR', where R' is an alkyl radical, e.g., an alkyl radical having 1 to 6 carbon atoms, and n is an integer having a value of 2 to 8, e.g., 2 to 4.

[0354] Article 68. An ethylene-based unsaturated compound according to Article 67, wherein the isocyanate-functional ethylene-based unsaturated compound comprises isocyanatoethyl methacrylate, isocyanatopropyl methacrylate, isocyanatobutyl methacrylate, isocyanatoethyl acrylate, isocyanatopropyl acrylate, isocyanatobutyl acrylate, or a mixture of any two or more of these.

[0355] Clause 69. An ethylene-based unsaturated compound in which, in any one of Clauses 62 through 68, the isocyanate-functional ethylene-based unsaturated compound comprises (i) a monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylate, and (ii) a reaction product of a reactant comprising a polyisocyanate.

[0356] Clause 70. In Clause 69, the monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylate is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl 2-chloroacrylate, 2-hydroxyethyl 2-ethylacrylate, 2-hydroxyethyl 2-propylacrylate, 2-hydroxyethyl 2-butylacrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl-2-propylacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl 2-butylacrylate, 3-hydroxypropyl 2-bromoacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 3-hydroxybutyl An ethylene-based unsaturated compound comprising 2-ethyl acrylate, 4-hydroxybutyl 2-butyl acrylate, 2-hydroxybutyl 2-propyl acrylate, 4-hydroxybutyl 2-chloro acrylate, hydroxyethyl caprolactone (meth)acrylate, caprolactone (meth)acrylate, polypropylene glycol monoacrylate, polyethylene glycol monoacrylate, bis(methacryloyloxy)propanol, bis(acryloyloxy)propanol, pentaerythritol triacrylate, or any combination of two or more of these.

[0357] Clause 71. In Clause 69 or Clause 70, the polyisocyanate is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, An ethylene-based unsaturated compound comprising 2,4,4-trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, bis(2-isocyanato-ethyl)fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, lysine isocyanate, triphenylmethane-4,4',4"-triisocyanate, an aromatic polyisocyanate based on toluene diisocyanate, a polyisocyanurate of toluene diisocyanate, or any combination of two or more of these.

[0358] Article 72. An ethylene-based unsaturated compound in which, in any one of Articles 69 to 71, the monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylate and polyisocyanate are used in a molar ratio of monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylate to polyisocyanate of 0.1:1 to 2:1, e.g. 0.5:1 to 1.5:1 or 1:1.

[0359] Clause 73. A method for producing an ethylene-based unsaturated compound according to any one of Clauses 1 through 27 and Clauses 62 through 72, wherein the method comprises reacting an isocyanate-functional ethylene-based unsaturated compound with an aspartate silane in the presence of optionally a catalyst to produce an ethylene-based unsaturated compound containing an aspartate group, wherein the aspartate silane has the following structure.

[0360]

[0361] Here, each R which may be the same or different 20 ...exhibits an organic group that is inert to isocyanate groups at temperatures below 100°C, and each R, which may be the same or different. 20b represents an organic group that is inert to hydrogen or isocyanate groups at temperatures below 100°C, and each X 6 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 6 represents an alkoxy group, and Y 5 It represents an organic group that is inert to isocyanate groups at temperatures below 100℃.

[0362] Clause 74. A method according to Clause 73, wherein an optional catalyst comprises an organometallic catalyst, an amine catalyst, or a combination thereof, for example, wherein the catalyst comprises a copper compound, e.g., copper naphthenate; a cobalt compound, e.g., cobalt naphthenate; a zinc compound, e.g., zinc naphthenate; a bismuth compound, e.g., bismuth neodecanoate; a tin compound, e.g., di-n-butyltin dilaurate; triethylamine; triethylenediamine; DABCO; DMEA; or a combination of any two or more of the above.

[0363] Clause 75. A method according to Clause 73 or Clause 74 in which the reaction takes place at a temperature of 10 to 120°C or 25 to 100°C.

[0364] Clause 76. A method in which, in any one of Clauses 73 to 75, the isocyanate-functional ethylene-based unsaturated compound and the aspartate silane are used in relative amounts providing a molar ratio of isocyanate-reactive groups to isocyanate groups of at least 1:1 or greater than 1:1 and less than 1.5:1.

[0365] Clause 77. A method comprising converting an aspartate group into a hydantoin group in any one of Clauses 73 to 76, wherein such conversion is carried out at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, or 80 to 100°C, optionally in the presence of a catalyst, such as Brønsted acid, a carboxylic acid, a sulfonic acid, a phenol, or a mixture of any two or more of these.

[0366] Clause 78. (a) a primary amine-containing aspartate and / or polyaspartate amine; (b) an isocyanate-functional ethylene-unsaturated compound; and (c) an ethylene-unsaturated compound comprising the reaction product of a reactant comprising an isocyanate-functional silane (or an ethylene-unsaturated compound of Clause 1, or any one of Clauses 28 to 61).

[0367] Clause 79. In Clause 78, the primary amine-containing aspartate is an ethylene-based unsaturated compound having the following structure:

[0368]

[0369] Here, Z 2...represents an organic group that is inert to isocyanate groups at temperatures below 100°C, or in some cases, a divalent organic group, and optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof, and C1 to C 18 Representing a hydrocarbon group comprising an alkylene group or a C5-C6 cycloalkylene group, each R which may be the same or different. 21 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, for example, where each R 21 represents the same or different alkyl groups, for example, alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, where each R 21 represents a methyl group, ethyl group, propyl group, or butyl group, and each R, which may be the same or different. 21a represents an organic group that is inert to hydrogen or an isocyanate group at a temperature of 100°C or lower, and m and n, which may be the same or different, are integers having values ​​from 1 to 4, for example, where m+n is 4 or less, for example, where m is 1 or 2, for example 1, and n is 1 or 2, for example 1.

[0370] Clause 80. In Clause 78 or Clause 79, the polyaspartate amine is an ethylene-based unsaturated compound having the following structure:

[0371]

[0372] Here, Z 3 It exhibits an organic group that is inert to isocyanate groups at temperatures below 100°C, and in some cases, a divalent organic group, and optionally contains isocyanate-inert oxygen, nitrogen, sulfur, or a combination thereof, and C1 to C 18 Representing a hydrocarbon group comprising an alkylene group or a C5-C6 cycloalkylene group, each R which may be the same or different. 22arepresents an organic group inert to hydrogen or isocyanate groups at temperatures below 100°C, and each R may be the same or different. 22 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, for example, where each R 22 represents the same or different alkyl groups, for example, alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, where each R 22 represents a methyl group, an ethyl group, a propyl group, or a butyl group, and m and n, which may be the same or different, are integers having values ​​from 1 to 4, for example, where m+n is 4 or less, for example, where m is 1 or 2, for example 1, and n is 1 or 2, for example 1.

[0373] Clause 81. In any one of Clauses 78 through 80, the primary amine-containing aspartate and / or polyaspartate amine is (i) formula: (NH2) m Z 3 (NH2) n (Here Z 3 is optionally an isocyanate-hydrocarbon group containing inert oxygen, nitrogen, sulfur, or a combination thereof, and m+n is at least an integer of value 2, e.g., 2 to 4) and a primary polyamine corresponding to and a maleic acid or fumaric acid ester of the following chemical formula (isomers of both are as indicated by wavy bonding):

[0374]

[0375] (Here, each R which may be the same or different) 23 ...exhibits an organic group that is inert to isocyanate groups at temperatures below 100°C, and each R, which may be the same or different. 24An ethylene-based unsaturated compound that is the reaction product of a reactant containing hydrogen or an organic group that is inert to isocyanate groups at a temperature of 100°C or lower.

[0376] Article 82. In Article 81, the primary polyamine is ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, bis-(3-aminopropyl)ether, 1,2-bis-(3-aminopropyloxy)ethane, 1,3-bis-(3-aminopropyloxy)-2,2'-dimethylpropane, 1,2-Bisaminocyclohexane, 1,3-Bisaminocyclohexane, 1,4-Bisaminocyclohexane, 1,3-Bisaminomethylcyclohexane, 1,4-Bisaminomethylcyclohexane, 1,3-Bisaminoethylcyclohexane, 1,4-Bisaminoethylcyclohexane, 1,3-Bisaminopropylcyclohexane, 1,4-Bisaminopropylcyclohexane, hydrogenated 4,4'-Diaminodiphenylmethane, 1-Amino-3,3,5-Trimethyl-5-Aminomethyl-cyclohexane, 2,4- and / or 2,6-Hexahydrotoluylenediamine, 2,4'- and / or 4,4'-Diamino-Dicyclohexylmethane, 3,3'-Dimethyl-4,4'-Diamino-Dicyclohexylmethane, Propane-1,2,3-Triamine, Pentane-1,3,5-triamine, benzene-1,3,5-triamine, isophoronediamine, menthandiamine, 1,4-bis-aminopropylpiperazine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, 2,4-toluenediamine, 2,4'- and / or 4,4'-diaminodiphenylmethane, m-aminobenzylamine, 4-chloro-o-phenylenediamine, tetrachloro-p-xylylenediamine, 4-methoxy-6-methyl-m-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, benzidine, 4,4'-bis(o-toluidine), dianisidine, 4,4'-Diaminodiphenylmethane, 2,2-(4,4'-Diaminodiphenyl)propane, 4,4'-Diaminodiphenyl ether, 4,4'-Thiodianiline, 4,4'-diaminodiphenylsulfone, 4,4'-diaminoditolylsulfone, methylenebis(o-chloroaniline), 3,9-bis(3-aminopropyl) 2,4,8,10-tetraoxaspiro[5,5]undecane, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,4-bis(aminoethylpiperazine), 1,4-bis(aminopropylpiperazine), 2,6-diaminopyridine, and bis(3,4-diaminophenyl)sulfone, relatively high molecular weight polyether polyamines containing aliphatic-bonded primary amino groups (e.g., JEFFAMINE® products commercially available from Huntsman Corp.), and combinations of any two or more of the above. Ethylene-based unsaturated compounds.

[0377] Article 83. An ethylene-based unsaturated compound according to Article 81 or Article 82, wherein the maleic acid or fumaric acid ester comprises a dimethyl ester of maleic acid, a diethyl ester of maleic acid, a di-n-butyl ester of maleic acid, a dimethyl ester of fumaric acid, a diethyl ester of fumaric acid, a di-n-butyl ester of fumaric acid, a maleic acid ester or fumaric acid ester corresponding to any of the above substituted by a methyl group at the 2- and / or 3-position, or a combination of any two or more of these.

[0378] Article 84. An ethylene-based unsaturated compound, wherein, in any one of Articles 81 to 83, the primary polyamine and the maleic acid or fumaric acid ester are present in an amount such that 0.8+m / n to 1.2+m / n, e.g., 1+m / n primary amino groups are present for each olefinic double bond of the primary amine-containing aspartate, or 0.8 to 1.2, e.g., 1 primary amino group is present for each olefinic double bond of the polyaspartate amine.

[0379] Clause 85. An ethylene unsaturated compound in which, in any one of Clauses 78 through 84, the isocyanate-functional ethylene unsaturated compound has the following structure:

[0380]

[0381] Here, R 25 represents H or CH3, and X 7 represents O, S, NH or NR', where R' is an alkyl radical, e.g., an alkyl radical having 1 to 6 carbon atoms, and n is an integer having a value of 2 to 8, e.g., 2 to 4.

[0382] Article 86. The ethylene-based unsaturated compound of Article 85, wherein the isocyanate-functional ethylene-based unsaturated compound comprises isocyanatoethyl methacrylate, isocyanatopropyl methacrylate, isocyanatobutyl methacrylate, isocyanatoethyl acrylate, isocyanatopropyl acrylate, isocyanatobutyl acrylate, or a mixture of any two or more of these.

[0383] Clause 87. An ethylene-based unsaturated compound in which, in any one of Clauses 78 through 86, the isocyanate-functional ethylene-based unsaturated compound comprises (i) a monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylate, and (ii) a reaction product of a reactant comprising a polyisocyanate.

[0384] Clause 88. In Clause 87, the monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylate is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl 2-chloroacrylate, 2-hydroxyethyl 2-ethylacrylate, 2-hydroxyethyl 2-propylacrylate, 2-hydroxyethyl 2-butylacrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl-2-propylacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl 2-butylacrylate, 3-hydroxypropyl 2-bromoacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 3-hydroxybutyl An ethylene-based unsaturated compound comprising 2-ethyl acrylate, 4-hydroxybutyl 2-butyl acrylate, 2-hydroxybutyl 2-propyl acrylate, 4-hydroxybutyl 2-chloro acrylate, hydroxyethyl caprolactone (meth)acrylate, caprolactone (meth)acrylate, polypropylene glycol monoacrylate, polyethylene glycol monoacrylate, bis(methacryloyloxy)propanol, bis(acryloyloxy)propanol, and pentaerythritol triacrylate.

[0385] Clause 89. In Clause 87 or Clause 88, the polyisocyanate is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, An ethylene-based unsaturated compound comprising 2,4,4-trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, bis(2-isocyanato-ethyl)fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, lysine isocyanate, triphenylmethane-4,4',4"-triisocyanate, an aromatic polyisocyanate based on toluene diisocyanate, a polyisocyanurate of toluene diisocyanate, or any combination of two or more of these.

[0386] Article 90. An ethylene-based unsaturated compound in which, in any one of Articles 87 to 89, the monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylate and diisocyanate are present in a molar ratio of monohydroxy-substituted monofunctional and / or polyfunctional (meth)acrylate to diisocyanate of 0.1:1 to 2:1, e.g. 0.5 to 1.5:1, or in some cases 1:1.

[0387] Clause 91. In any one of Clauses 78 through 90, the isocyanate-functional silane has the structure: OCN-Y 6 -Si(X 8It has )3, where Y 6 represents a linear or branched linker containing one or more carbon atoms, for example, where Y 6 ... comprises linear or branched alkylene radicals having 1 to 8 carbon atoms, for example, linear alkylene radicals having 2 to 4 or, in some cases, 3 carbon atoms, or branched alkylene radicals having 5 to 6 carbon atoms, and each X 8 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 8 represents an alkoxy group, for example, where each X 8 represents the same or different alkyl, acyloxy, or alkoxy group, for example, the same or different alkyl, acyloxy, or alkoxyl group having 1 to 9 or 1 to 4 carbon atoms, provided that at least 1 X 8 represents an alkoxy group, for example, here at least two X 8 represents an alkoxy, such as a methoxy, ethoxy, or propyloxy group, or each X 8 Ethylene-based unsaturated compounds that represent an alkoxy group, such as methoxy, ethoxy, or propyloxy.

[0388] Article 92. An ethylene-based unsaturated compound according to Article 91, wherein the isocyanate-functional silane comprises 3-isocyanatopropyl-methyldimethoxysilane, 3-isocyanatopropyl-trimethoxysilane, 3-isocyanatopropyl-triethoxysilane, or a mixture of any two or more of these.

[0389] Article 93. A method for producing an ethylene-based unsaturated compound according to any one of Article 1, Articles 28 to 61, or Articles 78 to 92, comprising reacting (a) a primary amine-containing aspartate and / or polyaspartate amine with (b) an isocyanate-functionalized ethylene-based unsaturated compound and (c) an isocyanate-functionalized silane in the presence of optionally a catalyst to produce an ethylene-based unsaturated compound containing aspartate groups.

[0390] Clause 94. A method according to Clause 93, wherein an optional catalyst comprises an organometallic catalyst, an amine catalyst, or a combination thereof, for example, wherein the catalyst comprises a copper compound, e.g., copper naphthenate; a cobalt compound, e.g., cobalt naphthenate; a zinc compound, e.g., zinc naphthenate; a bismuth compound, e.g., bismuth neodecanoate; a tin compound, e.g., di-n-butyltin dilaurate; triethylamine; triethylenediamine; DABCO; DMEA; or a combination of any two or more of the above.

[0391] Clause 95. A method according to Clause 93 or Clause 94 in which the reaction takes place at a temperature of 10 to 120°C or 25 to 100°C.

[0392] Clause 96. A method in which, in any one of Clauses 93 to 952, a primary amine-containing aspartate and / or polyaspartate amine, an isocyanate-functional ethylene-based unsaturated compound, and an isocyanate-functional silane are used in relative amounts providing at least 1:1, e.g., a molar ratio of isocyanate-reactive groups to isocyanate groups greater than 1:1 and less than 1.5:1.

[0393] Clause 97. A method in any one of Clauses 93 to 96, further comprising converting at least a portion of the aspartate groups into hydantoin groups, wherein such conversion is carried out at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, 80 to 100°C, 90 to 120°C, or 100 to 120°C, optionally in the presence of a catalyst, such as Brønsted acid, carboxylic acid, sulfonic acid, phenol, or a mixture of any two or more of these.

[0394] Clause 98. (a) A composition such as a coating composition comprising an ethylene-based unsaturated compound of any one of Clauses 1 to 72 or Clauses 78 to 92, or an ethylene-based unsaturated compound prepared by the method of any one of Clauses 73 to 77 or Clauses 93 to 97.

[0395] Clause 99. A composition according to Clause 98, wherein the ethylene-based unsaturated compound is present in an amount of 0.01 to 99 weight%, 0.1 to 20 weight%, 1 to 50 weight%, 5 to 30 weight%, 40 to 70 weight%, 60 to 80 weight%, 65 to 99 weight%, or 0.01 to 20 weight% based on the total weight of the solids in the composition.

[0396] Clause 100. A composition according to Clause 98 or Clause 99, wherein (b) an ethylene-based unsaturated oligomer different from the ethylene-based unsaturated compound, for example, an ethylene-based unsaturated oligomer having a number average molecular weight (Mn) of 1,000 g / mol to 35,000 g / mol, 1,000 g / mol to 30,000 g / mol, 1,000 g / mol to 25,000 g / mol, 1,000 g / mol to 20,000 g / mol, 2,200 to 10,000 g / mol, or 2,200 to 5,500 g / mol when measured by size exclusion chromatography (SEC) according to the procedure described herein.

[0397] Clause 101. A composition according to Clause 100, wherein the ethylene-based unsaturated oligomer comprises a urethane (meth)acrylate oligomer comprising a (meth)acrylate group, a urethane group, and a backbone, for example, wherein the backbone is a reaction product of (1) a polyol, e.g., a diol, (2) a polyisocyanate, e.g., a diisocyanate, and (3) a hydroxyl group-containing (meth)acrylate.

[0398] Clause 102. A composition according to Clause 101, wherein the polyol comprises a polyether polyol, a polyester polyol, a polycarbonate polyol, a polycaprolactone polyol, an acrylic polyol, or a mixture of any two or more of these, for example, wherein the polyol comprises polypropylene glycol.

[0399] Clause 103. A composition according to Clause 101 or Clause 102, wherein the number average molecular weight derived from the hydroxyl value of the polyol is 50 to 15,000 g / mol or 1,000 to 8,000 g / mol.

[0400] Clause 104. In any one of Clauses 101 to 103, the polyisocyanate used to produce the urethane acrylate oligomer is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), A composition comprising 2,2,4-trimethylhexamethylene diisocyanate, bis(2-isocyanato-ethyl)fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, lysine isocyanate, hexamethylene diisocyanate trimer, triphenylmethane-4,4',4"-triisocyanate, hexamethylene diisocyanate trimer, aromatic polyisocyanates based on toluene diisocyanate, polyisocyanurates of toluene diisocyanate, as well as any combination of two or more of these.

[0401] Clause 105. A composition in which, in any one of Clauses 101 to 104, the hydroxyl group-containing (meth)acrylate used to produce the urethane (meth)acrylate oligomer comprises an epoxy (meth)acrylate comprising a (meth)acrylate derived from (meth)acrylic acid and / or an alkylene oxide, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl acrylate, and 2-hydroxy-3-oxyphenyl (meth)acrylate.

[0402] Clause 106. A composition in which, in any one of Clauses 101 to 105, the polyol, polyisocyanate, and hydroxyl group-containing (meth)acrylate used to produce a urethane (meth)acrylate oligomer are used in relative amounts such that 0.1 to 0.9 equivalents of hydroxyl groups contained in the hydroxyl group-containing (meth)acrylate and 1.0 to 1.5 equivalents of total hydroxyl groups present in the polyol and hydroxyl group-containing (meth)acrylate are used for every 1 equivalent of isocyanate groups contained in the polyisocyanate.

[0403] Clause 107. A composition in which, in any one of Clauses 100 to 106, the ethylene-based unsaturated oligomer is present in an amount of 1 to 99 weight%, 1 to 90 weight%, 5 to 95 weight%, 10 to 90 weight%, 10 to 80 weight%, or 30 to 90 weight%, or 50 to 80 weight% based on the total weight of the solid in the composition.

[0404] Clause 108. Any one of Clauses 98 to 107, wherein (c) a reactive diluent compound comprising one or more ethylene-based unsaturated groups.

[0405] Clause 109. In Clause 108, the reactive diluent comprises one double bond, e.g., alkyl or hydroxyalkyl (meth)acrylate, e.g., methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, isobornyl (meth)acrylate, lauryl (meth)acrylate, ethoxylated nonyl-phenol (meth)acrylate, phenoxyethyl (meth)acrylate, diethylene-glycol-ethyl-hexyl acrylate (DEGEHA), acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamide, vinyl ester (e.g., vinyl acetate), styrene, alkylstyrene, halostyrene, N-vinylpyrrolidone, N-vinyl caprolactam, vinyl chloride, A composition comprising vinylidene chloride, or a mixture of any two or more of these.

[0406] Clause 110. A composition according to Clause 108, wherein the reactive diluent comprises one or more double bonds, e.g., ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexamethylene glycol di(meth)acrylate, bisphenol A di(meth)acrylate, 4,4'-bis(2-acryloyloxyethoxy)diphenylpropane, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, vinyl (meth)acrylate, divinyl benzene, divinyl succinate, diallyl phthalate, trialyl phosphate, trialyl isocyanurate, tris(2-acryloylethyl)isocyanurate, or a mixture of any two or more of these.

[0407] Clause 111. A composition in which, in any one of Clauses 108 to 110, the reactive diluent is present in an amount of 1 to 99 weight%, 5 to 90 weight%, 10 to 90 weight%, 10 to 80 weight%, or in some cases 10 to 60 weight%, 10 to 40 weight%, or 10 to 30 weight% based on the total weight of the solid in the composition.

[0408] Clause 112. Any one of Clauses 98 to 111, wherein (d) a composition further comprising a photoinitiator.

[0409] Clause 113. A composition according to Clause 112, wherein the photoinitiator comprises an acylphosphine oxide, such as bisylphosphine oxide (BAPO) and / or monoacylphosphine oxide (MAPO), an α-hydroxy ketone, or a mixture of any two or more of these.

[0410] Clause 114. The composition of Clause 113, wherein the photoinitiator comprises a bisylphosphine oxide having the following structure:

[0411]

[0412] Here, R 50 C1-C 12 It is alkyl, cyclohexyl, or phenyl, which is unsubstituted or substituted by 1 to 4 halogen atoms, or C1-C8 alkyl; R 51 and R 52 are each independently a C1-C8 alkyl or a C1-C8 alkoxy; R 53 is hydrogen or C1-C8 alkyl; R 54 is hydrogen or methyl, for example, where bis-acylphosphine oxide includes bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-(2,4-bis-pentyloxyphenyl)phosphine oxide, or a mixture thereof.

[0413] Clause 115. A composition in which, in any one of Clauses 112 to 114, the photoinitiator is present in an amount of 0.1 to 10 weight%, e.g. 0.1 to 5 weight%, or in some cases 1 to 5 weight%, based on the total weight of the radiation-curable composition.

[0414] Clause 116. Any one of Clauses 98 through 115, wherein (e) a composition further comprising gamma-mercaptopropyltrimethoxysilane, trimethoxysilylpropyl acrylate, 3-trimethoxysilylpropane-1-thiol, poly-silane, or a mixture of any two or more of these, e.g., wherein the poly-silane comprises the following:

[0415] (a) At least two, in some cases two, moiety of the following structure (1):

[0416] ; and

[0417] (b1) Moiety of the following structure (2):

[0418] ;

[0419] (b2) Moiety of the following structure (3):

[0420] ; or

[0421] (b3) A combination of the moiety of structure (2) and the moiety of structure (3), where (i) Y 7 represents a linear or branched linker containing one or more carbon atoms, and (ii) each X 9 represents an alkoxy group or an organic group inert to isocyanate groups at temperatures of 100°C or lower, provided that at least one X 9 represents an alkoxy group, and (iii) R, which may be the same or different. 26 and R 27 Each represents an organic group that is inert to isocyanate groups at temperatures below 100°C; (iv) R which may be the same or different 28and R 29 Each represents an organic group that is inert to hydrogen or an isocyanate group at a temperature of 100°C or lower; (v) each " " indicates a connection to another part of the polysilane.

[0422] Clause 117. A composition having a total silane content of 10 mmol or less per 100 grams of the radiation-curable composition, e.g., 1 to 10 mmol, 1 to 8 mmol, or in some cases 2 to 6 mmol (determined as described in the Examples section of this specification), or a total urea+urethane content of 20 to 200 mmol per 100 grams of the composition, e.g., 30 to 150 mmol, or in some cases 40 to 100 mmol (determined as described in the Examples section of this specification).

[0423] Clause 118. A composition comprising, in any one of Clauses 98 to 117, further comprising an additive comprising a photosensitizer, a radiation-cured amine synergist, a UV absorber, an antioxidant, a UV stabilizer, a heat stabilizer, a filler, a heat transfer thiol compound, a surface-active compound, a viscosity modifier, an additional additive promoter, a water scavenger, such as TEOS and orthoformate, an oxygen quencher, or a functional material including a pigment, a dye, a photochromic dye, a laser dye, a liquid crystal, a luminescent material, a nanomaterial, a quantum dot, a fluorescent material, a dichroic dye, an antistatic material, a refractive index modifier, and a bioactive material.

[0424] Clause 119. A composition comprising an organic solvent in addition to any one of Clauses 98 to 118.

[0425] Clause 120. In any one of Clauses 98 to 119, having a viscosity of at least >0.1 Pascal-second (Pa·s), at least 0.2, at least 0.5, at least 1 Pa·s, and / or less than 15 Pa·s, less than 12 Pa·s, or less than 10 Pa·s, or 1 to 15 Pa·s, 2 to 12 Pa·s, or 3 to 10 Pa·s, wherein the viscosity is at 25°C and 50s -1 A composition that is measured at the shear rate of

[0426] Clause 121. A cured coating formed from a composition of any one of Clauses 98 to 120.

[0427] Clause 122. A substrate at least partially coated with the cured coating of Clause 121, for example, wherein the substrate comprises an optical fiber.

[0428] Clause 123. The substrate of Clause 122, further comprising a secondary coating in contact with and surrounding the cured coating, and optionally an ink layer disposed on the secondary coating.

[0429] Clause 124. Clause 122 or Clause 123, wherein the cured coating has a tensile modulus of less than 5 MPa, less than 2 MPa, less than 1.5 MPa, or less than 1.0 MPa.

[0430] Clause 125. In any one of Clauses 122 to 124, the description that the cured coating exhibits a peel strength of at least 40 gf / in or at least 55 gf / in when measured after at least 7 days as described in the Examples section of this specification.

[0431] Clause 126. A description in any one of Clauses 122 through 125 in which the cured coating exhibits an elongation at break of at least 35%, e.g., at least 50%, when measured as described in the Examples section of this specification.

[0432] Clause 127. A method for coating an optical fiber, comprising: (a) providing a glass optical fiber by drawing the glass optical fiber, for example, through a draw tower; (b) applying a primary coating composition on the surface of the glass optical fiber; (c) optionally applying a dose of UV light sufficient to at least partially cure the primary coating composition; (d) applying a secondary coating composition to the primary coating composition; (e) exposing the secondary coating composition to at least one radiation source capable of emitting ultraviolet radiation to induce curing of the secondary coating composition and optionally the primary coating composition, thereby forming a cured primary coating on the surface of the optical fiber and forming a cured secondary coating on the surface of the cured primary coating, wherein the primary coating composition and / or the secondary coating composition comprises a composition of any one of Clauses 98 to 120.

[0433] Clause 128. (a) a glass core and a cladding layer in contact with and surrounding the glass core; and (b) a coating portion that at least partially coats the cladding layer, comprising: (i) a primary coating layer in contact with the cladding layer; and (ii) a secondary coating layer in contact with and surrounding the primary coating layer, wherein the primary coating layer and / or the secondary coating layer are a cured product of a composition of any one of Clauses 98 to 120.

[0434] Clause 129. A coated optical fiber according to Clause 128, wherein the core comprises pure silica glass (SiO2) or silica glass having one or more dopants, e.g., wherein the dopant comprises GeO2, Al2O3, P2O5, TiO2, ZrO2, Nb2O5, Ta2O5, or any combination of two or more of these.

[0435] Clause 130. A method or coated optical fiber according to Clause 127 or Clause 128 or Clause 129, wherein the cured primary coating has an in-situ glass transition temperature of less than -35°C, less than -40°C, less than -45°C, or less than or equal to -50°C, and / or the cured primary coating has a thickness of 20 to 50 μm, 20 to 40 μm, 20 to 30 μm, 25 or 32.5 μm, or 15 to 25 μm.

[0436] Article 131. A method or coated optical fiber, wherein, in any one of Article 127 or Article 130 or Articles 128 to 129, the secondary coating exhibits an in-situ tensile modulus of greater than 800 MPa, greater than 1110 MPa, greater than 1300 MPa, greater than 1400 MPa, or greater than 1500 MPa, 1000 MPa to 8000 MPa, 1200 MPa to 5000 MPa, or 1500 MPa to 3000 MPa, and / or an in-situ Tg of 50°C to 120°C or 50°C to 100°C, and / or a thickness of 40 μm or less, 20 to 40 μm, or 20 to 30 μm.

[0437] Clause 132. In Clause 128 or Clause 129, a mode-field diameter of 8 to 10 μm at a wavelength of 1310 nm, a mode-field diameter of 9 to 13 μm at a wavelength of 1550 nm, and / or 20 to 200 μm 2 Coated optical fiber having an effective area.

[0438] The following non-limiting and non-inclusive examples are intended to further describe various non-limiting and non-inclusive modes of implementation without limiting the scope of implementations described herein.

[0439] Examples

[0440] Table 1 - Materials Used

[0441]

[0442] Many of the materials used herein were manufactured to produce mixtures having a statistical distribution of molecular weights that can be easily recognized by a person skilled in the art. Structures in this section and elsewhere in this application represent only designed average or "ideal" structures, unless otherwise indicated.

[0443] Example 1: Synthesis of Mono-Aspartic Acid Precursor

[0444] IPDA (149 g, 0.87 mol) was added to a 4-neck flask (1000 mL), purged with dry air, and cooled to 5°C using an ice bath. Subsequently, diethyl maleate (152 g, 0.88 mol) was added dropwise, and the mixture was maintained below 10°C. Upon addition, the mixture was stirred for 2 hours and heated to 20-25°C to obtain a final product mixture containing the compound of structure (A) as a viscous liquid. The product was subsequently available for use in subsequent formulations without further purification. Structure (A) is shown below:

[0445]

[0446] Example 2: Synthesis of Polyaspartic Acid Precursor

[0447] IPDA (738 g, 4.3 mol) was added to a 4-neck flask (5000 mL), purged with dry air, and cooled to 10°C using an ice bath. Subsequently, diethyl maleate (1500 g, 8.7 mol) was added dropwise, and the mixture was maintained below 15°C. Upon addition, the mixture was stirred for 4 hours and heated to 20-25°C to obtain a final product mixture containing the compound of structure (B) as a viscous liquid. The product was subsequently available for use in subsequent formulations without further purification. Structure (B) is shown below:

[0448]

[0449] Example 3: Synthesis of Tri-Aspartic Acid Precursor

[0450] Zepamin T-403 (240 g, 0.5 mol) and BHT (0.5 g, 1000 ppm) were added to a 4-neck flask (1000 mL) and purged with dry air. Subsequently, diethyl maleate (260 g, 1.5 mol) was added dropwise. Upon addition, the mixture was stirred for 6 hours and stored for 6 months to obtain a final product mixture containing structure (C) as a viscous liquid. The product was subsequently available for use in subsequent formulations without further purification. Structure (C) is shown below:

[0451]

[0452] Example 4: Synthesis of Silane Precursor

[0453] KBM-903 (182 g, 1 mol) was placed in a 4-neck flask (500 ml), cooled to 0–5°C (ice bath) under nitrogen, and then diethyl maleate (175 g, 1 mol) was added dropwise. The resulting mixture was then stirred at 0–10°C for 0.5–3 hours to obtain a final product mixture containing the compound of structure (D) as a viscous liquid. Subsequently, the product was available for use in subsequent formulations without further purification. Structure (D) is shown below:

[0454]

[0455] Example 5: Synthesis of Ethylene-based Unsaturated Compound 1

[0456] To produce Compound 1, the silane precursor (70.2 g, 0.2 mol) from Example 4 was placed in a 4-neck flask (250 ml) and purged with a gaseous mixture of air and nitrogen in a 3:1 volume ratio. Subsequently, DBTDL (0.06 g, 600 ppm), BHT (0.10 g, 1000 ppm), and AOI (28.6 g, 0.20 mol) were added sequentially. While still purging with the 3:1 air / nitrogen mixture, the reaction mixture was further stirred at 70°C for an additional 2–4 hours to obtain a final product mixture containing the compound of structure (E) as a viscous liquid. The product was then available for use in subsequent formulations without further purification. Structure (E) is shown below:

[0457]

[0458] Example 6: Synthesis of Ethylene-based Unsaturated Compound 2

[0459] To produce Compound 2, a mixture of TDI (81.5 g, 0.47 mol) and BHT (1000 ppm) was placed in a 4-neck flask (500 ml) and purged with dry air. The resulting mixture was then stirred at 20–25°C for 10 minutes, after which HEA (54.3 g, 0.47 mol) and Koscat 83 (0.1 g, 300 ppm) were added sequentially while actively cooling. The resulting mixture was then stirred at 85°C for 1–2 hours. Subsequently, the silane precursor (164.4 g, 0.47 mol) from Example 4 was added. While still purging with dry air, the reaction mixture was further stirred at 60°C for an additional 1–2 hours to obtain a final product mixture containing a complex of structure (F) as a viscous liquid. The product was subsequently available for use in subsequent formulations without further purification. Structure (F) is shown below:

[0460]

[0461] Example 7: Synthesis of Ethylene-based Unsaturated Compound 3

[0462] To produce Compound 3, a mixture of IPDI (64.4 g, 0.29 mol), BHT (0.2 g, 1000 ppm), and Coscat 83 (0.13 g, 600 ppm) was placed in a 4-neck flask (500 ml) and purged with dry air. The resulting mixture was then stirred at 20–25°C for 10 minutes, after which HEA (33.6 g, 0.29 mol) was added. The resulting mixture was then stirred at 60°C for 1–2 hours. Subsequently, the silane precursor (101.8 g, 0.29 mol) from Example 4 was added. While still purging with dry air, the reaction mixture was further stirred at 60°C for an additional 5–8 hours to obtain a final product mixture containing the compound of structure (G) as a viscous liquid. The product was subsequently available for use in subsequent formulations without further purification. Structure (G) is shown below:

[0463]

[0464] Example 8: Synthesis of Ethylene-based Unsaturated Compound 4

[0465] To produce Compound 4, Compound 1 (150 g) from Example 5 was placed in a 4-neck flask (500 ml) and purged with dry air. The resulting mixture was then heated to 70–80°C, after which acrylic acid (1.5 g, 1%) was added. The resulting mixture was then stirred at 85°C for 8 hours to obtain a final product mixture containing the compound of structure (H) as a viscous liquid. The product was subsequently available for use in subsequent formulations without further purification. Structure (H) is shown below:

[0466]

[0467] Example 9: Synthesis of Ethylene-based Unsaturated Compound 5

[0468] To produce Compound 5, the mono-aspartic acid precursor of Example 1 (50 g, 0.15 mol) was added to a 4-neck flask (500 ml) and purged with dry air. Subsequently, AOI was added dropwise (20 g, 0.15 mol). The resulting mixture was then stirred at 60°C for 3 hours. TMSPI (28 g, 0.14 mol) was then added dropwise, and the mixture was stirred at 60°C for 5 hours to obtain a final product mixture containing the compound of structure (I) as a viscous liquid. The product was subsequently available for use in subsequent formulations without further purification. Structure (I) is shown below:

[0469]

[0470] Example 10: Synthesis of Ethylene-based Unsaturated Compound 6

[0471] To produce Compound 6, the polyaspartic acid precursor of Example 2 (57 g, 0.11 mol) was added to a 4-neck flask (500 ml) and purged with dry air. Subsequently, AOI was added dropwise (16 g, 0.11 mol). The resulting mixture was then stirred at 60°C for 4 hours. Subsequently, TESPI (27 g, 0.11 mol) was added dropwise. The resulting mixture was then stirred at 60°C for 13 hours to obtain a final product mixture containing structure (J) as a viscous liquid. The product was subsequently available for use in subsequent formulations without further purification. Structure (J) is shown below:

[0472]

[0473] Example 11: Synthesis of Ethylene-based Unsaturated Compound 7

[0474] To produce Compound 7, Compound 6 (57 g) from Example 10 was placed in a 4-neck flask (500 ml) and purged with dry air. The resulting mixture was then heated to 70–80°C, after which acrylic acid (5.6 g, 1%) was added. The resulting mixture was then stirred at 85°C for 2 hours to obtain a final product mixture containing the compound of structure (K) as a viscous liquid. The product was subsequently available for use in subsequent formulations without further purification. Structure (K) is shown below:

[0475]

[0476] Example 12: Synthesis of Ethylene-based Unsaturated Compound 8

[0477] To produce Compound 8, the tri-aspartic acid precursor of Example 3 (128 g, 0.13 mol) and BHT (0.2 g, 1000 ppm) were placed in a 4-neck flask (500 ml) and purged with dry air. Subsequently, a mixture of AOI (18 g, 0.13 mol) and TMPSI (53 g, 0.26 mol) was added to the flask. The resulting mixture was then stirred at 70°C for 15 hours to obtain a final product mixture containing the compound of structure (L) as a viscous liquid. The product was subsequently available for use in subsequent formulations without further purification. Structure (L) is shown below:

[0478]

[0479] Example 13: Synthesis of Oligomer 1

[0480] To produce oligomer 1, a mixture of PPG 4000 (3474 g, 0.9 mol), TDI (313 g, 1.8 mol), and BHT (4 g, 1000 ppm) was placed in a 4-neck flask (5000 ml) and purged with dry air. The resulting mixture was then stirred at 20–25°C for 15 minutes, after which a mixture of DBTDL (1.6 g, 400 ppm) was added. The resulting mixture was then stirred for 15 minutes without external heat, followed by stirring at 60°C for 1–2 hours. Subsequently, HEA (208 g, 1.8 mol) was added. While still purging with dry air, the reaction mixture was stirred at 85°C for an additional 1–2 hours to obtain a final product mixture containing the compound of structure (M) as a viscous liquid. The product was subsequently available for use in subsequent formulations without further purification. Structure (M) is shown below:

[0481]

[0482] Example 14: Synthesis of Oligomer 2

[0483] To produce oligomer 2, a mixture of PPG 4000 (74.3 kg, 19.1 mol), HEA (2.2 kg, 19.1 mol), BHT (80 g, 1000 ppm), acrylic acid (40 g, 0.56 mol), TDI (3.3 kg, 19.1 mol), and DBTDL (64 g, 800 ppm) was sequentially added to a batch reactor (180 L). The resulting mixture was then stirred at 70°C for 2–4 hours to obtain a final product mixture containing a compound having structure (N) as a viscous liquid. Subsequently, the product was available for use in subsequent formulations without further purification. Structure (N) is shown below:

[0484]

[0485] The reactants for preparing all compounds and oligomer examples are listed in Tables 2 and 3. In the case of ethylene-based unsaturated compounds containing silanes, the silane content in the compound was determined by dividing the number of silane groups in the compound (where "silane group" refers to a group of the structure Si(X)3, where X represents an alkoxy group or an organic group inert to an isocyanate group at temperatures below 100°C, provided that at least one X represents an alkoxy group) by the theoretical molecular mass (g / mol) of the compound. The calculated number was then converted to mmol / 100g of compound by multiplying the unit by 100,000. The theoretical molecular mass of the compound was calculated using the theoretical molecular mass values ​​for the reactants used to produce the compounds from Table 2. When used as an adhesion promoter, it is desirable that the ethylene-based unsaturated compound does not significantly affect other formulation properties; therefore, it is desirable to keep the weight percentage of the ethylene-based unsaturated compound in the formulation low. To maintain a consistent level of silane content in the formulated product, it is desirable that the higher the silane content in the compounds, the lower the weight percentage of ethylene-based unsaturated compounds in the formulation. All ethylene-based unsaturated compounds 1-8 have a silane content greater than 60 mmol / 100 gram compounds. Compounds 1 and 4 had a silane content of >160 mmol / 100 gram compounds.

[0486] Table 2 - Reactants for Ethylene-based Unsaturated Compounds 1-8 (Molar Ratios) and Silane Content

[0487]

[0488] Table 3 - Reactants for Oligomers 1-2 (Molar Ratios)

[0489]

[0490] Preparation 1-27

[0491] Each formulation listed in Table 4A-4G is a SpeedMixer TM It was prepared by mixing a 100 g sample in a 100 ml mixing cup suitable for use with. Specifically, the oligomer and monomer components, excluding the ethylene-based unsaturated compound of the present invention, were added to other components and mixed as specified in Tables 4A-4G below. After adding to the cup, the cup was closed, and a speed mixer TM Mixing was performed at 3000 RPM for 3 minutes in a DAC150 FVZ. Afterward, the mixing operation was stopped, the resulting mixture was transferred to a suitable receptacle, heated in an oven to 60°C, and maintained at this temperature for approximately 6 hours to ensure that all components were completely dissolved. Subsequently, the sample was removed from the oven and mixed again in a speed mixer for an additional 3 minutes using the same method, after which the ethylene-based unsaturated compound of the present invention was added to obtain a total of 100 g. Finally, the mixture was mixed again in a speed mixer for an additional 3 minutes using the same method.

[0492] These formulations were then characterized according to their respective total silane content and total urea + urethane content according to the methodology described below. Subsequently, all formulations were tested according to the method described below to determine their peel strength, percentage elongation, film modulus, toughness, tensile strength, and viscosity. Unless otherwise indicated, values ​​for total silane content were rounded to the first decimal place, and values ​​for urea + urethane content were rounded to the nearest integer. Meanwhile, values ​​for film modulus, toughness, and tensile strength were rounded to two decimal places. Viscosity is presented in the nearest 1 centipoise unit. Finally, values ​​for percentage elongation are presented rounded to the nearest 1% unit. Values ​​for each of these measured characteristics are reported in Tables 4A-4G below.

[0493] The “total silane” for a given composition was determined by first calculating the molar amount of silane groups in each silane-containing component (Y) according to the following formula (wherein “silane group” refers to a group of structure Si(X)3, where X represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X represents an alkoxy group):

[0494]

[0495] Here, Wt = weight-based amount of each component Y per 100 g of the total relevant composition; N = number of silane groups present in one molecule of component Y; and MW is the theoretical molecular mass (g / mol) of component Y. The total silane content is reported in units of mmol / 100 g. The theoretical molecular mass values ​​for the reactants used to produce the compounds and oligomers (including silane-containing compounds and oligomers) of the formulations of the present invention are reported in Table 2-3.

[0496] Next, the total silane value for the entire composition was calculated by summing the molar values ​​of silane groups for each silane-containing component according to the following formula:

[0497]

[0498] Values ​​for total silanes in this application are reported in units of mmol / 100 g. Values ​​for total silanes may arbitrarily be expressed in units of mol / 100 g by dividing the sum by 1000, but values ​​in this application are not reported in this manner unless specifically indicated otherwise. Alternatively, for clarity, where "equivalent" or "milliequivalent" is specified in this application, values ​​should be interpreted based on 100 g of the associated composition unless otherwise indicated. Total silane values ​​for each formulation are presented in Tables 4A-4G below.

[0499] It should be noted that if the complete recipe of the composition is not known in advance, the equivalent weight of the silane moiety may be analytically determined through any suitable method recognized by a person skilled in the art to which the present invention applies, such as size exclusion chromatography (SEC), infrared spectroscopy, HPLC, MALDI-TOF mass spectrometry, or nuclear magnetic resonance (NMR) methods.

[0500] The value for the urea + urethane content was determined through the same method as specified for the "total silane," except that instead of evaluating the silane groups or silane-containing components, the total isocyanate groups used in the preparation of the ethylene-based unsaturated compound reacting with the isocyanate-reactive compound were counted.

[0501] Viscosity was measured using an Anton Paar Rheolab QC. The instrument was configured with Z3 and Z4 systems, and both were used. Samples for the Z3 system were weighed to a volume of 14.7 g ± 0.2 g and loaded into disposable aluminum cups, while samples for the Z4 system had a mass of 3.5 g ± 0.2 g. The samples in the cups were inspected; if bubbles were determined to be present upon visual inspection, the sample and cup were subjected to centrifugation or left to stand long enough for the bubbles to escape from the bulk of the liquid. Bubbles appearing on the top surface of the liquid were considered acceptable. Subsequently, the bob was gently loaded into the liquid in the measuring cup, and the cup and bob were installed in the instrument. Viscosity was measured at 25°C ± 0.1°C and 55°C ± 0.1°C for 50 sec, accompanied by a 5-minute equilibration period to ensure constant temperature. -1The process was carried out at a shear rate. Ten readings were recorded at each temperature, and the reported results represent the average viscosity value of the ten different readings. Unless otherwise specified, values ​​are in millipascal-seconds (mPa·s) and 50 s -1 It was recorded as the shear rate.

[0502] To generate films for testing various physical properties, each sample was tested using a Conveyor Fusion Unit Model DRS-10 / 12QN, a 600W UV-lamp system equipped with a 1600M radiator (600 W / inch, which is equivalent to 240 W / cm, for a total of 600 W) and 1 J / cm² as the lamp. 2 The samples were cured under a constant flow of nitrogen gas with UV dose, and the D-bulb was used for sample curing, out of the options with an H-bulb and a D-bulb UV lamp. Subsequently, the UV dose was measured using an International Light IL390 radiometer. Then, individual test strips were cut from the film with a width of approximately 1.27 cm (0.5 inches ± 1 / 32") and a length of approximately 12.7 cm (5 inches ± 1 / 8"). The exact thickness of each specimen was measured using a calibrated micrometer.

[0503] The method for determining the film modulus used herein is described in EP2089333B1, paragraphs

[0132] –

[0133] and

[0135] , the cited portions of which are incorporated herein by reference, except that the cured film was conditioned for at least 24 hours prior to testing. Tensile properties (tensile strength, elongation at break percentage, and segment modulus) were MTS criterions for test strips of the cured film of each sample having a thickness of 3 mil as prepared according to the "film sample preparation" procedure described above. TMIt was determined to be Model 43.104. Due to these relatively soft coatings (e.g., having a modulus of less than about 10 MPa), the coating was drawn down and cured on a glass plate, and after applying a thin layer of talc, individual specimens were cut from the glass plate using a scalpel. An Instron 4442 tensile testing machine with a 0.9 kg (2-lb) load cell was used, and the modulus was calculated at 2.5% elongation as the minimum square foot of the stress-strain plot. The cured films were conditioned for 16 to 24 hours prior to testing at 23.0°C ± 0.1°C and 50.0% ± 0.5% relative humidity. To test the specimens, the gauge length was 5.1 cm (2-inch), and the crosshead speed was 25.4 mm / min. All tests were performed at a temperature of 23.0°C ± 0.1°C and a relative humidity of 50.0% ± 0.5%. All measurements were determined from the average of at least six test specimens. The value for tensile strength was determined by the maximum stress generated by the sample prior to fracture. The value for toughness was determined by the total area under the stress-strain curve.

[0504] Adhesive properties were determined using an Instron Model 4442 tensile tester with test strips of cured films of each sample having a thickness of 3 mil, prepared according to the "Film Sample Preparation" procedure described above. The cured films were then conditioned at 23.0°C ± 2.0°C and 50% ± 5% RH for at least 7 days. If, after 7 days, the peel strength result was too high to test, a new sample was prepared and conditioned at 23.0°C ± 2.0°C and 50% ± 5% RH for 24 hours. Next, the test samples were cut using a scalpel and a 1.00" wide steel bar, with a 1 / 4" gap between the cut specimens and 6" cuts on both sides of the bar. To minimize the influence of minute sample defects, the sample specimens were cut parallel to the direction in which the drawdown of the cured film was manufactured. To reduce blocking during the adhesion test, a thin layer of talc was applied to the first and third strips on each drawdown using a face-tip applicator. For the test, the Instron tensile testing machine Model 4442 was set to a 2 lb load cell, a 20 psi pneumatic grip, and a crosshead speed of 10.00" / min. A clip attached to a braided nylon string was run through the pulley, and the nylon string was clamped to the upper jaw of the Instron testing machine. The first strip was peeled back approximately 1 inch from the glass plate, and the specimen was placed horizontally on the table with the peeled end facing away from the pulley. A binder clip was attached to the peeled end at the rear of the specimen and placed flat on the sample. The plate was pulled to apply tension to the braided nylon string until the load on the Instron was read as positive; at this point, the software method was initiated and continued until the average force value became relatively constant. The test was terminated by clicking the stop button in the software or by loosening the tension on the string. The reported peel strength value is the average of the plateau forces for eight sample runs.

[0505] Table 4A - Preparations 1-7. All listed amounts are in parts by weight.

[0506]

[0507] * Preparations 1 and 5 are comparative examples.

[0508] Table 4B - Preparations 8-10. All listed amounts are in parts by weight.

[0509]

[0510] * Formulation 8 is a comparative example.

[0511] Table 4C - Preparations 11-16. All listed amounts are in parts by weight.

[0512]

[0513] * Preparations 15 and 16 are comparative examples.

[0514] Table 4D - Preparations 17-20. All listed amounts are in parts by weight.

[0515]

[0516] * Preparations 19 and 20 are comparative examples.

[0517] Table 4E - Comparison of Preparations 1, 3, and 4 with Preparations 21-22 (Amounts in parts by weight)

[0518]

[0519] * Preparations 1 and 21-22 are comparative examples.

[0520] Table 4F - Preparations 1, 19 and 23-26. All listed amounts are in parts by weight.

[0521]

[0522] * Preparations 1 and 19 are comparative examples.

[0523] + The 7-day adhesion strength could not be measured because the peel strength was too high and exceeded the cohesive strength of the cured film.

[0524] Table 4G - Preparation 27. All listed amounts are in parts by weight.

[0525]

[0526] * Formulation 15 is a comparative example.

[0527] + The 7-day adhesion strength could not be measured because the peel strength was too high and exceeded the cohesive strength of the cured film.

[0528] As can be seen, compositions according to various aspects of the present invention tend to possess characteristics that make them particularly suitable for use in optical fiber coating applications, particularly as primary coatings adhered to optical fibers, when considering their desirable peel strength, viscosity, tensile strength, elongation, modulus, and toughness.

[0529] Specifically, according to Table 4A, coatings from formulations 2-4 exhibited improved adhesion compared to the coating from formulation 1, and coatings from formulations 6-7 exhibited improved adhesion compared to the coating from formulation 5. As a result of sequentially replacing a portion of oligomer 2 with compound 1 in formulations 1 through 4, peel strength increased with increasing compound 1 content while maintaining a similar level of mechanical performance. Similarly, as a result of sequentially replacing a portion of oligomer 1 with compound 1 in formulations 5 through 7, peel strength also increased with increasing compound 1 content, even though the modulus of formulation 7 was lower than that of formulation 5. Improvements in adhesion were observed despite these compositions possessing a wide range of physical properties, such as viscosity and modulus.

[0530] Improved adhesion was also demonstrated for different compounds of the present invention according to Table 4B, comprising the compositions of formulations 9 and 10 compared with formulation 8. Among the formulations of formulations 9 and 10, the compounds of the present invention contained TDI and IPDI, respectively, where these compounds were also shown to bring about an increase in peel strength compared to the control group while maintaining similar levels of mechanical properties.

[0531] Tables 4C and 4D also demonstrate that formulations containing the compounds of the present invention provided coatings with improved adhesion compared to comparative formulations using acrylated silane TMPSA or mercaptosilane adhesion promoters, which are often used in UV applications. Since both acrylated silane TMPSA and the compounds of the present invention possess the same acrylate UV-curable functional groups, it is more reasonable to use TMPSA as a control than mercaptosilane because mercaptosilane does not possess acrylate functional groups. However, the thiol groups of mercaptosilane are chain-transferred upon UV curing and consequently attached to the terminal ends of the polymer chains. Mercaptosilane often functions much better than acrylated silane TMPSA as adhesion promoters in optical fiber coating applications. Therefore, to demonstrate the remarkable adhesion results from the compounds of the present invention, mercaptosilane was also used as a comparative example. As is evident, the coatings from formulations 11 to 14 exhibited improved adhesion compared to the coatings from formulations 15 and 16, which used the acrylated silane TMPSA and mercaptosilane at a constant total silane content of 2 mmol / 100 g. Additionally, formulation 17, having a higher total silane content of 6.1 mmol / 100 g, provided a coating exhibiting improved adhesion compared to the coatings from formulations 19 and 20 at an equivalent total silane content. The coating from formulation 18 also exhibited improved adhesion compared to the coating from formulation 19, which used the acrylated silane TMPSA.

[0532] Additionally, as demonstrated by formulations 13 and 14 in Table 4C, attaching an aspartate moiety to the nitrogen inside the urea linkage for silane also improved adhesion results. Additionally, as demonstrated by formulation 26 in Table 4F, converting the aspartate moiety inside the urea linkage to hydantoin also improved adhesion results.

[0533] The silane esters were also changed from methoxy to ethoxy in formulations 14 and 26 of Tables 4C and 4F, respectively. Traditionally, ethoxysilanes provide lower adhesion and poorer build-up than methoxysilanes; however, the use of the compounds of the present invention in formulations 14 and 26 surprisingly resulted in coatings with improved adhesion compared to similar coatings using acrylated silanes TMPSA and mercaptosilane, both of which are methoxysilanes. Additionally, the use of these compounds of the present invention is expected to provide superior stability and shelf life due to slower hydrolysis compared to methoxysilanes.

[0534] When coatings prepared from formulations 21-22 using acrylated silane TMPSA were compared with coatings prepared from formulations 3 and 4 (Table 4E) using compound 1 of the present invention, it was observed that significantly improved adhesion results were achieved at similar total silane content levels. Specifically, formulation 3 achieved a 100% improvement compared to formulation 21 simply by replacing the acrylated silane TMPSA with compound 1 of the present invention at a similar silane content of ~4.1-4.3 mmol / 100 g composition. Furthermore, compound 1 of the present invention was much more efficient in improving adhesion, requiring only a 50% increase in total silane to increase peel strength by 65%, whereas acylated silane required a 300% increase in total silane to increase peel strength by 58%. As a result, compared to formulation 22, formulation 4 had about 100% less silane content (6.1 vs 12.8) among formulations, but produced a coating with about 100% greater peel strength (135 vs 63).

[0535] Table 4F addresses whether the hydantoin-containing versions of the compounds of the present invention (Compounds 4 and 7) improved adhesion. As is evident, coatings from formulations 23-26 using Compound 4 or Compound 7 of the present invention at silane levels of 1.1-6.7 mmol / 100 g exhibited improved adhesion compared to coatings from formulation 1, which lacked an adhesion promoter, and from formulation 19, which contained the acrylated silane TMPSA at a silane level of 6.1 mmol / 100 g. Furthermore, as indicated by formulations 23-25, when Compound 1 of the present invention was converted to a hydantoin-containing compound (Compound 4 of the present invention), not only did the peel strength increase again, but Compound 4 also appeared to be more efficient in increasing peel strength compared to that exhibited by Compound 1. In fact, the 7-day adhesion could not be measured for the coatings prepared from formulations 24 and 25 because the peel strength was too high to exceed the cohesive strength of the cured film, a problem that did not occur with its aspartate counterparts, namely formulations 2-4. Additionally, the coatings from formulations 24 and 25 exhibited greater peel strength after 24 hours than the coatings from formulations 2 and 4 at similar total silane levels. The coating from formulation 26 using compound 7 of the present invention (produced by converting compound 6 of the present invention into a hydantoin-containing version) also exhibited improved adhesion compared to the coatings from formulations 1 and 14.

[0536] Table 4G shows the aspartate adhesive monomer of the present invention, in which two silanes are attached to the acrylate. As shown by Formulation 27, the adhesive strength after only 24 hours using Compound 8 exceeded the adhesive strength of the control Formulation 15, which had already been aged for 7 days. For Formulation 27 and Compound 8, the adhesive strength after 7 days was too high to be tested, so the 24-hour adhesive strength was used. The additional silanes attached to the acrylate monomer enabled greater adhesion and higher adhesion to the glass substrate.

[0537] Although the present invention has been described in detail above for illustrative purposes, such details are for that purpose only and should be understood that modifications may be made by those skilled in the art without departing from the spirit and scope of the invention, except as limited by the claims.

Claims

Claim 1 A composition comprising the following: (I) an ethylene-based unsaturated compound comprising the following: (a) Moiety of the following structure (1): ; and (b1) Moiety of the following structure (2): ; or (b2) Moiety of the following structure (3): ; or (b3) A combination of the moiety of structure (2) and the moiety of structure (3), Here, (i) Y represents a linear or branched linker comprising one or more carbon atoms, (ii) each X, which may be the same or different, represents an alkoxy group or an organic group inert to isocyanate groups at a temperature of 100°C or lower, provided that at least one X represents an alkoxy group, and (iii) R, which may be the same or different 1 and R 2 Each represents an organic group that is inert to isocyanate groups at temperatures of 100°C or lower; (iv) R which may be the same or different 3 and R 4 Each represents an organic group that is inert to hydrogen or an isocyanate group at a temperature of 100°C or lower; (v) each " " indicates a link to another part of an ethylene-based unsaturated compound; and (II) an ethylene-based unsaturated oligomer and / or photoinitiator different from the ethylene-based unsaturated compound (I). Claim 2 In paragraph 1, R 3 and R 4 A composition in which both are hydrogen. Claim 3 The composition of claim 1, wherein the ethylene-based unsaturated compound further comprises the following: (c) a segment having the following structure: Here, G is O, S, or NR, where R represents hydrogen or an organic group inert to isocyanate groups at temperatures below 100°C, and each " " indicates a connection to another part of the ethylene-based unsaturated compound. Claim 4 A composition according to claim 1, wherein the molecular weight of the ethylene-based unsaturated compound calculated from the molecular formula of the ethylene-based unsaturated compound is less than 400 to 2000 g / mol, for example, 400 to 1000 g / mol. Claim 5 A composition according to claim 1, wherein the ethylene-based unsaturated compound (I) has the following structure (4A) or structure (4B): Here (i) R 5 represents H or CH3, and (ii) R 6 represents a group containing a branched or straight-chain alkylene radical, and (iii) Y 1 represents a linear or branched linker containing one or more carbon atoms, and (iv) R which may be the same or different 7 and R 8 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, and (v) R which may be the same or different 9 and R 10 Each represents an organic group that is inert to hydrogen or an isocyanate group at a temperature of 100°C or lower, and (vi) each X which may be the same or different. 1 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 1 represents an alkoxy group, and (vii) each q, which may be the same or different, is an integer having a value from 1 to 6, e.g. 1 to 3, e.g.

1. Claim 6 A composition according to claim 1, wherein the ethylene-based unsaturated compound (I) has the following structure (5): Here (i) R 5 represents H or CH3, and (ii) R 6 represents a group containing a branched or straight-chain alkylene radical, and (iii) Y 1 represents a linear or branched linker containing one or more carbon atoms, and (iv) R 7 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, and (v) R which may be the same or different 9 and R 10 Each represents an organic group that is inert to hydrogen or an isocyanate group at a temperature of 100°C or lower, and (vi) each X which may be the same or different. 1 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 1 represents an alkoxy group, and (vii) each q, which may be the same or different, is an integer having a value from 1 to 6, e.g. 1 to 3, e.g.

1. Claim 7 A composition according to claim 1, wherein the ethylene-based unsaturated compound (I) has the following structure (6): Here (i) R 5 represents H or CH3, and (ii) R 6 represents a group containing a branched or straight-chain alkylene radical, and (iii) R, which may be the same or different. 7 and R 8 ☐ exhibits an organic group that is inert to isocyanate groups at temperatures below 100°C, and (iv) R which may be the same or different 9 and R 10 represents, respectively, hydrogen or an organic group inactive to isocyanate groups at temperatures below 100°C, (v) Z represents an organic group inactive to isocyanate groups at temperatures below 100°C, and (vi) each Y which may be the same or different 1 represents a linear or branched linker containing one or more carbon atoms, and (vii) each X, which may be the same or different. 1 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 1 (viii) each q, which may be the same or different, is an integer having a value from 1 to 6, e.g. 1 to 3, e.g. 1, and (ix) q1 is 0 or 1. Claim 8 A composition according to claim 1, wherein the ethylene-based unsaturated compound (I) has the following structure (7): Here (i) R 5 represents H or CH3, and (ii) R 6 represents a group containing a branched or straight-chain alkylene radical, and (iii) R, which may be the same or different. 7 and R 8 ☐ exhibits an organic group that is inert to isocyanate groups at temperatures below 100°C, and (iv) R which may be the same or different 9 and R 10 represents, respectively, hydrogen or an organic group inactive to isocyanate groups at temperatures below 100°C, (v) Z represents an organic group inactive to isocyanate groups at temperatures below 100°C, and (vi) each Y which may be the same or different 1 represents a linear or branched linker containing one or more carbon atoms, and (vii) each X, which may be the same or different. 1 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 1 (viii) each q, which may be the same or different, is an integer having a value from 1 to 6, e.g. 1 to 3, e.g. 1, and (ix) q1 is 0 or 1. Claim 9 A composition according to claim 1, wherein the ethylene-based unsaturated compound (I) has the following structure (8): Here, (i) each R which may be the same or different 5 represents H or CH3, and (ii) each R, which may be the same or different. 6 represents a group containing a branched or straight-chain alkylene radical, and (iii) Z 1 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, and (iv) each Y which may be the same or different 1 represents a linear or branched linker containing one or more carbon atoms, and (v) each R which may be the same or different. 7 and R 8 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, and (vi) each R which may be the same or different 9 and R 10 represents an organic group that is inert to hydrogen or isocyanate groups at temperatures below 100°C, and (vii) each X which may be the same or different. 1 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 1 (viii) m and n, which may be the same or different, are integers having values ​​from 1 to 4, and (ix) each q may be the same or different, and is an integer having values ​​from 1 to 6, e.g. 1 to 3, e.g.

1. Claim 10 A composition according to claim 1, wherein the ethylene-based unsaturated compound (I) has the following structure (9): Here, (i) each R which may be the same or different 5 represents H or CH3, and (ii) each R, which may be the same or different. 6 represents a group containing a branched or straight-chain alkylene radical, and (iii) Z 1 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, and (iv) each Y which may be the same or different 1 represents a linear or branched linker containing one or more carbon atoms, and (v) each R which may be the same or different. 7 and R 8 represents an organic group that is inert to isocyanate groups at temperatures below 100°C, and (vi) each R which may be the same or different 9 and R 10 represents an organic group that is inert to hydrogen or isocyanate groups at temperatures below 100°C, and (vii) each X which may be the same or different. 1 It represents an alkoxy group or an organic group inert to isocyanate groups at temperatures below 100°C, provided that at least one X 1 (viii) m and n, which may be the same or different, are integers having values ​​from 1 to 4, and (ix) each q, which may be the same or different, is an integer having a value from 1 to 6, e.g. 1 to 3, e.g.

1. Claim 11 A composition according to claim 1, wherein the ethylene-based unsaturated compound (I) is present in an amount of 0.01 to 99 weight%, 0.1 to 20 weight%, 1 to 50 weight%, 5 to 30 weight%, 40 to 70 weight%, 60 to 80 weight%, 65 to 99 weight%, or 0.01 to 20 weight% based on the total weight of the solid in the composition. Claim 12 A composition comprising a urethane (meth)acrylate oligomer comprising a reaction product of a reactant comprising (1) a polyol, (2) a polyisocyanate, and (3) a hydroxyl group-containing (meth)acrylate, wherein an ethylene-based unsaturated oligomer (II) is present. Claim 13 A composition according to claim 12, wherein the polyol comprises a diol and the polyisocyanate comprises a diisocyanate. Claim 14 A composition according to claim 12, wherein the urethane (meth)acrylate oligomer is present in an amount of 30 to 95 weight percent based on the total weight of the solid in the composition. Claim 15 A composition according to claim 1, further comprising a reactive diluent compound having one or more ethylene-based unsaturated groups, wherein the reactive diluent compound is present in an amount of 5 to 90 weight percent based on the total weight of the solid in the composition. Claim 16 A composition in which a photoinitiator is present in the composition, as in Clause 12. Claim 17 A cured coating formed from the composition of claim 1. Claim 18 A substrate that is at least partially coated with the cured coating of claim 17, wherein the substrate comprises an optical fiber. Claim 19 A method for coating an optical fiber, comprising: (a) providing a glass optical fiber; (b) applying a primary coating composition onto the surface of the glass optical fiber; (c) optionally applying a dose of UV light sufficient to at least partially cure the primary coating composition; (d) applying a secondary coating composition to the primary coating composition; and (e) exposing the secondary coating composition to at least one radiation source capable of emitting ultraviolet radiation to induce curing of the secondary coating composition and optionally the primary coating composition, wherein the primary coating composition and / or the secondary coating composition comprises the composition of claim 1. Claim 20 A coated optical fiber comprising: (a) a glass core and a cladding layer in contact with and surrounding the glass core; and (b) a coating portion that at least partially coats the cladding layer, (i) a primary coating layer in contact with the cladding layer; and (ii) A secondary coating layer that contacts and surrounds the primary coating layer. A coated optical fiber comprising a coating portion including, wherein the primary coating layer and / or secondary coating layer is the cured coating of claim 17. Claim 21 A composition according to claim 1, wherein at least one carbon-carbon double bond of the ethylene-based unsaturated compound (I) exists as a =CH2 terminal group, and there are no additional substituents on the carbon. Claim 22 A composition according to claim 1, wherein the ethylene-based unsaturated compound (I) comprises the terminal group of structure (1) and the terminal group of structure (1a): Here, E represents a group containing a polymerizable carbon-carbon double bond, such as an acryloyl, methacryloyl, or vinyl group, and represents a link to another part of the ethylene-based unsaturated compound. Claim 23 In claim 22, a composition in which the terminal group of structure (1a) has structure (1b): Here, R 3 It is H or CH3, and represents a connection to another part of the ethylene-based unsaturated compound (I).

23. The composition of Claim 1, wherein the ethylene-based unsaturated compound (I) comprises a moiety of structure 3A: Here, X, Y, R 1 , R 2 and " " is as described in paragraph 1 for each structure (1)-(3). Claim 24 A composition according to claim 1, provided that the ethylene-based unsaturated compound (I) has at least one moiety of structure 3B: Here, X, Y, R 1 , R 2 and " " is as described for each structure (1)-(3). Claim 25 A composition according to claim 1, provided that the ethylene-based unsaturated compound (I) has at least one moiety of the following structure 2A: Here, X, Y, R 1 , R 2 and " " is as described for each structure (1)-(3). Claim 26 A composition according to claim 1, provided that the ethylene-based unsaturated compound (I) has 0 or 2 to 4 moiety groups of the structure 2B below: Here, X, Y, R 1 , R 2 and " " is as described for each structure (1)-(3).

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