Polysilanes, process for their preparation and their use in coating compositions

Abstract

Polysilane compounds containing aspartate groups and / or hydantoin groups are described. Methods of making and using such compounds are also disclosed, for example their use in coating compositions, such as in coating compositions suitable for optical glass fiber substrates.

Description

Technical Field

[0001] This specification relates to polysilane compounds that can be used as adhesion-promoting compounds. It also relates to methods for preparing such compounds and their use in, for example, coating compositions. Background Technology

[0002] The general formula is R-Si(OR) 1 )3 organosilanes, where R is an organic group, R 1 Alkyl groups, such as methyl or ethyl, have a variety of uses, including as adhesion promoters, surface modifiers, release agents, rheology modifiers, crosslinking agents, and hydrophobic agents in coating compositions. These alkoxysilanes can form siloxane bonds (—Si—O—Si—) with water molecules on glass or metal surfaces through a hydrolytic reaction, thereby achieving tight adhesion to non-porous surfaces such as glass, polymers, or metals. Therefore, continuous efforts are made to improve the properties of organosilanes, often to enhance their adhesion-promoting characteristics.

[0003] In view of the above, there is an urgent need to provide adhesive-promoting compounds containing alkoxysilanes that can be synthesized conveniently and efficiently, and that exhibit significantly improved adhesive properties compared to other adhesive promoters (including other adhesive promoters containing alkoxysilanes). Summary of the Invention

[0004] In some respects, this specification relates to polysilane compounds. The polysilane compounds comprise: (a) at least two portions of structure (1): (1); and (b1) Part of structure (2): (2); or (b2) Part of structure (3): (3); or (b3) The combination of parts of structure (2) and parts of structure (3), Wherein (i) Y represents a straight-chain or branched linking group containing one or more carbon atoms, (ii) each X may be the same or different, representing an alkoxy group or an organic group that is inert to isocyanate groups at 100°C or lower, provided that at least one X represents an alkoxy group, and (iii) each R 1 They may be the same or different, indicating organic groups that are inert to the isocyanate group at 100°C or lower; (iv) each R 2 They may be the same or different, representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower; and (v) " "" indicates a connection to another part of the polysilane compound.

[0005] This specification also relates to methods for preparing such polysilane compounds, compositions containing such polysilane compounds (such as coating compositions), and substrates at least partially coated with a coating deposited from such coating compositions. Detailed Implementation

[0006] This specification describes and illustrates various embodiments to provide a comprehensive understanding of the structure, function, nature, and use of the disclosed invention. It should be understood that the various embodiments described and illustrated in this specification are non-limiting and non-exhaustive. Therefore, the invention is not limited to the description of the various non-limiting and non-exhaustive embodiments disclosed in this specification. Features and characteristics described in connection with various embodiments may be combined with features and characteristics of other embodiments. These modifications and variations are intended to be included within the scope of this specification. Therefore, the claims may be modified to record any feature or characteristic explicitly or implicitly described in this specification, or otherwise explicitly or implicitly supported. Furthermore, the applicant reserves the right to modify the claims to expressly exclude features or characteristics that may be present in the prior art. Therefore, any such modifications are in compliance with the requirements of 35 USC § 112 and 35 USC § 132(a). The various embodiments disclosed and described in this specification may comprise, consist of, or substantially consist of the features and characteristics differently described herein.

[0007] Unless otherwise stated, any patent, publication, or other disclosure referenced in this specification is incorporated herein by reference in its entirety, provided that the incorporated material does not conflict with any existing definitions, statements, or other disclosures expressly set forth in this specification. Therefore, if necessary, the express disclosures set forth in this specification shall supersede any conflicting material incorporated herein by reference. Any material or portion thereof incorporated herein by reference that conflicts with any existing definitions, statements, or other disclosures set forth herein shall be incorporated only to the extent that such conflict will not arise. The applicant reserves the right to amend this specification to expressly describe any subject matter or portion thereof incorporated herein by reference.

[0008] In this specification, unless otherwise stated, all numerical parameters should be understood to be modified in all cases by the term "about," meaning that the numerical parameter has the variability inherent in the underlying measurement technique used to determine the value of the parameter. At least, and not at all, the application of the doctrine of equivalence should be limited to the scope of the claims, each numerical parameter described in this specification should be interpreted at least according to the number of significant figures reported and by applying conventional rounding techniques.

[0009] Furthermore, any numerical range described in this specification is intended to include all subranges falling within that range and having the same numerical precision. For example, the range “1.0 to 10.0” is intended to include all subranges between the stated minimum value of 1.0 and the stated maximum value of 10.0, i.e., ranges having a minimum value greater than or equal to 1.0 and a maximum value less than or equal to 10.0, such as 2.4 to 7.6. Any maximum numerical limit described in this specification is intended to include all lower numerical limits contained therein, and any minimum numerical limit described in this specification is intended to include all higher numerical limits contained therein. Therefore, the applicant reserves the right to modify this specification (including the claims) to expressly describe any subranges within the ranges expressly described herein. All such ranges are intended to be inherently described in this specification such that modifications made to expressly describe any such subranges will comply with the requirements of 35 USC § 112 and 35 USC § 132(a).

[0010] The grammatical articles “a,” “one,” “a,” and “the” used in this specification include “at least one” or “one or more”, unless otherwise expressly stated. Therefore, these articles are used in this specification to refer to one or more of their grammatical objects (i.e., “at least one”).

[0011] In this specification, "Si" refers to silicon, "H" refers to hydrogen, "N" refers to nitrogen, "O" refers to oxygen, and "S" refers to sulfur.

[0012] As previously stated, certain embodiments of this specification relate to polysilane compounds. In some embodiments, the molecular weight (calculated based on the molecular formula of the polysilane compound) of the polysilane compound described herein is from 400 to less than 2000 g / mol, for example, from 400 to 1000 g / mol. The polysilane compound contains at least two (in some cases exactly two) alkoxysilane (“Si(X)3”) groups.

[0013] More specifically, the polysilane compounds of this specification comprise: (a) at least two parts of structure (1): (1); and (b1) Part of structure (2): (2); or (b2) Part of structure (3): (3); or (b3) The combination of parts of structure (2) and parts of structure (3), Wherein (i) Y represents a straight-chain or branched linking group containing one or more carbon atoms, (ii) each X may be the same or different, representing an alkoxy group or an organic group that is inert to isocyanate groups at 100°C or lower, provided that at least one X represents an alkoxy group, and (iii) each R 1 They may be the same or different, indicating organic groups that are inert to the isocyanate group at 100°C or lower; (iv) each R 2 They may be the same or different, representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower; and (v) " "" indicates a connection to another part of the polysilane compound, for example, wherein the molecular weight of the polysilane compound (calculated according to the molecular formula of the polysilane compound) is 400 to less than 2000 g / mol, for example 400 to 1000 g / mol. In some embodiments, the polysilane compound has 1 to 4, for example 1 to 2 parts of structure (2), and / or 1 to 4, for example 1 to 2 parts of structure (3).

[0014] As described above, each X may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X represents an alkoxy group. As used herein, a group “inert to the isocyanate group at 100°C or lower” means that it is inert to the isocyanate group at that temperature when the group is covalently attached to another atom in the structure under discussion, as shown in the various structures illustrated herein. It should be understood that the zeravitinov active hydrogen is not inert to the isocyanate group at such a temperature; therefore, any organic group described herein as inert to the isocyanate group at 100°C or lower does not contain zeravitinov active hydrogen (the definition of zeravitinov active hydrogen is found in Rompp's Chemical Dictionary (Rommp Chemie Lexikon), 10th edition, Georg Thieme Verlag Stuttgart, 1996). Generally, groups having zeravitinov active hydrogen in the art are understood to refer to hydroxyl (OH), amino (NH4) groups, etc. X ) and thiol (SH) groups.

[0015] In some implementations, R in structures (2) and (3) 1 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, such as R in structures (2) and (3). 1 They may be the same or different, representing methyl, ethyl, propyl or butyl, and R in structures (2) and (3) 2They may be the same or different, representing hydrogen or alkyl, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, such as R in structures (2) and (3). 2 The terms may be the same or different, representing methyl, ethyl, propyl, or butyl. Furthermore, in some embodiments, each X in structure (1) represents the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X represents an alkoxy group, for example, at least two Xs representing alkoxy groups such as methoxy, ethoxy, or propoxy, or each X represents an alkoxy group such as methoxy, ethoxy, or propoxy. Additionally, in some cases, Y in structure (1) comprises a straight-chain or branched alkylene group having 1 to 8 carbon atoms, for example, a straight-chain alkylene group having 2 to 4 or, in some cases, 3 carbon atoms, or a branched alkylene group having 5 to 6 carbon atoms.

[0016] In addition, in some embodiments of any polysilane compound described in this specification, the polysilane compound further comprises: (c) a segment with the following structure: Where G is O, S, or NR, and R represents hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, and each " "" indicates a connection to another part of the polysilane compound. In some embodiments, the polysilane compound has 1 to 4 such segments.

[0017] In some embodiments, any polysilane compound described herein (e.g., any polysilane containing the portion of structure (3)) contains the portion of structure 3A: (3A) Where X, Y, R 1 R 2 and" "Each is as described above regarding structures (1)-(3). In some embodiments, the polysilane compound has 1 to 4 such structural 3A portions."

[0018] In some embodiments, any polysilane compound described herein (e.g., any polysilane containing a portion of structure (3)) comprises the following condition: the polysilane compound has only one portion of structure 3B: (3B) Where X, Y, R 1 R 2 and" "Each is as described above regarding structure (1)-(3)."

[0019] In some embodiments, any polysilane compound described herein (e.g., any polysilane containing a portion of structure (2)) comprises the following condition: the polysilane compound has only one portion of structure 2A: (2A) Where X, Y, R 1 R 2 and" "Each is as described above regarding structure (1)-(3)."

[0020] In some embodiments, any polysilane compound described herein (e.g., any polysilane containing a portion of structure (2)) comprises the following condition: the polysilane compound has only one portion of structure 2B: (2B) Among them, X, Y and " "Each is as described above regarding structures (1)-(3), and R..." 0 It is not hydrogen. More specifically, in some embodiments, part of structure 2B has structure 2B(i): (2B(i)) Where X, Y, R 1 R 2 and" "Each is as described above regarding structure (1)-(3)."

[0021] In some embodiments, the polysilane compound of this specification has structure (4): (4) Where (i) is each Y 1 They can be the same or different, representing straight-chain or branched linking groups containing one or more carbon atoms, (ii) each R 3 They may be the same or different, indicating organic groups that are inert to isocyanate groups at 100°C or lower, (iii) each R 4 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, (iv) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 (v) Z represents an alkoxy group, which is inert to the isocyanate group at 100°C or lower, and in some cases is a divalent organic group, for example optionally containing a hydrocarbon group of oxygen, nitrogen, sulfur or a combination thereof that is inert to the isocyanate group, and comprising C1 to C2. 18Alkylene or C5-C6 cycloalkylene, and (vi) m and n may be the same or different, each being an integer from 1 to 5, for example 1 to 3, or 1. In some embodiments, m+n is 2 to 10, for example 2 to 4, or 2.

[0022] Furthermore, in some embodiments of the polysilane compound represented by structure (4), each R in structure (4) 3 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, each R 3 They may be the same or different, representing methyl, ethyl, propyl, or butyl. Furthermore, in some embodiments, each X in structure (4) 1 Representing the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 To indicate an alkoxy group, for example, at least two X groups. 1 Indicates alkoxy groups such as methoxy, ethoxy, or propoxy, or each X 1 This indicates an alkoxy group, such as methoxy, ethoxy, or propoxy. Furthermore, in some cases, each Y in structure (4) 1 They may be the same or different, containing straight-chain or branched alkylene groups having 1 to 8 carbon atoms, such as straight-chain alkylene groups having 2 to 4 carbon atoms or, in some cases, 3 carbon atoms, or branched alkylene groups having 5 to 6 carbon atoms.

[0023] In some embodiments of the polysilane compound represented by structure (4), Z is: ; ; , where the value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. ; ; ; ; ; ; ; , Each of these " "" indicates a connection to another part of the polysilane compound.

[0024] In other embodiments, the polysilane compound of this specification has structure (5): (5) Where R 3 R 4 Y 1 X 1 Z, m and n are each as described above regarding structure (4).

[0025] In other embodiments, the polysilane compound of this specification has the structure (6): (6) Where: (i) Each Y 1 They can be the same or different, representing straight-chain or branched connecting groups containing one or more carbon atoms, (ii) Y 2 Groups representing the following structures: ,in Indicates Y 1 The connection, Indicates a connection with N, where G is O, S, or NR, where R is hydrogen or an organic group inert to isocyanate groups at 100°C or lower, Z represents an organic group inert to isocyanate groups at 100°C or lower, such as a hydrocarbon group or an oxygen-containing hydrocarbon group in the structure, (iii) p is 0 or 1, (iv) each R 3 They may be the same or different, indicating organic groups that are inert to the isocyanate group at 100°C or lower; (v) each R 4 They may be the same or different, representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower; and (vi) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 It represents an alkoxy group.

[0026] In some embodiments of the polysilane compound represented by structure (6), each R in structure (6) 3 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, such as each R in structure (6). 3 They may be the same or different, representing methyl, ethyl, propyl, or butyl. Furthermore, in some embodiments, each X in structure (6) 1Representing the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 To indicate an alkoxy group, for example, at least two X groups. 1 Indicates alkoxy groups such as methoxy, ethoxy, or propoxy, or each X 1 This indicates an alkoxy group, such as methoxy, ethoxy, or propoxy. Furthermore, in some embodiments, each Y in structure (6) 1 They may be the same or different, containing straight-chain or branched alkylene groups having 1 to 8 carbon atoms, such as straight-chain alkylene groups having 2 to 4 carbon atoms or, in some cases, 3 carbon atoms, or branched alkylene groups having 5 to 6 carbon atoms.

[0027] In some embodiments of the polysilane compound represented by structure (6), Z is: ; ; , where the value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. ; ; ; ; ; ; ; , of which each "" indicates a connection to another part of the polysilane compound.

[0028] In other further embodiments, the polysilane compound of this specification has the structure (7): (7) Where R 3 R 4 X 1 Y 1 Y 2 p and p are as described above regarding structure (6).

[0029] In other embodiments, the polysilane compound of this specification has the structure (8): Where: (i) Each Y 1 They can be the same or different, representing straight-chain or branched connecting groups containing one or more carbon atoms, (ii) each Y 2 The groups can be the same or different, representing the following structures: ,in Indicates Y 1 The connection, Indicates a connection with N, where G is O, S, or NR, where R is hydrogen or an organic group inert to isocyanate groups at 100°C or lower, and Z represents an organic group inert to isocyanate groups at 100°C or lower, such as a hydrocarbon group or an oxygen-containing hydrocarbon group in the structure; (iii) each p can be the same or different, and can be 0 or 1; (iv) each R 3 Can be the same or different, indicating an organic group that is inert to the isocyanate group at 100°C or lower, (v) each R 4 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, (vi) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 (vii) Z represents an alkoxy group, which is inert to the isocyanate group at 100°C or lower, and in some cases is a divalent organic group, for example, optionally containing a hydrocarbon group of oxygen, nitrogen, sulfur or a combination thereof that is inert to the isocyanate group, and comprising C1 to C2. 18 Alkylene or C5-C6 cycloalkylene, and (viii) m and n may be the same or different, each being an integer from 1 to 5, for example 1 to 3, or 1. In some embodiments, m+n is 2 to 10, for example 2 to 4, or 2.

[0030] Furthermore, in some embodiments of the polysilane compound represented by structure (8), each R in structure (8) 3 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, each R 3 They may be the same or different, representing methyl, ethyl, propyl, or butyl. Furthermore, in some embodiments, each X in structure (8) 1 Representing the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 To indicate an alkoxy group, for example, at least two X groups.1 Indicates alkoxy groups such as methoxy, ethoxy, or propoxy, or each X 1 This indicates an alkoxy group, such as methoxy, ethoxy, or propoxy. Furthermore, in some cases, each Y in structure (8) represents an alkoxy group. 1 They may be the same or different, containing straight-chain or branched alkylene groups having 1 to 8 carbon atoms, such as straight-chain alkylene groups having 2 to 4 carbon atoms or, in some cases, 3 carbon atoms, or branched alkylene groups having 5 to 6 carbon atoms.

[0031] In some embodiments of the polysilane compound represented by structure (8), Z is: ; ; , where the value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. ; ; ; ; ; ; ; Each of these " "" indicates a connection to another part of the polysilane compound.

[0032] In a further embodiment, the polysilane compound of this specification has the structure (9): Where R 3 R 4 X 1 Y 1 Y 2 Z, m, n and p are each as described above regarding structure (8).

[0033] In other embodiments, the polysilane compound of this specification has the structure (10): Where (i) each Y 1They can be the same or different, representing straight-chain or branched connecting groups containing one or more carbon atoms, (ii) each Y 2 The groups can be the same or different, representing the following structures: ,in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) each p may be the same or different, and may be 0 or 1; (iv) each R 3 Can be the same or different, indicating an organic group that is inert to the isocyanate group at 100°C or lower, (v) each R 4 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, (vi) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 (vii) Z represents an alkoxy group, which is inert to the isocyanate group at 100°C or lower, and in some cases is a divalent organic group, for example, optionally containing a hydrocarbon group of oxygen, nitrogen, sulfur or a combination thereof that is inert to the isocyanate group, and comprising C1 to C2. 18 Alkylene or C5-C6 cycloalkylene, and (viii) m+n is 2 to 10, for example 2 to 4, or 2.

[0034] Furthermore, in some embodiments of the polysilane compound represented by structure (10), each R in structure (10) 3 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, each R 3 They may be the same or different, representing methyl, ethyl, propyl, or butyl. Furthermore, in some embodiments, each X in structure (10) 1 Representing the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 To indicate an alkoxy group, for example, at least two X groups. 1 Indicates alkoxy groups such as methoxy, ethoxy, or propoxy, or each X 1 This indicates an alkoxy group, such as methoxy, ethoxy, or propoxy. Furthermore, in some embodiments, each Y in structure (10) represents an alkoxy group. 1They may be the same or different, containing straight-chain or branched alkylene groups having 1 to 8 carbon atoms, such as straight-chain alkylene groups having 2 to 4 carbon atoms or, in some cases, 3 carbon atoms, or branched alkylene groups having 5 to 6 carbon atoms.

[0035] In some embodiments of the polysilane compound represented by structure (10), Z is: , where the value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. ; ; ; Each of these " "" indicates a connection to another part of the polysilane compound.

[0036] In other embodiments, the polysilane compound of this specification has the structure (11): Where R 3 R 4 X 1 Y 1 Y 2 Z, m, n and p are each as described above regarding structure (10).

[0037] Some embodiments of the polysilane compounds in this specification are reaction products comprising reactants containing: (a) a polyisocyanate, such as a diisocyanate; and (b) an aspartic ester silane. In these embodiments, the aspartic ester silane has the following structure: Each R 15 and each X 4They may be the same or different, representing organic groups that are inert to isocyanate groups at 100°C or lower, provided that at least one X 4 Y represents an alkoxy group. 4 This indicates a straight-chain or branched linking group containing one or more carbon atoms, and each R 15b They can be the same or different, indicating hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower.

[0038] The aforementioned aspartic acid ester silane may contain reaction products containing reactants of the following formula: (i) H2N-(CH2)n-Si(X) 5 )3 aminoalkylalkoxysilanes, and (ii) formula R 16 OOC-CR 18 =CR 18 -COOR 17 Maleate or fumarate, wherein R 16 and R 17 This refers to the same or different organic groups that are inert to isocyanates below 100°C, such as R. 16 and R 17 Represents the same or different alkyl groups having 1 to 4 carbon atoms, each R 18 They may be the same or different, representing hydrogen or an organic group that is inert to isocyanates below 100°C, each X 5 This refers to the same or different organic groups that are inert to isocyanates below 100°C, provided that at least one X group is present. 5 It is an alkoxy group, for example, each X 5 To represent the same or different alkyl or alkoxy groups having 1 to 4 carbon atoms, provided that at least one X 5 It is an alkoxy group, and n is an integer from 2 to 4, for example, 3.

[0039] Specific examples of suitable aminoalkylalkoxysilanes include, but are not limited to: 2-aminoethyldimethylmethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, or any mixture of two or more thereof. Specific examples of suitable maleic esters or fumarates include, but are not limited to: dimethyl maleate, diethyl maleate, di-n-butyl maleate, dimethyl fumarate, diethyl fumarate, di-n-butyl fumarate, or any mixture of two or more thereof.

[0040] The reaction of maleate or fumarate with aminoalkylalkoxysilane can be carried out in a temperature range, for example, from 0°C to 100°C. The amount of ester to aminoalkylalkoxysilane can be selected such that the molar ratio of ester to aminoalkylalkoxysilane is 0.8 to 1.2:1, for example, 1.0 to 1.2:1, or in some cases 1.01 to 1.2:1. The reaction can be carried out with or without a solvent (such as dioxane). The reaction can, of course, be carried out using mixtures of different 3-aminoalkylalkoxysilanes and mixtures of fumarate and / or maleate.

[0041] Suitable polyisocyanates for reacting with aspartic ester silanes to prepare polysilane compounds according to certain embodiments of this specification can be represented by the following structures: Wherein Z represents an organic group that is inert to the isocyanate group at 100°C or lower, and in some cases is a divalent organic group, for example optionally containing a hydrocarbon group of oxygen, nitrogen, sulfur or a combination thereof that is inert to the isocyanate group, and comprising C1 to C2. 18 Alkylene or C5-C6 cycloalkylene, where m and n may be the same or different, each being an integer from 1 to 5, for example, 1 to 3, or 1. In some embodiments, m+n is 2 to 10, for example, 2 to 4, or 2. In some cases, Z in the aforementioned polyisocyanate structure is: , where the value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. ; ; ; Each of these " "" indicates a connection to another part of the polysilane compound.

[0042] Specific examples of suitable polyisocyanates for reaction with aspartic acid ester silanes include, but are not limited to: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene 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′-diphenylmethane diisocyanate, and 4,4′-diphenylmethane diisocyanate. Benzene diisocyanate, 1,6-hexanediisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl)isocyanate, 2,2,4-trimethylhexamethylene diisocyanate, bis(2-ethyl isocyanate) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4,4′-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated diphenylene diisocyanate, tetramethyl diphenylene diisocyanate, lysine isocyanate, hexamethylene diisocyanate trimer (Desmodur®) N3300A, commercially available from Covestro, triphenylmethane-4,4′,4″-triisocyanate (Desmodur® RE, commercially available from Covestro), hexamethylene diisocyanate trimer (Desmodur® N3200, commercially available from Covestro), aromatic polyisocyanates based on toluene diisocyanate (Desmodur® ILBA, commercially available from Covestro), polyisocyanurates based on toluene diisocyanate (Desmodur® RC, commercially available from Covestro), and any combination of two or more of them.

[0043] The reaction of polyisocyanates with aspartic ester silanes can 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, such as catalysts comprising copper compounds (e.g., copper naphthenate), cobalt compounds (e.g., cobalt naphthenate), zinc compounds (e.g., zinc naphthenate), bismuth compounds (e.g., bismuth neodecanoate), tin compounds (e.g., di-n-butyltin dilaurate), triethylamine, triethylenediamine, 1,4-diazabicyclo[2.2.2]octane (DABCO), dimethylethanolamine (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. Furthermore, in some embodiments, the relative amounts of reactants are such that the molar ratio of the isocyanate reactive group to the isocyanate group is at least 1:1, for example, greater than 1 and less than 1.5. The resulting polysilane compound comprises an aspartic ester group from the aspartic ester silane, for example, as shown in the previously described structure (4).

[0044] In some embodiments, the resulting polysilane compound containing aspartic ester groups is further processed to convert the aspartic ester groups into hydantoin groups, wherein the conversion is optionally carried out in the presence of a catalyst (e.g., a Bronsted acid, carboxylic acid, sulfonic acid, phenol, or any two or more of the thereof) at a reaction temperature of 0 to 200 °C, 70 to 130 °C, 90 to 120 °C, or 100 to 120 °C. The resulting polysilane compound contains hydantoin groups, for example, as shown in the previously described structure (5).

[0045] Therefore, this specification also relates to methods for preparing polysilane compounds. These methods involve reacting a polyisocyanate with an aspartic ester silane, optionally in the presence of a catalyst, to produce a polysilane compound comprising an aspartic ester group. In these methods, the aspartic ester silane has the following structure: Each R 17 They can be the same or different, representing organic groups that are inert to the isocyanate group at 100°C or lower. Each X 6 This indicates an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 6 Y represents an alkoxy group. 5 This indicates an organic group that is inert to the isocyanate group at 100°C or lower. In some embodiments, the method further includes converting the aspartic ester group to a hydantoin group, wherein the conversion is optionally carried out in the presence of a catalyst to produce a polysilane compound comprising the hydantoin group.

[0046] In other embodiments, the polysilane compounds of this specification comprise reaction products containing: (a) aspartic ester silanes; and (b) isocyanate-functionalized silanes. In these embodiments, suitable aspartic ester silanes include, but are not limited to, those previously described that react with polyisocyanates. Suitable isocyanate-functionalized silanes for reacting with aspartic ester silanes include, but are not limited to, those with the following structures: Where Y 1 This refers to a straight-chain or branched linking group containing one or more carbon atoms, such as Y. 1 Contains a straight-chain or branched alkylene group having 1 to 8 carbon atoms, such as a straight-chain alkylene group having 2 to 4 carbon atoms, or in some cases 3 carbon atoms, or a branched alkylene group having 5 to 6 carbon atoms, (ii) Y 2 Groups representing the following structures: in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) p is 0 or 1, and (iv) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 Indicates alkoxy groups, for example, each X 1 Representing the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 To indicate an alkoxy group, for example, at least two X groups. 1 Indicates alkoxy groups such as methoxy, ethoxy, or propoxy, or each X 1 It indicates an alkoxy group, such as methoxy, ethoxy, or propoxy.

[0047] Specific examples of suitable isocyanate-functionalized silanes include, but are not limited to: 3-propylmethyldimethoxysilane, 3-propyltrimethoxysilane, 3-propyltriethoxysilane, reaction products of silanes containing active hydrogen (e.g., hydroxyl, thiol, primary or secondary amine functionalized silanes) with polyisocyanates (e.g., any polyisocyanates mentioned above) to provide isocyanate-functionalized silanes containing urethane, thiourethane, urea, or in some cases aspartic urea groups, and mixtures of any two or more of the above isocyanate-functionalized silanes.

[0048] The reaction of isocyanate-functionalized silanes with aspartic ester silanes (if desired) can be carried out in the presence of a catalyst. Suitable catalysts include, but are not limited to, organometallic catalysts, amine catalysts, or combinations thereof, such as catalysts comprising copper compounds (e.g., copper naphthenate), cobalt compounds (e.g., cobalt naphthenate), zinc compounds (e.g., zinc naphthenate), bismuth compounds (e.g., bismuth neodecanoate), tin compounds (e.g., di-n-butyltin dilaurate), triethylamine, triethylenediamine, 1,4-diazabicyclo[2.2.2]octane (DABCO), dimethylethanolamine (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. Furthermore, in some embodiments, the relative amounts of reactants are such that the molar ratio of the isocyanate reactive group to the isocyanate group is at least 1:1, for example, greater than 1 and less than 1.5. The resulting polysilane compound comprises an aspartic ester group from the aspartic ester silane, for example, as shown in the previously described structure (6).

[0049] In some embodiments, the resulting polysilane compound containing aspartic ester groups is further processed to convert the aspartic ester groups into hydantoin groups, wherein the conversion is optionally carried out in the presence of a catalyst (e.g., a Bronsted acid, carboxylic acid, sulfonic acid, phenol, or any two or more of the thereof) at a reaction temperature of 0 to 200 °C, 70 to 130 °C, 90 to 120 °C, or 100 to 120 °C. The resulting polysilane compound contains hydantoin groups, for example, as shown in the previously described structure (7).

[0050] Therefore, this specification also relates to a method for preparing a polysilane compound, comprising reacting (a) an aspartic ester silane as described above with (b) an isocyanate-functionalized silane as described above, optionally in the presence of a catalyst, to produce a polysilane compound comprising an aspartic ester group. In some embodiments, the method further comprises converting the aspartic ester group to a hydantoin group, wherein the conversion is optionally carried out in the presence of a catalyst to produce a polysilane compound comprising a hydantoin group.

[0051] In other embodiments, the polysilane compounds of this specification comprise reaction products containing reactants of: (a) aspartic acid esters and / or polyaspartic acid esters containing primary amines; and (b) isocyanate-functionalized silanes. In these embodiments, suitable isocyanate-functionalized silanes include, but are not limited to, those previously described that react with aspartic acid ester silanes.

[0052] Primary amine-containing aspartic esters and / or polyaspartic esters suitable for preparing such polysilane compounds are represented by the following structures: , Z 1 R represents a hydrocarbon group (in some cases a divalent hydrocarbon group), which may optionally be substituted with oxygen, nitrogen, sulfur, or a combination thereof. 18 and R 19 They can be the same or different, indicating organic groups that are inert to the isocyanate group at 100°C or lower, such as R. 18 and R 19 Represents the same or different alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, R. 18 and R 19 They can be the same or different, each being methyl, ethyl, propyl, or butyl, R 20 and R 21 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower. m and n may be the same or different, each being an integer from 0 to 4, provided that m+n is at least 2.

[0053] Aspartic acid esters containing primary amines can be made into (NH2)mZ1 (NH2) n primordine (of which Z) 1 Optionally containing a hydrocarbon group that is inert to isocyanate, such as oxygen, nitrogen, sulfur, or a combination thereof, and where m+n is an integer of at least 2 (e.g., 2 to 4) and formula (Both isomers are represented by tilde bonds) are prepared by reacting maleate or fumarate esters, wherein each R 22 They can be the same or different, representing organic groups that are inert to the isocyanate group at 100°C or lower. Each R 23 They can be the same or different, indicating hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower.

[0054] Suitable examples of tert-doamines include, but are not limited to: ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,2-butanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 2,5-diamino-2,5-dimethylhexane, 2,2,4-and / or 2,4,4-trimethyl-1,6-hexanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, bis-(3-aminopropyl) ether, 1,2-bis-(3-aminopropoxy)ethane, 1,3-bis-(3-aminopropoxy)-2,2′-dimethylpropane, 1,2-diaminocyclohexane, 1 3-Diaminocyclohexane, 1,4-Diaminocyclohexane, 1,3-Diaminomethylcyclohexane, 1,4-Diaminomethylcyclohexane, 1,3-Diaminoethylcyclohexane, 1,4-Diaminoethylcyclohexane, 1,3-Diaminopropylcyclohexane, 1,4-Diaminopropylcyclohexane, hydrogenated 4,4′-diaminodiphenylmethane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4-and / or 2,6-hexahydrotoluenediamine, 2,4′-and / or 4,4′-diaminodicyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, propane-1,2,3-triamine, pentane-1,3,5-triamine, benzene -1,3,5-Triamine, Isophorone diamine, Menthane diamine, 1,4-Diaminopropylpiperazine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-Toluenediamine, 2,6-Toluenediamine, 2,4-Toluenediamine, 2,4′-and / or 4,4′-Diaminodiphenylmethane, m-Aminobenzylamine, 4-Chloro-o-phenylenediamine, Tetrachloro-p-phenylenediamine, 4-Methoxy-6-methyl-m-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,5-Naphthylenediamine, 2,6-Naphthylenediamine, Benzidine, 4,4′-Bis(o-toluidine), Dianisidine, 4,4′-Diaminodiphenylmethane, 2,2-(4,4′-Diaminodiphenyl)propane, 4,4′ -Diaminodiphenyl ether, 4,4′-thiodiphenylamine, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodimethylmethyl sulfone, methylene bis(o-chloroaniline), 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, diethylenetriamine, iminodipropylamine, methyliminodipropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,4-bis(aminoethylpiperazine), 1,4-bis(aminopropylpiperazine), 2,6-diaminopyridine, 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.

[0055] Specific examples of suitable maleic esters or fumarates include, but are not limited to, dimethyl, diethyl, and di-n-butyl esters of maleic acid and fumarate, and the corresponding maleic esters or fumarates substituted with methyl groups at the 2- and / or 3-positions.

[0056] The preparation of aspartic esters and / or polyaspartic ester amines containing primary amines from the above starting materials can be carried out at temperatures, for example, from -20°C to 100°C, with the starting materials used in proportions of 0.8+m / n to 1.2+m / n, for example, 1+m / n, primary amines per olefinic double bond, where m and n are as defined above with respect to the formulas for primary polyamines. The reaction can be carried out in the absence of a solvent or in the presence of a suitable solvent (such as methanol, ethanol, propanol, dioxane, and mixtures thereof). The reaction can optionally be carried out in the presence of a catalyst, such as an organometallic catalyst, wherein the catalyst comprises a copper compound (such as copper naphthenate), a cobalt compound (such as cobalt naphthenate), a zinc compound (such as zinc naphthenate), a bismuth compound (such as bismuth neodecanoate), a tin compound (such as di-n-butyltin dilaurate), or any combination of two or more of the above.

[0057] The reaction of primary amine-containing aspartic esters and / or polyaspartic esters with isocyanate-functionalized silanes (if desired) can be carried out in the presence of a catalyst. Suitable catalysts include, but are not limited to, organometallic catalysts, amine catalysts, or combinations thereof, such as catalysts comprising copper compounds (e.g., copper naphthenate), cobalt compounds (e.g., cobalt naphthenate), zinc compounds (e.g., zinc naphthenate), bismuth compounds (e.g., bismuth neodecanoate), tin compounds (e.g., di-n-butyltin dilaurate), triethylamine, triethylenediamine, 1,4-diazabicyclo[2.2.2]octane (DABCO), dimethylethanolamine (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. Furthermore, in some cases, the relative amounts of reactants are such that the molar ratio of the isocyanate reactive group to the isocyanate group is at least 1:1, for example, greater than 1 and less than 1.5. The resulting polysilane compound comprises an aspartic ester group, for example, as shown in the previously described structure (8).

[0058] In some embodiments, the resulting polysilane compound containing aspartic ester groups is further processed to convert the aspartic ester groups into hydantoin groups, wherein the conversion is optionally carried out in the presence of a catalyst (e.g., a Bronsted acid, carboxylic acid, sulfonic acid, phenol, or any two or more of the thereof) at a reaction temperature of 0 to 200°C, 70 to 130°C, 90 to 120°C, or 100 to 120°C. The resulting polysilane compound contains hydantoin groups, for example, as shown in the previously described structure (9).

[0059] Therefore, this specification also relates to a method for preparing a polysilane compound, comprising reacting (a) an aspartic ester containing a primary amine as described above with (b) an isocyanate-functionalized silane as described above, optionally in the presence of a catalyst, to produce a polysilane compound comprising an aspartic ester group. In some embodiments, the method further comprises converting the aspartic ester group to a hydantoin group, wherein the conversion is optionally carried out in the presence of a catalyst to produce a polysilane compound comprising a hydantoin group.

[0060] In other embodiments, the polysilane compound of this specification comprises a reaction product containing: (a) an isocyanate-functionalized silane, such as any isocyanate-functionalized silane previously described that reacts with aspartic ester silanes; and (b) a polyaspartic ester of structure (12): Where (i) is each R 3 They may be the same or different, representing organic groups that are inert to isocyanate groups at 100°C or lower, (ii) each R 4 They may be the same or different, each representing hydrogen or an organic group inert to the isocyanate group at 100°C or lower, (iii) Z representing an organic group inert to the isocyanate group at 100°C or lower, in some cases being a divalent organic group, for example optionally containing a hydrocarbon group of oxygen, nitrogen, sulfur or a combination thereof inert to the isocyanate group, and comprising C1 to C2. 18 Alkylene or C5-C6 cycloalkylene, and (iv) m+n is 2 to 10, for example 2 to 4, or 2. In some cases, each R in the aforementioned polyaspartic ester structure 3 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, each R 3 They can be the same or different, representing methyl, ethyl, propyl or butyl.

[0061] The aforementioned polyaspartic ester can be produced by making the formula (NH2)mZ 1 (NH2)n primary polyamines (where Z) 1 Optionally containing a hydrocarbon group that is inert to isocyanate, such as oxygen, nitrogen, sulfur, or a combination thereof, and where m+n is an integer of at least 2 (e.g., 2 to 4) and formula (Both isomers are represented by tilde bonds) are prepared by reacting maleate or fumarate esters, wherein each R 22 They can be the same or different, representing organic groups that are inert to the isocyanate group at 100°C or lower. Each R 23 They can be the same or different, indicating hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower.

[0062] Suitable examples of tert-doamines include, but are not limited to: ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,2-butanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 2,5-diamino-2,5-dimethylhexane, 2,2,4-and / or 2,4,4-trimethyl-1,6-hexanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, bis-(3-aminopropyl) ether, 1,2-bis-(3-aminopropoxy)ethane, 1,3-bis-(3-aminopropoxy)-2,2′-dimethylpropane, 1,2-diaminocyclohexane, 1 3-Diaminocyclohexane, 1,4-Diaminocyclohexane, 1,3-Diaminomethylcyclohexane, 1,4-Diaminomethylcyclohexane, 1,3-Diaminoethylcyclohexane, 1,4-Diaminoethylcyclohexane, 1,3-Diaminopropylcyclohexane, 1,4-Diaminopropylcyclohexane, hydrogenated 4,4′-diaminodiphenylmethane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4-and / or 2,6-hexahydrotoluenediamine, 2,4′-and / or 4,4′-diaminodicyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, propane-1,2,3-triamine, pentane-1,3,5-triamine, benzene -1,3,5-Triamine, Isophorone diamine, Menthane diamine, 1,4-Diaminopropylpiperazine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-Toluenediamine, 2,6-Toluenediamine, 2,4-Toluenediamine, 2,4′-and / or 4,4′-Diaminodiphenylmethane, m-Aminobenzylamine, 4-Chloro-o-phenylenediamine, Tetrachloro-p-phenylenediamine, 4-Methoxy-6-methyl-m-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,5-Naphthylenediamine, 2,6-Naphthylenediamine, Benzidine, 4,4′-Bis(o-toluidine), Dianisidine, 4,4′-Diaminodiphenylmethane, 2,2-(4,4′-Diaminodiphenyl)propane, 4,4′ -Diaminodiphenyl ether, 4,4′-thiodiphenylamine, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodimethylmethyl sulfone, methylene bis(o-chloroaniline), 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, diethylenetriamine, iminodipropylamine, methyliminodipropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,4-bis(aminoethylpiperazine), 1,4-bis(aminopropylpiperazine), 2,6-diaminopyridine, 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.

[0063] Specific examples of suitable maleic esters or fumarates include, but are not limited to, dimethyl, diethyl, and di-n-butyl esters of maleic acid and fumarate, and the corresponding maleic esters or fumarates substituted with methyl groups at the 2- and / or 3-positions.

[0064] The preparation of polyaspartic esters from the above-described starting materials can be carried out at temperatures, for example, from -20°C to 100°C, with the starting materials used in proportions of 0.8 to 1.2 double bonds per olefin, for example, one primary amine. The reaction can be carried out in the absence of solvent or in the presence of a suitable solvent (such as methanol, ethanol, propanol, dioxane, and mixtures thereof). The reaction can optionally be carried out in the presence of a catalyst, such as an organometallic catalyst, wherein the catalyst comprises a copper compound (such as copper naphthenate), a cobalt compound (such as cobalt naphthenate), a zinc compound (such as zinc naphthenate), a bismuth compound (such as bismuth neodecanoate), a tin compound (such as di-n-butyltin dilaurate), or any combination of two or more of the above.

[0065] The reaction of polyaspartic esters with isocyanate-functionalized silanes can 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, such as catalysts comprising copper compounds (e.g., copper naphthenate), cobalt compounds (e.g., cobalt naphthenate), zinc compounds (e.g., zinc naphthenate), bismuth compounds (e.g., bismuth neodecanoate), tin compounds (e.g., di-n-butyltin dilaurate), triethylamine, triethylenediamine, 1,4-diazabicyclo[2.2.2]octane (DABCO), dimethylethanolamine (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. Furthermore, in some embodiments, the relative amounts of reactants are such that the molar ratio of the isocyanate reactive group to the isocyanate group is at least 1:1, for example, greater than 1 and less than 1.5. The resulting polysilane compound comprises an aspartic ester group, for example, as shown in the previously described structure (10).

[0066] In some embodiments, the resulting polysilane compound containing aspartic ester groups is further processed to convert the aspartic ester groups into hydantoin groups, wherein the conversion is optionally carried out in the presence of a catalyst (e.g., a Bronsted acid, carboxylic acid, sulfonic acid, phenol, or any two or more of the thereof) at a reaction temperature of 0 to 200 °C, 70 to 130 °C, 90 to 120 °C, or 100 to 120 °C. The resulting polysilane compound contains hydantoin groups, for example, as shown in the previously described structure (11).

[0067] Therefore, this specification also relates to a method for preparing a polysilane compound, comprising reacting (a) a polyaspartic ester as described above with (b) an isocyanate-functionalized silane as described above, optionally in the presence of a catalyst, to produce a polysilane compound comprising an aspartic ester group. In some embodiments, the method further comprises converting the aspartic ester group to a hydantoin group, wherein the conversion is optionally carried out in the presence of a catalyst to produce a polysilane compound comprising a hydantoin group.

[0068] This specification also relates to the use of the various polysilane compounds described above. More particularly, in some aspects, this specification relates to the use of such compounds in, for example, coating compositions. Such coating compositions may, of course, contain a variety of other components. For example, in some embodiments, such coating compositions may contain other components for increasing the adhesion of the resulting coating to a substrate. Such components may be included as components of the coating compositions described herein, or may be applied to the substrate prior to applying the coating compositions of this specification to the substrate. Examples of such adhesion promoters include, but are not limited to, other silane-containing compounds, epoxy-functionalized compounds, thiol-functionalized compounds, and olefinically unsaturated compounds, including any combination and mixture of two or more. Specific examples of such adhesion promoters are alkoxysilanes, such as 3-methacryloyloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltriethoxysilane, and any combination of two or more.

[0069] In some embodiments, such adhesion-promoting compounds can react with other components in the coating composition to become part of the film-forming binder of the coating composition.

[0070] The coating compositions described in this specification contain film-forming materials, such as various thermoplastic and / or thermosetting resins. As used herein, “thermosetting” means a resin in which the polymer chains are covalently linked together after curing or crosslinking, such that once cured, the resin does not melt upon heating and is insoluble in solvents. On the other hand, “thermoplastic” resins include polymers that are not covalently linked and are capable of liquid flow upon heating.

[0071] The coating compositions described herein may contain a variety of film-forming resins, including but not limited to various polyurethanes, polyesters, polyethers, polycarbonates, polyamides, polysiloxanes, epoxy resins, vinyl resins, (meth)acrylate polymers, and copolymers and mixtures of any two or more of them.

[0072] In some embodiments, the film-forming resin containing reactive functional groups (such as any of the aforementioned resins) may include hydroxyl, isocyanate (which may be terminal), carboxylic acid, amino, epoxy, alkoxy, thiol, amide, urea, etc., including any combination and mixture of two or more. In such embodiments, the coating composition may also include a curing agent, i.e., a crosslinking agent, which contains reactive functional groups that can react with the reactive functional groups on the film-forming resin. In other cases, the film-forming resin has interreactive functional groups, and therefore the film-forming resin is self-crosslinking. As used herein, a "crosslinking agent" or "curing agent" is a molecule containing two or more functional groups that can react with other functional groups and that can link two or more compound or polymer molecules by chemical bonds.

[0073] The coating composition of the present invention can be cured under environmental conditions by heating or by other means such as photochemical radiation, which refers to electromagnetic radiation that can initiate chemical reactions, including but not limited to visible light, ultraviolet (UV) light, X-rays, infrared (IR) rays and gamma rays.

[0074] The coating compositions described in this specification may contain a variety of other components, including but not limited to plasticizers, surface conditioners, pigments, dyes, fillers, antioxidants, light stabilizers, UV absorbers and stabilizers, surfactants, flow and surface control agents, thixotropic agents, organic solvents, reactive diluents, reaction inhibitors, and corrosion inhibitors.

[0075] The components forming the coating composition may be combined and mixed in a liquid medium prior to applying the coating composition to a substrate to form a coating. For example, in some embodiments, the components may be combined and mixed in an organic solvent. In some embodiments, the organic solvent is present in an amount greater than 50% by weight based on the total weight of the liquid medium. Specific examples of suitable organic solvents include, but are not limited to: glycols, glycol ethers, alcohols, ketones, glycol diethers, esters and diesters, as well as aromatic hydrocarbons and aliphatic hydrocarbons. However, in other embodiments, the liquid medium may consist primarily of water, i.e., the liquid medium contains greater than 50% by weight, greater than 60% by weight, greater than 70% by weight, greater than 80% by weight, greater than 90% by weight, greater than 95% by weight, or 100% by weight of water based on the total weight of the liquid medium.

[0076] In some embodiments, one or more components forming the coating composition may be stored separately before being mixed together to form the coating composition. After mixing, the coating composition can be applied to a variety of substrates, such as metallic and non-metallic substrates, including substrates made of polymeric materials, wood, veneer, particleboard, medium-density fiberboard, cement, stone, glass, paper, cardboard, textiles, leather, including composite materials and any combination of two or more thereof.

[0077] In some cases, coating compositions may be applied to a substrate as a single coat along with additional coatings to form a multi-layer coating system. For example, the coating compositions of this specification may be applied to a substrate as a primer layer, and one or more additional coatings, such as basecoats and / or topcoats, may be applied thereon. As used herein, “primer” refers to an undercoat used to prepare a substrate surface for the application of a protective or decorative coating system. “Basecoat” refers to a coating applied over a primer and / or directly to a substrate, containing colorants to provide visual effects, and may be covered with protective and decorative topcoats. These additional coatings may be formed from coating compositions containing the same or different film-forming resins as the primer layer.

[0078] The coating compositions described in this specification can be applied to a variety of products or components, such as automobiles and automobile parts, industrial substrates, aircraft and aircraft parts, marine substrates and components, storage tanks, windmills, nuclear power plants, packaging substrates, wood flooring and furniture, clothing, electronic components, glass and transparent materials, sporting equipment and buildings, etc.

[0079] However, in some embodiments, the coating compositions of this specification may be embodied as radiation-curable coating compositions, including compositions particularly suitable for application to optical fiber substrates. In particular, the polysilane compounds described in this specification are currently considered particularly advantageous as adhesion-promoting compounds in such compositions. Indeed, it has been surprisingly observed that, while such polysilane compounds of at least some embodiments can be readily and efficiently synthesized, cured coatings with significantly improved adhesion properties compared to similar coatings using other adhesion promoters, including those conventionally used in radiation-curable coating compositions suitable for optical fiber substrates.

[0080] Therefore, certain specific aspects of this specification relate to radiation-curable coating compositions comprising the polysilane compounds described above, for example, wherein such polysilane compounds are present in amounts 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 radiation-curable coating composition. In these embodiments, the radiation-curable coating composition comprises one or more compounds having radiation-curable groups, for example, wherein such radiation-curable compounds are present in amounts of, for example, up to 90 wt%, 75 wt%, or 70 wt%, based on the total weight of the radiation-curable coating composition. Examples of such radiation-curable compounds are oligomers and polymers, including but not limited to polyether (meth)acrylates, polyester (meth)acrylates, urethane (meth)acrylates, epoxy (meth)acrylates, and known radiation-curable reactive diluents (see Rompp Lexikon Chemie, p. 491, 10th edition, 1998, Georg-Thieme-Verlag, Stuttgart).

[0081] More specifically, in some embodiments, such radiation-curable coating compositions comprise olefinically unsaturated oligomers. As used herein, "oligomer" refers to a molecule of medium relative molecular mass whose structure comprises a plurality of units actually or conceptually derived from molecules of lower relative molecular mass. In some embodiments, the number-average molecular weight (Mn) of the reactive oligomers described herein is 1000 g / mol to 35,000 g / mol, 1000 g / mol to 30,000 g / mol, 1000 g / mol to 25,000 g / mol, 1000 g / mol to 20,000 g / mol, 2,200 to 10,000 g / mol, or 2,200 to 5,500 g / mol, as measured by size exclusion chromatography (SEC). Each molecule of the olefinically unsaturated oligomer comprises at least one olefinically unsaturated group, and in some cases, two or more olefinically unsaturated groups.

[0082] In some embodiments, the olefinic unsaturated oligomer comprises a urethane (meth)acrylate oligomer containing (meth)acrylate groups, urethane groups, and a backbone, for example, wherein the backbone is derived from a polyol reacted with an isocyanate (e.g., a polyisocyanate, such as a diisocyanate) and a hydroxyl-containing (meth)acrylate. As used in this specification, "(meth)acrylate" includes acrylates and methacrylates.

[0083] Examples of suitable polyols include, but are not limited to, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, acrylic polyols, and mixtures of any two or more. In some embodiments, the backbone of the urethane acrylate oligomer comprises a compound derived from polypropylene glycol (PPG). As used herein, compounds derived from PPG include end-capped PPG, such as EO-end-capped PPG. There are no particular limitations on the polymerization of the structural units in these polyols. Random polymerization, block polymerization, or graft polymerization are all acceptable.

[0084] As used herein, a block copolymer refers to a portion of an oligomer or polymer comprising a plurality of structural units, wherein at least one structural unit contains a feature not present in adjacent portions. As used herein, monoblock, diblock, and triblock copolymers refer to the average number of specific blocks in an oligomer. In some embodiments, a specific block refers to a polyether block derived from one or more polyols described elsewhere herein, such as polyether polyols. In some embodiments, the blocks referred to in monoblock, diblock, and / or triblock copolymers are polyether blocks derived from one or more polyols described elsewhere herein. 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 specific block (e.g., polyether block) units. In another embodiment, a diblock copolymer can be described as a copolymer having an average of about 2, or at least 1.5 to less than 2.5 specific block (e.g., polyether block) units, while in yet another embodiment, a triblock copolymer can be described as a copolymer having an average of about 3, or at least 2.5 to less than 3.5 specific block (e.g., polyether block) units. The number of polyether units in a given oligomer can be determined by the number of polyether polyol molecules used to synthesize a single oligomer.

[0085] Suitable polyether polyols include, but are not limited to, polyethylene glycol, polypropylene glycol, polypropylene glycol-ethylene glycol copolymer, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydemomethylene glycol, and polyether glycol obtained by ring-opening copolymerization of two or more ionicly polymerizable cyclic compounds (e.g., cyclic ethers), including but not limited to ethylene oxide, isobutylene oxide, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexane oxide, styrene oxide, epichlorohydrin, isoprene monooxide, vinyloxetane, vinyltetrahydrofuran, vinylcyclohexane oxide, phenyl glycidyl ether, butyl glycidyl ether, and glycidyl benzoate. Specific examples of combinations of two or more ionically polymerizable cyclic compounds include, but are not limited to, combinations for producing binary copolymers, such as tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, and tetrahydrofuran and ethylene oxide; and combinations for producing ternary copolymers, such as combinations of tetrahydrofuran, 2-methyltetrahydrofuran and ethylene oxide, and combinations of tetrahydrofuran, butene-1-oxide, and ethylene oxide. The ring-opening copolymers of these ionically polymerizable cyclic compounds can be random copolymers or block copolymers.

[0086] Suitable polyester glycols include, but are not limited to, those obtained by reacting polyols and polyacids. Suitable polyols 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 any mixtures of two or more of them. Suitable polyacids include, but are not limited to, phthalic acid, dimer acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, and any mixtures of two or more of them.

[0087] Suitable polycarbonate polyols include, but are not limited to, polycarbonates of tetrahydrofuran, poly(hexanediol carbonate), poly(nonanediol carbonate), poly(3-methyl-1,5-pentanemethylene carbonate), and any mixtures of two or more.

[0088] Suitable polycaprolactone diols include, but are not limited to, those with a melting point of 0°C or higher, obtained by reacting e-caprolactone with a diol compound. Suitable diol compounds include, but are not limited to, ethylene glycol, polyethylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-butanediol, and any mixtures of two or more of them.

[0089] Other suitable polyols include, but are not limited to, ethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, polyoxyethylene bisphenol A ether, polyoxypropylene bisphenol A ether, polyoxyethylene bisphenol F ether, polyoxypropylene bisphenol F ether, and mixtures of any two or more thereof. In some embodiments, these other polyols contain an epoxide structure in their molecules, such as polytetramethylene glycol and polyols containing copolymer diols of butane oxide and ethylene oxide.

[0090] In some embodiments, the number-average molecular weight derived from the hydroxyl value of the polyol is 50 to 15,000 g / mol, for example, 1,000 to 8,000 g / mol.

[0091] Suitable polyisocyanates for preparing urethane (meth)acrylate oligomers include, but are not limited to: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene 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′-biphenyl diisocyanate, 1,6-hexanediisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl)isocyanate, 2,2,4-trimethylhexamethylene diisocyanate, bis(2-ethyl isocyanate) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane Diisocyanates, hydrogenated diphenylmethane diisocyanates, hydrogenated diphenylmethylene diisocyanates, tetramethylphenylmethylene diisocyanates, lysine isocyanates, hexamethylene diisocyanate trimers (Desmodur® N3300A, commercially available from Covestro), triphenylmethane-4,4′,4″-triisocyanates (Desmodur® RE, commercially available from Covestro), hexamethylene diisocyanate trimers (Desmodur® N3200, commercially available from Covestro), aromatic polyisocyanates based on toluene diisocyanates (Desmodur® ILBA, commercially available from Covestro), polyisocyanurates based on toluene diisocyanates (Desmodur® RC, commercially available from Covestro), and any combination of two or more of them.

[0092] Suitable hydroxyl-containing methacrylates for preparing urethane (meth)acrylate oligomers include, but are not limited to, methacrylates derived from (meth)acrylic acid and epoxy, as well as methacrylates containing epoxides, such as, in particular, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl acrylate, and 2-hydroxy-3-oxyphenyl (meth)acrylate.

[0093] In order to prepare urethane (meth)acrylate oligomers, in some embodiments, the ratio of polyol, polyisocyanate and hydroxyl (meth)acrylate is determined as follows: for each amount of isocyanate group contained in the polyisocyanate, 0.1 to 0.9 equivalents of hydroxyl groups contained in the hydroxyl (meth)acrylate are used, and 1.0 to 1.5 equivalents of total hydroxyl groups from the polyol and the hydroxyl (meth)acrylate are used.

[0094] In some embodiments, a carbamate catalyst is present during the reaction of the three components described above. Suitable such catalysts include, for example, copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin dilaurate, bismuth neodecanoate, triethylamine, triethylenediamine-2-methyltriethylenediamine, and mixtures of any two or more thereof. In some embodiments, the amount of carbamate catalyst used is 0.01 to 1% by weight based on the total weight of the reactants. In some cases, the reaction is carried out at a temperature of 10 to 90°C, for example, 30 to 80°C.

[0095] In addition to or instead of the previously described urethane (meth)acrylates, other olefinically unsaturated oligomers that can be used in embodiments of the radiation-curable compositions of this specification include polyester (meth)acrylates, epoxy (meth)acrylates, polyamide (meth)acrylates, siloxane polymers having (meth)acryloyloxy groups, reactive polymers obtained by reacting copolymers of (meth)acrylic acid with glycidyl methacrylate and other polymerizable compounds, and mixtures of any two or more. In some embodiments, the oligomers comprise bisphenol A acrylate oligomers, such as alkoxylated bisphenol A diacrylate and diglycidyl bisphenol A diacrylate.

[0096] In some embodiments, the oligomer may comprise unsaturated, urethane-free oligomers, such as unsaturated, urethane-free polyester acrylate oligomers and / or unsaturated, urethane-free alkyd acrylate oligomers. Examples of such oligomeric unsaturated compounds are acrylic epoxy resins, acrylic polyethers, and acrylic 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. This type of unsaturated oligomer is also referred to as a prepolymer. Typical examples of unsaturated compounds are esters of olefinically unsaturated carboxylic acids with polyols or polyepoxides, and polymers containing olefinically unsaturated groups in the main chain or side groups, including unsaturated polyesters, polyamides and their copolymers, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers containing (meth)acrylic groups in the side chains, and mixtures of one or more such polymers. Exemplary examples of olefinic 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 alicyclic polyols. Aromatic polyols are typically hydroquinone, 4,4′-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane, as well as phenolic varnishes and cresol. Polyepoxides include those based on the aforementioned polyols, such as those based on aromatic polyols and epichlorohydrin.

[0097] One or more of the aforementioned olefinic unsaturated oligomers may be used in the compositions according to the invention in any suitable amount, and may be selected individually or in combination of one or more types listed herein. In some embodiments, the olefinic unsaturated oligomers are present in amounts of 5 to 95 wt%, 10 to 90 wt%, 10 to 80 wt%, 30 to 95 wt%, 30 to 90 wt%, 65 to 95 wt%, or 50 to 80 wt%, based on the total weight of solids in the radiation-curable composition.

[0098] Furthermore, in some embodiments, the radiation-curable coating composition comprises a reactive diluent compound containing one or more olefinically unsaturated groups. Examples of such compounds include those containing a double bond, such as alkyl or hydroxyalkyl (meth)acrylates, suitable examples of which include, but are not limited to, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate and ethyl methacrylate, lauryl acrylate, ethoxylated nonylphenol acrylate, phenoxyethyl (meth)acrylate, diethylene glycol ethylhexyl acrylate (DEGEHA), acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamide, vinyl esters such as vinyl acetate, styrene, alkylstyrene, halostyrene, N-vinylpyrrolidone, N-vinylcaprolactam, vinyl chloride, vinylidene chloride, and any mixtures of two or more. Examples of reactive diluent compounds containing multiple single double bonds 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 pentaerythritol tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, tris(2-acryloylethyl) isocyanurate, and any mixtures of two or more.

[0099] In some embodiments, the reactive diluent compound is present in amounts of 5 to 90 wt%, 10 to 90 wt%, 10 to 80 wt%, 10 to 60 wt%, 10 to 40 wt%, or 10 to 30 wt%, based on the total weight of the solids in the radiation-curable composition.

[0100] 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 acylphosphine oxide, such as bisacylphosphine oxide (BAPO) and / or monoacylphosphine oxide (MAPO), α-hydroxy ketone, or any mixture of two or more. In some embodiments, the sum of the amounts of the polysilane compound and the photoinitiator is 1 to 99% by weight, based on the total weight of the solids in the radiation-curable composition.

[0101] In some embodiments, the photoinitiator comprises diacylphosphine oxide having the following structure: Where R 50 For C1-C 12 Alkyl, cyclohexyl, or phenyl, unsubstituted or substituted with 1 to 4 halogen atoms, or C1-C8 alkyl; R 51 and R52 Each is independently a C1-C8 alkyl or C1-C8 alkoxy; R 53 It is hydrogen or C1-C8 alkyl; R 54 It is hydrogen or methyl. For example, in some embodiments, R 50 For C2-C 10 Alkyl, cyclohexyl, or unsubstituted or phenyl groups substituted with 1 to 4 C1-C4 alkyl, Cl, or Br. In another embodiment, R 50 It is a C3-C8 alkyl, cyclohexyl, or phenyl group substituted with or unsubstituted with a C1-C4 alkyl group at the 2-, 3-, 4-, or 2, 5-position. In some cases, R 50 C4-C 12 Alkyl or cyclohexyl, R 51 and R 52 Each is independently a C1-C8 alkyl or C1-C8 alkoxy, R 53 It is hydrogen or C1-C8 alkyl. In some embodiments, R 51 and R 52 It is a C1-C4 alkyl or C1-C4 alkoxy, R 53 It is hydrogen or C1-C4 alkyl. Another embodiment is in which R 51 and R 52 It is methyl or methoxy, R 53 It is hydrogen or methyl, for example, where R 51 R 52 and R 53 It is methyl. Another embodiment is in which R... 51 R 52 and R 53 For methyl, R 54 It is hydrogen. In other embodiments, R 50 It is a C3-C8 alkyl group, for example, where R 51 and R 52 It is a methoxy group, R 53 and R 54 For hydrogen, R 50 It is isooctyl. In some cases, R 50 It is isobutyl or phenyl. Specific examples of suitable diacylphosphine oxides include, but are not limited to, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-(2,4-dipentoxyphenyl)phosphine oxide, or mixtures thereof.

[0102] 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 a weight ratio, for example, from 1:11 to 1:7. In other embodiments, 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 a weight ratio, for example, from 3:1:15 to 4:1:16. In 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 a weight ratio of, for example, 1:3 to 1:5.

[0103] Other suitable photoinitiators include, but are not limited to, other mono- or diacylphosphine oxides, such as diphenyl-2,4,6-trimethylbenzoylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; α-hydroxy ketones, such as 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone; α-amino ketones, such as 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, such as benzophenone, 2,4,6-Trimethylbenzophenone, 4-Methylbenzophenone, 2-Methylbenzophenone, 2-Methoxycarbonylbenzophenone, 4,4′-bis(chloromethyl)-benzophenone, 4-chlorobenzophenone, 4-phenylbenzophenone, 4,4′-bis(dimethylamino)-benzophenone, 4,4′-bis(diethylamino)benzophenone, methyl 2-benzoylbenzoate, 3,3′-dimethyl-4-methoxybenzophenone, 4-(4- Benzyl methylbenzyl ketone, 2,4,6-trimethyl-4′-phenyl-benzophenone and 3-methyl-4′-phenyl-benzophenone; ketal compounds, such as 2,2-dimethoxy-1,2-diphenyl ethyl ketone; and complex or diphenyl glyoxylates, such as methyl phenyl glyoxylate, 5,5′-oxo-di(ethyleneoxydicarbonylphenyl) and 1,2-(benzoylcarboxyl)ethane, or any mixture of two or more of them.

[0104] Other suitable photoinitiators include, but are not limited to, the oxime esters disclosed in U.S. Patent No. 6,596,445. Also suitable are phenyl glyoxylates, such as those disclosed in U.S. Patent No. 6,048,660, and germanium-based photoinitiators disclosed in Dalton Trans. 2021, 50, 12392-12398.

[0105] In some embodiments, the free radical photoinitiator is present in an amount of 0.1 to 10% by weight, for example 0.1 to 5% by weight, or in some cases 1 to 5% by weight, based on the total weight of the radiation-curable composition.

[0106] Photoinitiators applicable to the radiation-curable compositions described herein are also described in paragraphs

[0080] -

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

[0107] It should be understood that the radiation-curable compositions of this specification may contain a variety of other components, including various additives that can impart certain desired properties to the composition, such as improved shelf life, improved coating oxidation and hydrolytic stability, improved curing speed, additional coating functional properties, etc. For example, in some embodiments, the radiation-curable compositions of this specification may contain one or more photosensitizers, radiation-curable amine synergists, UV absorbers, antioxidants, UV stabilizers, light stabilizers, filler materials, chain-transferred thiols, surfactants, viscosity modifiers, additional addition accelerators, dehydrating agents such as tetraethyl orthosilicate (TEOS) and orthoformates, oxygen quenchers, or 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, etc. Some suitable additives are described in paragraphs

[0122] -

[0134] of U.S. Patent Application Publication No. US 2021 / 0088720 A1, the referenced portion of which is incorporated herein by reference.

[0108] The radiation-curable compositions of this specification may contain adhesion promoters other than the polysilane compounds previously described herein. Suitable adhesion promoters include silane coupling agents (other than the polysilane compounds previously described), such as hydrolyzable silane compounds containing mercapto groups and / or multiple alkoxy groups, such as those described in U.S. Patent Application Publication No. 2002 / 0013383 A1, the relevant portions of which are incorporated herein by reference. Specific examples of such adhesion promoters are γ-mercaptopropyltrimethoxysilane, trimethoxysilylpropyl acrylate, 3-trimethoxysilylpropane-1-thiol, and any mixtures of two or more. In some embodiments, the radiation-curable composition may contain an olefinically unsaturated silane, such as a portion of structure (1): and (b)(1) Part of structure (2): or (b)(2) Part of structure (3): or (b)(3) A combination of parts of structure (2) and parts of structure (3), wherein (i) Y represents a straight-chain or branched linking group containing one or more carbon atoms, (ii) each X may be the same or different, representing an alkoxy group or an organic group that is inert to isocyanate groups at 100°C or lower, provided that at least one X represents an alkoxy group, (iii) R 1 and R 2 They may be the same or different, each representing an organic group that is inert to the isocyanate group at 100°C or lower; (iv) R 3 and R 4 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower; and (v) each " The term "" indicates a connection to another part of an olefinically unsaturated silane. Such olefinically unsaturated silanes and methods for their preparation are described in a concurrently filed U.S. Provisional Patent Application entitled "ETHYLENICALLY UNSATURATED COMPOUNDS, METHODSFOR THEIR PREPARATION, AND THE USE THEREOF IN COATING COMPOSITIONS," which is incorporated herein by reference.

[0109] In some embodiments, the total silane content of the radiation-curable composition of this specification (as determined as described in the Examples section of this specification) is at most 10 mmol per 100 grams of the radiation-curable composition, for example, 1 to 10 mmol, 1 to 8 mmol, or 2 to 6 mmol. Furthermore, in some embodiments, the total urea + carbamate content of the radiation-curable composition of this specification (as determined as described in the Examples section of this specification) is 20 to 200 mmol per 100 grams of the radiation-curable composition, for example, 30 to 150 mmol, or in some cases, 40 to 100 mmol.

[0110] Furthermore, in some embodiments, the cured coating deposited by the coating composition exhibits a peel strength of at least 40 gf / in (“gf / in”) or at least 55 gf / in after at least 7 days, as measured as described in the Examples section of this specification. Additionally, in some embodiments, the cured coating deposited by the coating composition exhibits an elongation at break of at least 35%, for example, at least 50%, as measured as described in the Examples section of this specification.

[0111] Furthermore, in some embodiments, the coating composition of this specification is configured to have a viscosity of at least >0.1 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 a viscosity of 1 to 15 Pa·s, 2 to 12 Pa·s or 3 to 10 Pa·s, wherein the viscosity is at 25°C and 50 s -1 Measured at the shear rate.

[0112] It should be understood that, in some aspects, this specification relates to a method for coating optical fibers. Such methods include providing glass optical fibers, for example, drawing glass optical fibers using a drawing tower; applying a primary coating composition to the surface of the glass optical fiber; optionally, applying a UV light dose 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 light to influence the curing of the secondary coating composition, and optionally to influence the curing of the primary coating composition. In these methods, the primary coating composition and / or the secondary coating composition are compositions of the type described in this specification.

[0113] It should also be understood that this specification also relates to coated optical fibers comprising a glass core and a cladding layer that contacts and surrounds the glass core; and a coating portion further comprising a primary coating layer that contacts the cladding layer; and a secondary coating layer that contacts and surrounds the primary coating layer. According to this aspect, the primary and / or secondary coating layers are cured products of coating compositions of the type described in this specification. In some cases, the optical fiber comprises a core, a cladding layer, a primary coating layer that contacts an outer ring cladding region, and a secondary coating layer. According to some of these embodiments, the core comprises pure silica glass (SiO2) or silica glass having one or more dopants that increase the refractive index of the glass core relative to 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 with one or more dopants that increase the refractive index (e.g., GeO2, Al2O3, P2O5, TiO2, ZrO2, Nb2O5, and / or Ta2O5), for example when the cladding layer is “top-doped,” or silica glass with dopants that decrease the refractive index (e.g., fluorine), for example when the inner cladding layer is “bottom-doped,” provided that the maximum relative refractive index [Δ1MAX] of the fiber core is greater than the maximum relative refractive index [Δ4MAX] of the cladding layer. According to one embodiment, the cladding layer is pure silica glass. According to some of these embodiments, the main coating has an in-situ (or on-fiber) tensile modulus of less than 5 MPa, less than 2 MPa, less than 1.5 MPa, or less than 1.0 MPa. Methods for describing in-situ modulus are well known in the art and are described in US 7,171,103 and US 6,961,508, which are incorporated herein by reference. In one embodiment, the cured master coating has an in-situ glass transition temperature of less than -10°C, less than -35°C, less than -40°C, or less than -45°C, and in other embodiments, no greater than -50°C. The master coating with a low in-situ modulus reduces microbending, a coupling mechanism between modes propagating in the optical fiber. The low in-situ glass transition temperature ensures that the in-situ modulus of the master coating remains low even when deploying optical fibers in very cold environments.

[0114] The main coating typically has a thickness of 20 to 50 μm (e.g., about 25 or 32.5 μm), with thinner thicknesses ranging from 15 to 25 μm for 200 μm optical fibers. In other embodiments, the main coating has a thickness of no more than 40 μm, for example, from 20 to about 40 μm, or in some cases 20 to 30 μm.

[0115] The secondary coating contacts and surrounds the primary coating. The secondary coating is, for example, a polymer of a coating composition whose molecules are highly cross-linked 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 from 1000 MPa to 8000 MPa, for example, from 1200 MPa to 5000 MPa or from 1500 MPa to 3000 MPa. The in-situ Tg of the secondary coating is from 50°C to 120°C in some embodiments, or from 50°C to 100°C in some cases. Furthermore, in some embodiments, the secondary coating has a thickness of no more than 40 μm, for example, from 20 to 40 μm, or in some cases, from 20 to 30 μm.

[0116] Suitable (secondary)coating materials and considerations associated with the selection of these materials are also described, for example, in U.S. Patent Nos. 4,962,992 and 5,104,433, each of which is incorporated herein by reference. As an alternative to these, high-modulus coatings can also be obtained using low-oligomer content coating systems, as described in U.S. Patent Nos. 6,775,451 and 6,689,463, each of which is incorporated herein by reference. High-modulus coatings produced using non-reactive oligomer components are also suitable, as described in U.S. Patent Application Publication No. US 2007 / 0100039 A1, which is incorporated herein by reference. Secondary coatings may also contain inks, as are known in the art, and in such cases may be referred to as “colored secondary coatings.”

[0117] If necessary, the coated optical fiber may contain one or more additional layers disposed on the sub-coating, such as a separate “ink” layer applied and cured separately from the sub-coating.

[0118] It is known in the art how to formulate typical primary and secondary coatings for optical fibers, as well as inks and matrix materials for curing with broadband UV lamps. A detailed discussion of this technique and related chemistry and testing methods can be found in Chapter 4, Section 4.6 through the end of A. Mendez and TF Morse's textbook, "Specialty Optical Fibers Handbook" (Elsevier Inc. © 2007, Elsevier).

[0119] Any type of optical fiber can be used in embodiments of the present invention. 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 an effective area of ​​20 to 200 μm². 2 Given the anticipated need for coating processes with higher line speeds or processing speeds, these fibers can be single-mode and / or large effective area fibers. However, other fiber types, such as multimode fibers, can also be used.

[0120] It should also be understood that this specification also relates to fiber optic cables, wherein the fiber optic cable comprises at least one fiber optic cable as described herein, and / or wherein the fiber optic cable is a cured product of a coating composition as described herein.

[0121] The various aspects of the subject matter described herein are listed in the following numbered clauses.

[0122] Clause 1. A polysilane compound comprising: (a) at least two parts of structure (1): and (b1) Part of structure (2): or (b2) Part of structure (3): or (b3) The combination of parts of structure (2) and parts of structure (3), Wherein (i) Y represents a straight-chain or branched linking group containing one or more carbon atoms, (ii) each X may be the same or different, representing an alkoxy group or an organic group that is inert to isocyanate groups at 100°C or lower, provided that at least one X represents an alkoxy group, and (iii) each R 1 They may be the same or different, indicating organic groups that are inert to isocyanate groups at 100°C or lower; (iv) each R 2 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower; and (v) " "" indicates a connection to another part of the polysilane compound.

[0123] Clause 2. The polysilane compound according to Clause 1, wherein R in structures (2) and (3) 1 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, such as R in structures (2) and (3). 1 They may be the same or different, representing methyl, ethyl, propyl or butyl, and R in structures (2) and (3) 2They may be the same or different, representing hydrogen or alkyl, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, such as R in structures (2) and (3). 2 They can be the same or different, representing methyl, ethyl, propyl or butyl.

[0124] Clause 3. A polysilane compound pursuant to Clause 1 or Clause 2, wherein each X in structure (1) represents the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X represents an alkoxy group, for example, at least two Xs represent alkoxy groups such as methoxy, ethoxy, or propoxy, or each X represents an alkoxy group such as methoxy, ethoxy, or propoxy.

[0125] Clause 4. A polysilane compound according to any one of Clauses 1 to 3, wherein Y in structure (1) comprises a straight-chain or branched alkylene having 1 to 8 carbon atoms, such as a straight-chain alkylene having 2 to 4 or, in some cases, 3 carbon atoms, or a branched alkylene having 5 to 6 carbon atoms.

[0126] Clause 5. A polysilane compound according to any one of Clauses 1 to 4, wherein said polysilane compound further comprises: (c) a segment with the following structure: Where G is O, S, or NR, and R represents hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, and each " "" indicates a connection to another part of the polysilane compound, for example, the polysilane compound containing 1 to 4 such segments.

[0127] Clause 6. A polysilane composition according to any one of Clauses 1 to 5, for example, wherein said polysilane compound comprises a portion of structure (3), provided that said polysilane compound comprises a portion of structure 3A: Where X, Y, R 1 R 2 and" "Each is as described in Clause 1 with respect to structures (1)-(3), for example, the polysilane compound having 1 to 4 portions of structure 3A."

[0128] Clause 7. A polysilane compound according to any one of Clauses 1 to 5, for example, wherein said polysilane compound comprises a portion of structure (3), provided that said polysilane compound has only one portion of structure 3B: Where X, Y, R 1 R 2 and" "Each is as described in Clause 1 regarding structure (1)-(3)."

[0129] Clause 8. A polysilane compound according to any one of Clauses 1 to 5, for example, wherein said polysilane compound comprises a portion of structure (2), provided that said polysilane compound has only one portion of structure 2A: Where X, Y, R 1 R 2 and" "Each is as described in Clause 1 regarding structure (1)-(3)."

[0130] Clause 9. A polysilane compound according to any one of Clauses 1 to 5, for example, wherein said polysilane compound comprises a portion of structure (2), provided that said polysilane compound has only one portion of structure 2B: Among them, X, Y and " "Each is as described in Clause 1 regarding structure (1)-(3), and R..." 0 It is not hydrogen, for example, the part of structure 2B has structure 2B(i): Where X, Y, R 1 R 2 and" "Each is as described in Clause 1 regarding structure (1)-(3)."

[0131] Clause 10. A polysilane compound according to any one of Clauses 1 to 9, wherein the molecular weight of said polysilane compound (calculated according to the molecular formula of said polysilane compound) is from 400 to less than 2000 g / mol, for example from 400 to 1000 g / mol.

[0132] Clause 11. A polysilane compound (or a polysilane compound according to any one of Clauses 1 to 5 and Clause 10), wherein said polysilane compound has the structure (4): Where (i) each Y 1 They can be the same or different, representing straight-chain or branched linking groups containing one or more carbon atoms, (ii) each R 3 They may be the same or different, indicating organic groups that are inert to isocyanate groups at 100°C or lower, (iii) each R 4They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, (iv) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 (v) Z represents an alkoxy group, which is inert to the isocyanate group at 100°C or lower, and in some cases is a divalent organic group, for example optionally containing a hydrocarbon group of oxygen, nitrogen, sulfur or a combination thereof that is inert to the isocyanate group, and comprising C1 to C2. 18 Alkylene or C5-C6 cycloalkylene, and (vi) m and n may be the same or different, each being an integer from 1 to 5, for example 1 to 3, or 1, for example where m+n is 2 to 10, for example 2 to 4, or 2, for example where the molecular weight of the polysilane compound (calculated according to the molecular formula of the polysilane compound) is 400 to less than 2000 g / mol, for example 400 to 1000 g / mol.

[0133] Clause 12. The polysilane compound according to Clause 11, wherein each R in structure (4) 3 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, each R 3 They can be the same or different, representing methyl, ethyl, propyl or butyl.

[0134] Clause 13. The polysilane compound pursuant to Clause 11 or Clause 12, wherein each X in structure (4) 1 Representing the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 To indicate an alkoxy group, for example, at least two X groups. 1 Indicates alkoxy groups such as methoxy, ethoxy, or propoxy, or each X 1 It indicates an alkoxy group, such as methoxy, ethoxy, or propoxy.

[0135] Clause 14. A polysilane compound according to any one of Clauses 11 to 13, wherein each Y in structure (4) 1 They may be the same or different, containing straight-chain or branched alkylene groups having 1 to 8 carbon atoms, such as straight-chain alkylene groups having 2 to 4 carbon atoms or, in some cases, 3 carbon atoms, or branched alkylene groups having 5 to 6 carbon atoms.

[0136] Clause 15. A polysilane compound according to any one of Clauses 11 to 14, wherein Z in structure (4) is: , where the value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. ; ; Each of these " "" indicates a connection to another part of the polysilane compound.

[0137] Clause 162. A polysilane compound (or a polysilane compound according to any one of Clauses 1 to 5 and Clause 10), wherein said polysilane compound has the structure (5): Where (i) is each Y 1 They can be the same or different, representing straight-chain or branched linking groups containing one or more carbon atoms, (ii) each R 3 They may be the same or different, indicating organic groups that are inert to isocyanate groups at 100°C or lower, (iii) each R 4 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, (iv) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 (v) Z represents an alkoxy group, which is inert to the isocyanate group at 100°C or lower, such as a hydrocarbon group optionally substituted with oxygen, nitrogen, sulfur or a combination thereof, and contains C1 to C2. 18Alkylene or C5-C6 cycloalkylene, and (vi) m and n may be the same or different, each being an integer from 1 to 5, for example 1 to 3, or 1, for example where m+n is 2 to 10, for example 2 to 4, or 2, for example where the molecular weight of the polysilane compound (calculated according to the molecular formula of the polysilane compound) is 400 to less than 2000 g / mol, for example 400 to 1000 g / mol.

[0138] Clause 17. The polysilane compound according to Clause 16, wherein each R in structure (5) 3 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, each R 3 They can be the same or different, representing methyl, ethyl, propyl or butyl.

[0139] Clause 18. The polysilane compound pursuant to Clause 16 or Clause 17, wherein each X in structure (5) 1 Representing the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 To indicate an alkoxy group, for example, at least two X groups. 1 Indicates alkoxy groups such as methoxy, ethoxy, or propoxy, or each X 1 It indicates an alkoxy group, such as methoxy, ethoxy, or propoxy.

[0140] Clause 19. A polysilane compound according to any one of Clauses 16 to 18, wherein each Y in structure (5) 1 They may be the same or different, containing straight-chain or branched alkylene groups having 1 to 8 carbon atoms, such as straight-chain alkylene groups having 2 to 4 carbon atoms or, in some cases, 3 carbon atoms, or branched alkylene groups having 5 to 6 carbon atoms.

[0141] Clause 20. A polysilane compound according to any one of Clauses 16 to 19, wherein Z in structure (5) is: , where the value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. Each of these " "" indicates a connection to another part of the polysilane compound.

[0142] Clause 21. A polysilane compound (or a polysilane compound according to any one of Clauses 1 to 5 and Clause 10), wherein said polysilane compound has the structure (6): Where: (i) Each Y 1 They can be the same or different, representing straight-chain or branched connecting groups containing one or more carbon atoms, (ii) Y 2 Groups representing the following structures: in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) p is 0 or 1; (iv) each R 3 They may be the same or different, indicating organic groups that are inert to the isocyanate group at 100°C or lower; (v) each R 4 They may be the same or different, representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower; and (vi) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 The alkoxy group indicates that, for example, the molecular weight (calculated according to the molecular formula of the polysilane compound) of the polysilane compound is 400 to less than 2000 g / mol, for example, 400 to 1000 g / mol.

[0143] Clause 22. The polysilane compound according to Clause 21, wherein each R in structure (6) 3 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, such as each R in structure (6). 3They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, such as each R in structure (6). 3 They can be the same or different, representing methyl, ethyl, propyl or butyl.

[0144] Clause 23. The polysilane compound pursuant to Clause 21 or Clause 22, wherein each X in structure (6) 1 Representing the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 To indicate an alkoxy group, for example, at least two X groups. 1 Indicates alkoxy groups such as methoxy, ethoxy, or propoxy, or each X 1 It indicates an alkoxy group, such as methoxy, ethoxy, or propoxy.

[0145] Clause 24. A polysilane compound according to any one of Clauses 21 to 23, wherein each Y in structure (6) 1 They may be the same or different, containing straight-chain or branched alkylene groups having 1 to 8 carbon atoms, such as straight-chain alkylene groups having 2 to 4 carbon atoms or, in some cases, 3 carbon atoms, or branched alkylene groups having 5 to 6 carbon atoms.

[0146] Clause 25. A polysilane compound according to any one of Clauses 21 to 24, wherein Z in structure (6) is: , where the value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. ; Each of these " "" indicates a connection to another part of the polysilane compound.

[0147] Clause 26. A polysilane compound (or a polysilane compound according to any one of Clauses 1 to 5 and Clause 10), wherein said polysilane compound has the structure (7): Where: (i) Each Y 1 They can be the same or different, representing straight-chain or branched connecting groups containing one or more carbon atoms, (ii) Y 2 Groups representing the following structures: in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) p is 0 or 1; (iv) each R 3 They may be the same or different, indicating organic groups that are inert to the isocyanate group at 100°C or lower; (v) each R 4 They may be the same or different, representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower; and (vi) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 The alkoxy group indicates that, for example, the molecular weight (calculated according to the molecular formula of the polysilane compound) of the polysilane compound is 400 to less than 2000 g / mol, for example, 400 to 1000 g / mol.

[0148] Clause 27. The polysilane compound according to Clause 26, wherein each R in structure (7) 3 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, such as each R in structure (7). 3 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, such as each R in structure (7). 3 They can be the same or different, representing methyl, ethyl, propyl or butyl.

[0149] Clause 28. The polysilane compound pursuant to Clause 26 or Clause 27, wherein each X in structure (7) 1 Representing the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X1 To indicate an alkoxy group, for example, at least two X groups. 1 Indicates alkoxy groups such as methoxy, ethoxy, or propoxy, or each X 1 It indicates an alkoxy group, such as methoxy, ethoxy, or propoxy.

[0150] Clause 29. A polysilane compound according to any one of Clauses 26 to 28, wherein each Y in structure (7) 1 They may be the same or different, containing straight-chain or branched alkylene groups having 1 to 8 carbon atoms, such as straight-chain alkylene groups having 2 to 4 carbon atoms or, in some cases, 3 carbon atoms, or branched alkylene groups having 5 to 6 carbon atoms.

[0151] Clause 30. A polysilane compound according to any one of Clauses 26 to 29, wherein Z in structure (7) is: The value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. Each of these " "" indicates a connection to another part of the polysilane compound.

[0152] Clause 31. A polysilane compound (or a polysilane compound according to any one of Clauses 1 to 5 and Clause 10), wherein said polysilane compound has the structure (8): Where: (i) Each Y 1 They can be the same or different, representing straight-chain or branched connecting groups containing one or more carbon atoms, (ii) each Y 2 The groups can be the same or different, representing the following structures: in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) each p may be the same or different, and may be 0 or 1; (iv) each R 3 Can be the same or different, indicating an organic group that is inert to the isocyanate group at 100°C or lower, (v) each R 4 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, (vi) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 (vii) Z indicates an alkoxy group, which is inert to the isocyanate group at 100°C or lower, and in some cases is a divalent organic group, such as one containing C1 to C2. 18 The alkylene or C5-C6 cycloalkylene hydrocarbon group, and (vii) m and n may be the same or different, each being an integer from 1 to 5, for example 1 to 3, or 1, for example where m+n is 2 to 10, for example 2 to 4, or 2, for example where the molecular weight of the polysilane compound (calculated according to the molecular formula of the polysilane compound) is 400 to less than 2000 g / mol, for example 400 to 1000 g / mol.

[0153] Clause 32. The polysilane compound according to Clause 31, wherein each R in structure (8) 3 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, each R 3 They can be the same or different, representing methyl, ethyl, propyl or butyl.

[0154] Clause 33. The polysilane compound pursuant to Clause 31 or Clause 32, wherein each X in structure (8) 1 Representing the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 To indicate an alkoxy group, for example, at least two X groups. 1 Indicates alkoxy groups such as methoxy, ethoxy, or propoxy, or each X 1 It indicates an alkoxy group, such as methoxy, ethoxy, or propoxy.

[0155] Clause 34. A polysilane compound according to any one of Clauses 31 to 33, wherein each Y in structure (8) 1 They may be the same or different, containing straight-chain or branched alkylene groups having 1 to 8 carbon atoms, such as straight-chain alkylene groups having 2 to 4 carbon atoms or, in some cases, 3 carbon atoms, or branched alkylene groups having 5 to 6 carbon atoms.

[0156] Clause 35. A polysilane compound according to any one of Clauses 31 to 34, wherein Z in structure (8) is: The value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. Each of these " "" indicates a connection to another part of the polysilane compound.

[0157] Clause 36. A polysilane compound (or a polysilane compound according to any one of Clauses 1 to 5 and Clause 10), wherein said polysilane compound has the structure (9): Where: (i) Each Y 1 They can be the same or different, representing straight-chain or branched connecting groups containing one or more carbon atoms, (ii) each Y 2 The groups can be the same or different, representing the following structures: in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) each p may be the same or different, and may be 0 or 1; (iv) each R 3 Can be the same or different, indicating an organic group that is inert to the isocyanate group at 100°C or lower, (v) each R 4 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, (vi) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 (vii) Z indicates an alkoxy group, which is inert to the isocyanate group at 100°C or lower, and in some cases is a divalent organic group, such as one containing C1 to C2. 18 The alkylene or C5-C6 cycloalkylene hydrocarbon group, and (vii) m and n may be the same or different, each being an integer from 1 to 5, for example 1 to 3, or 1, for example where m+n is 2 to 10, for example 2 to 4, or 2, for example where the molecular weight of the polysilane compound (calculated according to the molecular formula of the polysilane compound) is 400 to less than 2000 g / mol, for example 400 to 1000 g / mol.

[0158] Clause 37. The polysilane compound pursuant to Clause 36, wherein each R in structure (9) 3 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, each R 3 They can be the same or different, representing methyl, ethyl, propyl or butyl.

[0159] Clause 38. A polysilane compound pursuant to Clause 36 or Clause 37, wherein each X in structure (9) 1 Representing the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 To indicate an alkoxy group, for example, at least two X groups. 1 Indicates alkoxy groups such as methoxy, ethoxy, or propoxy, or each X 1 It indicates an alkoxy group, such as methoxy, ethoxy, or propoxy.

[0160] Clause 39. A polysilane compound according to any one of Clauses 36 to 38, wherein each Y in structure (9)1 They may be the same or different, containing straight-chain or branched alkylene groups having 1 to 8 carbon atoms, such as straight-chain alkylene groups having 2 to 4 carbon atoms or, in some cases, 3 carbon atoms, or branched alkylene groups having 5 to 6 carbon atoms.

[0161] Clause 40. A polysilane compound according to any one of Clauses 36 to 39, wherein Z in structure (9) is: The value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. Each of these " "" indicates a connection to another part of the polysilane compound.

[0162] Clause 41. A polysilane compound (or a polysilane compound according to any one of Clauses 1 to 5 and Clause 10), wherein said polysilane compound has the structure (10): Where (i) each Y 1 They can be the same or different, representing straight-chain or branched connecting groups containing one or more carbon atoms, (ii) each Y 2 The groups can be the same or different, representing the following structures: in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) each p may be the same or different, and may be 0 or 1; (iv) each R 3 Can be the same or different, indicating an organic group that is inert to the isocyanate group at 100°C or lower, (v) each R 4 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, (vi) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 (vii) Z indicates an alkoxy group, which is inert to the isocyanate group at 100°C or lower, and in some cases is a divalent organic group, such as one containing C1 to C2. 18 The hydrocarbon group is alkylene or C5-C6 cycloalkylene, and (vii) m+n is 2 to 10, for example 2 to 4, or 2, for example, the molecular weight of the polysilane compound (calculated according to the molecular formula of the polysilane compound) is 400 to less than 2000 g / mol, for example 400 to 1000 g / mol.

[0163] Clause 42. The polysilane compound according to Clause 41, wherein each R in structure (10) 3 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, each R 3 They can be the same or different, representing methyl, ethyl, propyl or butyl.

[0164] Clause 43. The polysilane compound pursuant to Clause 41 or Clause 42, wherein each X in structure (10) 1 Representing the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 To indicate an alkoxy group, for example, at least two X groups. 1 Indicates alkoxy groups such as methoxy, ethoxy, or propoxy, or each X 1 It indicates an alkoxy group, such as methoxy, ethoxy, or propoxy.

[0165] Clause 44. A polysilane compound according to any one of Clauses 41 to 43, wherein each Y in structure (10) 1They may be the same or different, containing straight-chain or branched alkylene groups having 1 to 8 carbon atoms, such as straight-chain alkylene groups having 2 to 4 carbon atoms or, in some cases, 3 carbon atoms, or branched alkylene groups having 5 to 6 carbon atoms.

[0166] Clause 45. A polysilane compound according to any one of Clauses 41 to 44, wherein Z in structure (10) is: The value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. Each of these " "" indicates a connection to another part of the polysilane compound.

[0167] Clause 46. A polysilane compound (or a polysilane compound according to any one of Clauses 1 to 5 and Clause 10), wherein said polysilane compound has the structure (11): Where (i) each Y 1 They can be the same or different, representing straight-chain or branched connecting groups containing one or more carbon atoms, (ii) each Y 2 The groups can be the same or different, representing the following structures: in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) each p may be the same or different, and may be 0 or 1; (iv) each R 3 Can be the same or different, indicating an organic group that is inert to the isocyanate group at 100°C or lower, (v) each R 4 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, (vi) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 (vii) Z indicates an alkoxy group, which is inert to the isocyanate group at 100°C or lower, and in some cases is a divalent organic group, such as one containing C1 to C2. 18 The hydrocarbon group is alkylene or C5-C6 cycloalkylene, and (vii) m+n is 2 to 10, for example 2 to 4, or 2, for example, the molecular weight of the polysilane compound (calculated according to the molecular formula of the polysilane compound) is 400 to less than 2000 g / mol, for example 400 to 1000 g / mol.

[0168] Clause 47. The polysilane compound according to Clause 46, wherein each R in structure (11) 3 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, each R 3 They can be the same or different, representing methyl, ethyl, propyl or butyl.

[0169] Clause 48. A polysilane compound pursuant to Clause 46 or Clause 47, wherein each X in structure (11) 1 Representing the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 To indicate an alkoxy group, for example, at least two X groups. 1 Indicates alkoxy groups such as methoxy, ethoxy, or propoxy, or each X 1 It indicates an alkoxy group, such as methoxy, ethoxy, or propoxy.

[0170] Clause 49. A polysilane compound according to any one of Clauses 46 to 48, wherein each Y in structure (11) 1They may be the same or different, containing straight-chain or branched alkylene groups having 1 to 8 carbon atoms, such as straight-chain alkylene groups having 2 to 4 carbon atoms or, in some cases, 3 carbon atoms, or branched alkylene groups having 5 to 6 carbon atoms.

[0171] Clause 50. A polysilane compound according to any one of Clauses 46 to 49, wherein Z in structure (11) is: The value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. Each of these " "" indicates a connection to another part of the polysilane compound.

[0172] Clause 51. A polysilane compound (or a polysilane compound according to any one of Clauses 1 to 50) comprising a reaction product containing: (a) a polyisocyanate, such as a diisocyanate; and (b) an aspartic ester silane having the following structure: Each R 15 and each X 4 They may be the same or different, representing organic groups that are inert to isocyanate groups at 100°C or lower, provided that at least one X 4 Y represents an alkoxy group. 4 This indicates a straight-chain or branched linking group containing one or more carbon atoms, and each R 15bThey may be the same or different, representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, for example, the molecular weight (calculated according to the molecular formula of the polysilane compound) of the polysilane compound is 400 to less than 2000 g / mol, for example 400 to 1000 g / mol.

[0173] Clause 52. The polysilane compound according to Clause 51, wherein said aspartic ester silane comprises a reaction product containing reactants of the following: (i) Formula aminoalkylalkoxysilanes, and (ii) formula Maleate or fumarate, wherein R 16 and R 17 This refers to the same or different organic groups that are inert to isocyanates below 100°C, such as R. 16 and R 17 Represents the same or different alkyl groups having 1 to 4 carbon atoms, each R 18 They may be the same or different, representing hydrogen or an organic group that is inert to isocyanates below 100°C, each X 5 This refers to the same or different organic groups that are inert to isocyanates below 100°C, provided that at least one X group is present. 5 It is an alkoxy group, for example, each X 5 To represent the same or different alkyl or alkoxy groups having 1 to 4 carbon atoms, provided that at least one X 5 It is an alkoxy group, and n is an integer from 2 to 4, for example, 3.

[0174] Clause 53. The polysilane compound according to Clause 52, wherein the aminoalkylalkoxysilane comprises 2-aminoethyldimethylmethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, or any mixture of two or more thereof.

[0175] Clause 54. A polysilane compound pursuant to Clause 52 or Clause 53, wherein the maleate or fumarate comprises dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, or any mixture of two or more thereof.

[0176] Clause 55. A polysilane compound according to any one of Clauses 52 to 54, wherein the maleate or fumarate is present with the aminoalkylalkoxysilane in a molar ratio of 0.8 to 1.2:1, 1.0 to 1.2:1 or 1.01 to 1.2:1 to the aminoalkylalkoxysilane.

[0177] Clause 56. A polysilane compound according to any one of Clauses 51 to 55, wherein said polyisocyanate has the following structure: Where Z represents an organic group that is inert to the isocyanate group at 100°C or lower, and in some cases is a divalent organic group, such as one containing C1 to C2. 18 An alkylene or C5-C6 cycloalkylene hydrocarbon group, wherein m and n may be the same or different, each being an integer from 1 to 5, for example 1 to 3, or 1, wherein m+n is 2 to 10, for example 2 to 4, or 2, and wherein Z in the aforementioned polyisocyanate structure is: The value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. Each of these " "" indicates a connection to another part of the polysilane compound.

[0178] Clause 57. A polysilane compound according to any one of Clauses 51 to 56, wherein said polyisocyanate comprises 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene 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′-biphenyl diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, methylene bis( 4-Cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis(2-ethyl isocyanate) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated diphenylmethylene diisocyanate, tetramethyl diphenylmethylene diisocyanate, lysine isocyanate, hexamethylene diisocyanate trimer, triphenylmethane-4,4′,4″-triisocyanate, hexamethylene diisocyanate trimer, aromatic polyisocyanates based on toluene diisocyanate, polyisocyanurates based on toluene diisocyanate, or any combination of two or more.

[0179] Clause 57. A method for preparing a polysilane compound according to any one of Clauses 51 to 52, comprising reacting the polyisocyanate with the aspartic ester silane, optionally in the presence of a catalyst, to produce a polysilane compound comprising an aspartic ester group.

[0180] Clause 58. The method according to Clause 57, wherein the optional catalyst comprises an organometallic catalyst, an amine catalyst, or a combination thereof, for example, a catalyst comprising a copper compound such as copper naphthenate, a cobalt compound such as cobalt naphthenate, a zinc compound such as zinc naphthenate, a bismuth compound such as bismuth neodecanoate, a tin compound such as di-n-butyltin dilaurate, triethylamine, triethylenediamine, DABCO, DMEA, or any combination of two or more of the foregoing.

[0181] Clause 59. The method according to Clause 57 or Clause 58, wherein the reaction is carried out at a temperature of 10 to 120°C or 25 to 100°C.

[0182] Clause 60. The method according to any one of Clauses 57 to 59, wherein the relative amounts of the polyisocyanate and the aspartic ester silane are such that the molar ratio of the isocyanate reactive group to the isocyanate group is at least 1:1, for example greater than 1:1 and less than 1.5:1.

[0183] Clause 61. The method according to any one of Clauses 57 to 60 further comprises converting at least some aspartic ester groups into hydantoin groups, wherein the conversion is optionally carried out in the presence of a catalyst, such as a Bronsted acid, carboxylic acid, sulfonic acid, phenol, or any two or more of the thereof, at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, 80°C to 100°C, 90 to 120°C, or 100 to 120°C.

[0184] Clause 62. A polysilane compound (or a polysilane compound according to any one of Clauses 1 to 50) comprising a reaction product containing: (a) an aspartic ester silane; and (b) an isocyanate-functionalized silane, wherein (1) the aspartic ester silane has the following structure: Where (i) is each R 15 and each X 4 They may be the same or different, representing organic groups that are inert to isocyanate groups at 100°C or lower, provided that at least one X 4 Indicates alkoxy group, (ii) Y 4 This indicates a straight-chain or branched linking group containing one or more carbon atoms, and (iii) each R 15b They may be the same or different, representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, and (2) the isocyanate-functionalized silane has the following structure: Where (i) Y 1 This refers to a straight-chain or branched linking group containing one or more carbon atoms, such as Y. 1 Contains a straight-chain or branched alkylene group having 1 to 8 carbon atoms, such as a straight-chain alkylene group having 2 to 4 carbon atoms, or in some cases 3 carbon atoms, or a branched alkylene group having 5 to 6 carbon atoms, (ii) Y 2 Groups representing the following structures in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) p is 0 or 1, and (iv) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1Indicates alkoxy groups, for example, each X 1 Representing the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 The alkoxy group indicates that the molecular weight (calculated according to the molecular formula of the polysilane compound) is 400 to less than 2000 g / mol, for example, 400 to 1000 g / mol.

[0185] Clause 63. The polysilane compound according to Clause 62, wherein said aspartic ester silane comprises a reaction product containing reactants of the following: (i) formula aminoalkylalkoxysilanes, and (ii) formula Maleate or fumarate, wherein R 16 and R 17 This refers to the same or different organic groups that are inert to isocyanates below 100°C, such as R. 16 and R 17 Represents the same or different alkyl groups having 1 to 4 carbon atoms, each R 18 They may be the same or different, representing hydrogen or an organic group that is inert to isocyanates below 100°C, each X 5 This refers to the same or different organic groups that are inert to isocyanates below 100°C, provided that at least one X group is present. 5 It is an alkoxy group, for example, each X 5 To represent the same or different alkyl or alkoxy groups having 1 to 4 carbon atoms, provided that at least one X 5 It is an alkoxy group, and n is an integer from 2 to 4, for example, 3.

[0186] Clause 64. The polysilane compound according to Clause 63, wherein the aminoalkylalkoxysilane comprises 2-aminoethyldimethylmethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, or any mixture of two or more thereof.

[0187] Clause 65. A polysilane compound pursuant to Clause 63 or Clause 64, wherein the maleate or fumarate comprises dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, or any mixture of two or more thereof.

[0188] Clause 66. A polysilane compound according to any one of Clauses 63 to 65, wherein the maleate or fumarate is present with the aminoalkylalkoxysilane in a molar ratio of 0.8 to 1.2:1, 1.0 to 1.2:1 or 1.01 to 1.2:1, including but not limited to those previously described that react with polyisocyanates.

[0189] Clause 67. A polysilane compound according to any one of Clauses 62 to 66, wherein at least two X 1 Indicates alkoxy groups such as methoxy, ethoxy, or propoxy, or each X 1 It indicates an alkoxy group, such as methoxy, ethoxy, or propoxy.

[0190] Clause 68. A polysilane compound according to any one of Clauses 62 to 67, wherein the isocyanate-functionalized silane comprises the reaction product of 3-propylmethyldimethoxysilane, 3-propyltrimethoxysilane, 3-propyltriethoxysilane, a silane containing active hydrogen (e.g., hydroxyl, thiol, primary or secondary amine functionalized silane) and a polyisocyanate, wherein the reaction product is an isocyanate-functionalized silane containing a carbamate, thiocarbamate, urea or aspartic urea group, or a mixture of any two or more of the above isocyanate-functionalized silanes.

[0191] Clause 69. The polysilane compound according to Clause 68, wherein said polyisocyanate has the following structure: Z represents an organic group that is inert to the isocyanate group at 100°C or lower, and in some cases is a divalent organic group, such as a hydrocarbon group optionally substituted with oxygen, nitrogen, sulfur or a combination thereof, and contains C1 to C2. 18 Alkylene or C5-C6 cycloalkylene, and m and n may be the same or different, each being an integer from 1 to 5, for example 1 to 3, or 1, for example where m+n is 2 to 10, for example 2 to 4, or 2, and for example where Z in the aforementioned polyisocyanate structure is: The value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. Each of these " "" indicates a connection to another part of the polysilane compound.

[0192] Clause 70. A polysilane compound pursuant to Clause 68 or Clause 69, wherein said polyisocyanate comprises 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene 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′-biphenyl diisocyanate, 1,6-hexanediisocyanate, isophorone diisocyanate, methylene bis(4- Cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis(2-ethyl isocyanate) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated diphenylmethylene diisocyanate, tetramethyl diphenylmethylene diisocyanate, lysine isocyanate, hexamethylene diisocyanate trimer, triphenylmethane-4,4′,4″-triisocyanate, hexamethylene diisocyanate trimer, aromatic polyisocyanates based on toluene diisocyanate, polyisocyanurates based on toluene diisocyanate, or any combination of two or more.

[0193] Clause 71. A method for preparing a polysilane compound according to any one of Clauses 62 to 70, comprising reacting the aspartic ester silane with the isocyanate-functionalized silane, optionally in the presence of a catalyst, to produce a polysilane compound comprising an aspartic ester group.

[0194] Clause 72. The method according to Clause 71, wherein the optional catalyst comprises an organometallic catalyst, an amine catalyst, or a combination thereof, for example, a catalyst comprising a copper compound such as copper naphthenate, a cobalt compound such as cobalt naphthenate, a zinc compound such as zinc naphthenate, a bismuth compound such as bismuth neodecanoate, a tin compound such as di-n-butyltin dilaurate, triethylamine, triethylenediamine, DABCO, DMEA, or any combination of two or more of the foregoing.

[0195] Clause 73. The method according to Clause 71 or Clause 72, wherein the reaction is carried out at a temperature of 10 to 120°C or 25 to 100°C.

[0196] Clause 74. The method according to any one of Clauses 71 to 73, wherein the relative amounts of the aspartic ester silane and the isocyanate functional silane are such that the molar ratio of the isocyanate reactive group to the isocyanate group is at least 1:1, for example greater than 1:1 and less than 1.5:1.

[0197] Clause 75. The method according to any one of Clauses 71 to 74 further comprises converting at least some aspartic ester groups into hydantoin groups, wherein the conversion is optionally carried out in the presence of a catalyst, such as a Bronsted acid, carboxylic acid, sulfonic acid, phenol, or any two or more of the thereof, at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, 80°C to 100°C, 90 to 120°C, or 100 to 120°C.

[0198] Clause 76. A polysilane compound (or a polysilane compound according to any one of Clauses 1 to 50) comprising a reaction product containing: (a) an aspartic ester containing a primary amine and / or a polyaspartic ester; and (b) an isocyanate-functionalized silane, wherein (1) the isocyanate-functionalized silane has the following structure: Where (i) Y 1 This refers to a straight-chain or branched linking group containing one or more carbon atoms, such as Y. 1 Contains a straight-chain or branched alkylene group having 1 to 8 carbon atoms, such as a straight-chain alkylene group having 2 to 4 carbon atoms, or in some cases 3 carbon atoms, or a branched alkylene group having 5 to 6 carbon atoms, (ii) Y 2 Groups representing the following structures: in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) p is 0 or 1, and (iv) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 Indicates alkoxy groups, for example, each X 1 Representing the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1The alkoxy group represents, and (2) the primary amine-containing aspartic esters and / or polyaspartic esters suitable for preparing such polysilane compounds are represented by the following structures: Z 1 Indicates that it optionally contains a hydrocarbon group (in some cases a divalent hydrocarbon group) that is inert to isocyanate, consisting of oxygen, nitrogen, sulfur, or a combination thereof. 18 and R 19 They can be the same or different, indicating organic groups that are inert to the isocyanate group at 100°C or lower, such as R. 18 and R 19 Represents the same or different alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, R. 18 and R 19 They can be the same or different, each being methyl, ethyl, propyl, or butyl, R 20 and R 21 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower. m and n may be the same or different, each being an integer from 0 to 4, provided that m+n is at least 2. For example, the molecular weight (calculated according to the molecular formula of the polysilane compound) of the polysilane compound is 400 to less than 2000 g / mol, for example, 400 to 1000 g / mol.

[0199] Clause 77. The polysilane compound according to Clause 76, wherein the primary amine-containing aspartic ester comprises (a) formula (NH2)mZ 1 (NH2) n primordine (of which Z) 1 The hydrocarbon group is optionally substituted with oxygen, nitrogen, sulfur, or a combination thereof, and in some cases is a divalent hydrocarbon group, and m+n is an integer of at least 2, for example 2 to 4) and formula (b). (Both isomers are represented by tilde bonds) the reaction products of maleate or fumarate, wherein each R 22 They can be the same or different, representing organic groups that are inert to the isocyanate group at 100°C or lower. Each R 23 They can be the same or different, indicating hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower.

[0200] Clause 78. The polysilane compound pursuant to Clause 77, wherein said primary amine comprises ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,2-butanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-hexanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, bis-(3-aminopropyl) ether, 1,2-bis-(3-aminopropoxy)ethane, 1,3-bis-(3-aminopropoxy)-2,2′-dimethylpropane, 1,2-diaminocyclohexane, etc. Hexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-diaminomethylcyclohexane, 1,4-diaminomethylcyclohexane, 1,3-diaminoethylcyclohexane, 1,4-diaminoethylcyclohexane, 1,3-diaminopropylcyclohexane, 1,4-diaminopropylcyclohexane, hydrogenated 4,4′-diaminodiphenylmethane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4-and / or 2,6-hexahydrotoluenediamine, 2,4′-and / or 4,4′-diaminodicyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, propane-1,2,3-triamine, pentane-1,3,5-triamine Benzene-1,3,5-triamine, isophorone diamine, menthane diamine, 1,4-diaminopropylpiperazine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, 2,4-toluenediamine, 2,4′-and / or 4,4′-diaminodiphenylmethane, m-aminobenzylamine, 4-chloro-o-phenylenediamine, tetrachloro-p-phenylenediethylenediamine, 4-methoxy-6-methyl-m-phenylenediamine, m-phenylenediethylenediamine, p-phenylenediethylenediamine, 1,5-naphthylenediamine, 2,6-naphthylenediamine, benzidine, 4,4′-bis(o-toluidine), dianisidine, 4,4′-diaminodiphenylmethane, 2,2-(4,4′-diaminodiphenyl)propane, 4,4 ′-Diaminodiphenyl ether, 4,4′-thiodiphenylamine, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodimethylmethyl sulfone, methylene bis(o-chloroaniline), 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, diethylenetriamine, iminodipropylamine, methyliminodipropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,4-bis(aminoethylpiperazine), 1,4-bis(aminopropylpiperazine), 2,6-diaminopyridine, bis(3,4-diaminophenyl) sulfone, relatively high molecular weight polyether polyamines containing aliphatic bonded primary amino groups (e.g., commercially available JEFFAMINE® products from Huntsman Corp.), and any combination of two or more of the above.

[0201] Clause 79. A polysilane compound pursuant to Clause 77 or Clause 78, wherein the maleate or fumarate comprises dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, or any mixture of two or more thereof.

[0202] Clause 80. A polysilane compound according to any one of Clauses 76 to 79, wherein the isocyanate-functionalized silane comprises the reaction product of 3-propylmethyldimethoxysilane, 3-propyltrimethoxysilane, 3-propyltriethoxysilane, a silane containing active hydrogen (e.g., hydroxyl, thiol, primary or secondary amine functionalized silane) and a polyisocyanate, wherein the reaction product is an isocyanate-functionalized silane containing a carbamate, thiocarbamate, urea or aspartic urea group, or a mixture of any two or more of the above isocyanate-functionalized silanes.

[0203] Clause 81. The polysilane compound according to Clause 80, wherein said polyisocyanate has the following structure: Where Z represents an organic group that is inert to the isocyanate group at 100°C or lower, and in some cases is a divalent organic group, such as one containing C1 to C2. 18 An alkylene or C5-C6 cycloalkylene hydrocarbon group, wherein m and n may be the same or different, each being an integer from 1 to 5, for example 1 to 3, or 1, wherein m+n is 2 to 10, for example 2 to 4, or 2, and wherein Z in the aforementioned polyisocyanate structure is: The value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. Each of these " "" indicates a connection to another part of the polysilane compound.

[0204] Clause 82. The polysilane compound pursuant to Clause 80 or Clause 81, wherein said polyisocyanate comprises 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene 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′-biphenyl diisocyanate, 1,6-hexanediisocyanate, isophorone diisocyanate, methylene bis(4- Cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis(2-ethyl isocyanate) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated diphenylmethylene diisocyanate, tetramethyl diphenylmethylene diisocyanate, lysine isocyanate, hexamethylene diisocyanate trimer, triphenylmethane-4,4′,4″-triisocyanate, hexamethylene diisocyanate trimer, aromatic polyisocyanates based on toluene diisocyanate, polyisocyanurates based on toluene diisocyanate, or any combination of two or more.

[0205] Clause 83. A method for preparing a polysilane compound according to any one of Clauses 76 to 82, comprising reacting the primary amine-containing aspartic ester and / or polyaspartic ester with the isocyanate-functionalized silane, optionally in the presence of a catalyst, to produce a polysilane compound comprising an aspartic ester group.

[0206] Clause 84. The method according to Clause 83, wherein the optional catalyst comprises an organometallic catalyst, an amine catalyst, or a combination thereof, for example, a catalyst comprising a copper compound such as copper naphthenate, a cobalt compound such as cobalt naphthenate, a zinc compound such as zinc naphthenate, a bismuth compound such as bismuth neodecanoate, a tin compound such as di-n-butyltin dilaurate, triethylamine, triethylenediamine, DABCO, DMEA, or any combination of two or more of the foregoing.

[0207] Clause 85. The method according to Clause 83 or Clause 84, wherein the reaction is carried out at a temperature of 10 to 120°C or 25 to 100°C.

[0208] Clause 86. The method according to any one of Clauses 83 to 85, wherein the relative amounts of the primary amine-containing aspartic ester and / or polyaspartic ester to the isocyanate-functionalized silane are such that the molar ratio of the isocyanate reactive group to the isocyanate group is at least 1:1, for example greater than 1:1 and less than 1.5:1.

[0209] Clause 87. The method according to any one of Clauses 83 to 86 further comprises converting at least some aspartic ester groups into hydantoin groups, wherein the conversion is optionally carried out in the presence of a catalyst, such as a Bronsted acid, carboxylic acid, sulfonic acid, phenol, or any two or more of the thereof, at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, 80°C to 100°C, 90 to 120°C, or 100 to 120°C.

[0210] Clause 88. A polysilane compound (or a polysilane compound pursuant to any one of Clauses 1 to 50) comprising a reaction product containing: (a) an isocyanate-functionalized silane having the following structure: Where (i) Y 1 This refers to a straight-chain or branched linking group containing one or more carbon atoms, such as Y. 1 Contains a straight-chain or branched alkylene group having 1 to 8 carbon atoms, such as a straight-chain alkylene group having 2 to 4 carbon atoms, or in some cases 3 carbon atoms, or a branched alkylene group having 5 to 6 carbon atoms, (ii) Y 2 Groups representing the following structures: in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) p is 0 or 1, and (iv) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 Indicates alkoxy groups, for example, each X 1 Representing the same or different alkyl, acyl, or alkoxy groups, for example, the same or different alkyl, acyl, or alkoxy groups having 1 to 9 or 1 to 4 carbon atoms, provided that at least one X 1 (b) Polyaspartic acid esters with the following structures: , where (i) each R 3 They may be the same or different, representing organic groups that are inert to isocyanate groups at 100°C or lower, (ii) each R 4They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, (iii) Z representing an organic group that is inert to the isocyanate group at 100°C or lower, and in some cases a divalent organic group, such as containing C1 to C2. 18 The hydrocarbon group is an alkylene group or a C5-C6 cycloalkylene group, and (iv)m+n is 2 to 10, for example 2 to 4, or 2, for example, where each R 3 They may be the same or different, representing alkyl groups, such as alkyl groups having 1 to 9 or 1 to 4 carbon atoms, for example, each R 3 They may be the same or different, representing methyl, ethyl, propyl or butyl, for example, the molecular weight of said polysilane compound (calculated according to the molecular formula of said polysilane compound) is 400 to less than 2000 g / mol, for example 400 to 1000 g / mol.

[0211] Clause 89. The polysilane compound according to Clause 88, wherein the isocyanate-functionalized silane comprises the reaction product of 3-propylmethyldimethoxysilane, 3-propyltrimethoxysilane, 3-propyltriethoxysilane, a silane containing active hydrogen (e.g., hydroxyl, thiol, primary or secondary amine functionalized silane) and a polyisocyanate, wherein the reaction product is an isocyanate-functionalized silane containing a carbamate, thiocarbamate, urea or aspartic urea group, or a mixture of any two or more of the above isocyanate-functionalized silanes.

[0212] Clause 90. The polysilane compound according to Clause 89, wherein said polyisocyanate has the following structure: Where Z represents an organic group that is inert to the isocyanate group at 100°C or lower, and in some cases is a divalent organic group, such as one containing C1 to C2. 18 An alkylene or C5-C6 cycloalkylene hydrocarbon group, wherein m and n may be the same or different, each being an integer from 1 to 5, for example 1 to 3, or 1, wherein m+n is 2 to 10, for example 2 to 4, or 2, and wherein Z in the aforementioned polyisocyanate structure is: The value of x ranges from 3 to 19; Each of X1, X2, X3 and X4 may be the same or different, and its value is from 1 to 10, provided that the molecular weight of the structure is from 200 to 1500. Each of these " "" indicates a connection to another part of the polysilane compound.

[0213] Clause 91. A polysilane compound pursuant to Clause 89 or Clause 90, wherein said polyisocyanate comprises 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene 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′-diphenylmethane diisocyanate, etc. Benzene diisocyanate, 1,6-hexanediisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl)isocyanate, 2,2,4-trimethylhexamethylene diisocyanate, bis(2-ethyl isocyanate) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated diphenylene diisocyanate, tetramethylbenzene diisocyanate, lysine isocyanate, hexamethylene diisocyanate trimer (Desmodur®) N3300A, commercially available from Covestro, triphenylmethane-4,4′,4″-triisocyanate (Desmodur® RE, commercially available from Covestro), hexamethylene diisocyanate trimer (Desmodur® N3200, commercially available from Covestro), aromatic polyisocyanates based on toluene diisocyanate (Desmodur® ILBA, commercially available from Covestro), polyisocyanates based on toluene diisocyanate (Desmodur® RC, commercially available from Covestro), or any combination of two or more.

[0214] Clause 92. A polysilane compound according to any one of Clauses 88 to 91, wherein said polyaspartic ester is (a) of formula (NH2)mZ 1 (NH2) n primordine (of which Z) 1 Optionally containing a hydrocarbon group that is inert to isocyanate, such as oxygen, nitrogen, sulfur, or a combination thereof, and where m+n is an integer of at least 2, for example, 2 to 4) and formula (b). The reaction products of maleate or fumarate (both isomers are represented by tilde bonds), Each R 22 They can be the same or different, representing organic groups that are inert to the isocyanate group at 100°C or lower. Each R 23 They can be the same or different, indicating hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower.

[0215] Clause 93. The polysilane compound according to Clause 92, wherein said primary amine comprises ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,2-butanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-hexanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, bis-(3-aminopropyl) ether, 1,2-bis-(3-aminopropoxy)ethane, 1,3-bis-(3-aminopropoxy)-2,2′-dimethylpropane, 1,2-diaminocyclohexane, etc. Hexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-diaminomethylcyclohexane, 1,4-diaminomethylcyclohexane, 1,3-diaminoethylcyclohexane, 1,4-diaminoethylcyclohexane, 1,3-diaminopropylcyclohexane, 1,4-diaminopropylcyclohexane, hydrogenated 4,4′-diaminodiphenylmethane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4-and / or 2,6-hexahydrotoluenediamine, 2,4′-and / or 4,4′-diaminodicyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, propane-1,2,3-triamine, pentane-1,3,5-triamine Benzene-1,3,5-triamine, isophorone diamine, menthane diamine, 1,4-diaminopropylpiperazine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, 2,4-toluenediamine, 2,4′-and / or 4,4′-diaminodiphenylmethane, m-aminobenzylamine, 4-chloro-o-phenylenediamine, tetrachloro-p-phenylenediethylenediamine, 4-methoxy-6-methyl-m-phenylenediamine, m-phenylenediethylenediamine, p-phenylenediethylenediamine, 1,5-naphthylenediamine, 2,6-naphthylenediamine, benzidine, 4,4′-bis(o-toluidine), dianisidine, 4,4′-diaminodiphenylmethane, 2,2-(4,4′-diaminodiphenyl)propane, 4,4 ′-Diaminodiphenyl ether, 4,4′-thiodiphenylamine, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodimethylmethyl sulfone, methylene bis(o-chloroaniline), 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, diethylenetriamine, iminodipropylamine, methyliminodipropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,4-bis(aminoethylpiperazine), 1,4-bis(aminopropylpiperazine), 2,6-diaminopyridine, bis(3,4-diaminophenyl) sulfone, relatively high molecular weight polyether polyamines containing aliphatic bonded primary amino groups (e.g., commercially available JEFFAMINE® products from Huntsman Corp.), and any combination of two or more of the above.

[0216] Clause 94. A polysilane compound pursuant to Clause 92 or Clause 93, wherein the maleate or fumarate comprises dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, or any mixture of two or more thereof.

[0217] Clause 95. A method for preparing a polysilane compound according to any one of Clauses 88 to 94, comprising reacting the isocyanate-functionalized silane with the polyaspartic ester, optionally in the presence of a catalyst, to produce a polysilane compound comprising an aspartic ester group.

[0218] Clause 96. The method according to Clause 95, wherein the optional catalyst comprises an organometallic catalyst, an amine catalyst, or a combination thereof, for example, a catalyst comprising a copper compound such as copper naphthenate, a cobalt compound such as cobalt naphthenate, a zinc compound such as zinc naphthenate, a bismuth compound such as bismuth neodecanoate, a tin compound such as di-n-butyltin dilaurate, triethylamine, triethylenediamine, DABCO, DMEA, or any combination of two or more of the foregoing.

[0219] Clause 97. The method according to Clause 95 or Clause 96, wherein the reaction is carried out at a temperature of 10 to 120°C or 25 to 100°C.

[0220] Clause 98. The method according to any one of Clauses 95 to 97, wherein the relative amounts of the primary amine-containing aspartic ester and / or polyaspartic ester to the isocyanate-functionalized silane are such that the molar ratio of the isocyanate reactive group to the isocyanate group is at least 1:1, for example greater than 1:1 and less than 1.5:1.

[0221] Clause 99. The method according to any one of Clauses 95 to 98 further includes converting at least some aspartic ester groups into hydantoin groups, wherein the conversion is optionally carried out in the presence of a catalyst, such as a Bronsted acid, carboxylic acid, sulfonic acid, phenol, or any two or more of the thereof, at a reaction temperature of 0 to 200°C, 70 to 130°C, 75 to 105°C, 80°C to 100°C, 90 to 120°C, or 100 to 120°C.

[0222] Clause 100. A composition, such as a radiation-curable composition, comprising: (a) a polysilane compound according to any one of Clauses 1 to 56, Clauses 62 to 70, Clauses 76 to 82, or Clauses 88 to 94, or (b) a polysilane compound prepared by any one of the methods of Clauses 57 to 61, Clauses 71 to 75, Clauses 83 to 87, or Clauses 95 to 99.

[0223] Clause 101. The composition according to Clause 100, wherein the polysilane 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 solids in the composition.

[0224] Clause 102. The composition according to Clause 100 or Clause 101, wherein said composition further comprises (b) an olefinic unsaturated oligomer, such as an olefinic unsaturated oligomer with 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, as measured by size exclusion chromatography (SEC).

[0225] Clause 103. The composition according to Clause 102, wherein the olefinic unsaturated oligomer comprises a urethane (meth)acrylate oligomer comprising (meth)acrylate groups, urethane groups and a backbone, wherein the backbone is, for example, a reaction product of (1) a polyol, such as a diol, (2) a polyisocyanate, such as a diisocyanate and (3) a hydroxyl-containing (meth)acrylate.

[0226] Clause 104. The composition according to Clause 103, wherein the polyol comprises a polyether polyol, a polyester polyol, a polycarbonate polyol, a polycaprolactone polyol, an acrylic polyol, or any mixture of two or more thereof, for example, wherein the polyol comprises polypropylene glycol.

[0227] Clause 105. The composition according to Clause 103 or Clause 104, 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.

[0228] Clause 106. The composition according to any one of Clauses 103 to 105, wherein the polyisocyanate used to prepare the urethane acrylate oligomer comprises 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene 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 Cyanide esters, 4,4′-biphenyl diisocyanate, 1,6-hexanediisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl)isocyanate, 2,2,4-trimethylhexamethylene diisocyanate, bis(2-ethyl isocyanate) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated diphenylene diisocyanate, tetramethylbenzene diisocyanate, lysine isocyanate, hexamethylene diisocyanate trimer (Desmodur®) N3300A, commercially available from Covestro, triphenylmethane-4,4′,4″-triisocyanate (Desmodur® RE, commercially available from Covestro), hexamethylene diisocyanate trimer (Desmodur® N3200, commercially available from Covestro), aromatic polyisocyanates based on toluene diisocyanate (Desmodur® IL BA, commercially available from Covestro), polyisocyanurates based on toluene diisocyanate (Desmodur® RC, commercially available from Covestro), and any combination of two or more of them.

[0229] Clause 107. The composition according to any one of Clauses 103 to 106, wherein the hydroxyl-containing methacrylate for preparing the urethane (meth)acrylate oligomer comprises a (meth)acrylate derived from (meth)acrylic acid and / or an epoxy (meth)acrylate containing an epoxide, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl acrylate and 2-hydroxy-3-oxyphenyl (meth)acrylate.

[0230] Clause 108. A composition according to any one of Clauses 103 to 107, wherein the relative amounts of the polyol, polyisocyanate, and hydroxyl-containing methacrylate used to prepare the urethane (meth)acrylate oligomer are such that for each amount of isocyanate group contained in the polyisocyanate, 0.1 to 0.9 equivalents of hydroxyl groups contained in the hydroxyl-containing methacrylate are used, and 1.0 to 1.5 equivalents of total hydroxyl groups from the polyol and the hydroxyl-containing methacrylate are used.

[0231] Clause 109. A composition according to any one of Clauses 102 to 108, wherein the olefinic unsaturated oligomer is present in an amount of 5 to 95% by weight, 10 to 90% by weight, 10 to 80% by weight, 30 to 95% by weight, 30 to 90% by weight, 65 to 95% by weight, or 50 to 80% by weight, based on the total weight of solids in the composition.

[0232] Clause 110. A composition according to any one of Clauses 100 to 109, wherein said composition further comprises (c) a reactive diluent compound comprising one or more olefinic unsaturated groups.

[0233] Clause 111. The composition according to Clause 110, wherein the reactive diluent comprises a double bond, such as an alkyl or hydroxyalkyl (meth)acrylate, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, isobornyl (meth)acrylate, lauryl (meth)acrylate, ethoxylated nonylphenol (meth)acrylate, phenoxyethyl (meth)acrylate, diethylene glycol ethylhexyl acrylate (DEGEHA), acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamide, vinyl esters (such as vinyl acetate), styrene, alkylstyrene, halostyrene, N-vinylpyrrolidone, N-vinylcaprolactam, vinyl chloride, vinylidene chloride, or any mixture of two or more.

[0234] Clause 112. The composition according to Clause 111, wherein said reactive diluent comprises more than one double bond, such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexamethylene glycol di(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, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, tris(2-acryloylethyl)isocyanurate, or any mixture of two or more.

[0235] Clause 113. A composition according to any one of Clauses 110 to 112, wherein the reactive diluent is present in an amount of 5 to 90% by weight, 10 to 90% by weight, 10 to 80% by weight, or in some cases 10 to 60% by weight, 10 to 40% by weight, or 10 to 30% by weight, based on the total weight of solids in the composition.

[0236] Clause 114. A composition according to any one of Clauses 100 to 113, wherein the composition further comprises (d) a photoinitiator, for example wherein the sum of the amounts of the polysilane compound and the photoinitiator is 1 to 99 by weight based on the total weight of the solids in the composition.

[0237] Clause 115. The composition according to Clause 114, wherein the photoinitiator comprises acylphosphine oxide, such as bisacylphosphine oxide (BAPO) and / or monoacylphosphine oxide (MAPO), α-hydroxy ketone, or any mixture of two or more thereof.

[0238] Clause 116. The composition according to Clause 115, wherein the photoinitiator comprises a bisacylphosphine oxide having the following structure: Where R 50 For C1-C 12 Alkyl, cyclohexyl, or phenyl, unsubstituted or substituted with 1 to 4 halogen atoms, or C1-C8 alkyl; R 51 and R 52 Each is independently a C1-C8 alkyl or C1-C8 alkoxy; R 53 It is hydrogen or C1-C8 alkyl; R 54 It is hydrogen or methyl, for example, the bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-(2,4-bispentoxyphenyl)phosphine oxide, or a mixture thereof.

[0239] Clause 117. A composition according to any one of Clauses 114 to 116, wherein the photoinitiator is present in an amount of 0.1 to 10% by weight, for example 0.1 to 5% by weight, or in some cases 1 to 5% by weight, based on the total weight of the radiation-curable composition.

[0240] Clause 118. A composition according to any one of Clauses 100 to 117, wherein said composition further comprises (e) γ-mercaptopropyltrimethoxysilane, trimethoxysilylpropyl acrylate, 3-trimethoxysilylpropane-1-thiol, or an olefinically unsaturated silane comprising the following structure: (a) a portion of structure (1): (1); and (b1) Part of structure (2): (2); or (b2) Part of structure (3): (3); or (b3) A combination of parts of structure (2) and parts of structure (3), wherein (i) Y represents a straight-chain or branched linking group containing one or more carbon atoms, (ii) each X may be the same or different, representing an alkoxy group or an organic group that is inert to isocyanate groups at 100°C or lower, provided that at least one X represents an alkoxy group, (iii) R 1 and R 2 They may be the same or different, each representing an organic group that is inert to the isocyanate group at 100°C or lower; (iv) R 3 and R 4 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower; and (v) each " "" indicates the connection with another part of the olefinic unsaturated silane.

[0241] Clause 119. A composition according to any one of Clauses 100 to 118, wherein the total silane content of the composition (as determined as described in the Examples section of this specification) is at most 10 mmol per 100 grams of radiation-curable composition, for example 1 to 10 mmol, 1 to 8 mmol, or in some cases 2 to 6 mmol, and / or the total urea + carbamate content of the composition (as determined as described in the Examples section of this specification) is 20 to 200 mmol per 100 grams of composition, for example 30 to 150 mmol, or in some cases 40 to 100 mmol.

[0242] Clause 120. A composition according to any one of Clauses 100 to 119, wherein the composition further comprises additives, said additives comprising photosensitizers, radiation-curing amine synergists, UV absorbers, antioxidants, UV stabilizers, heat stabilizers, adhesion promoters, filler materials, chain-transferred thiols, surfactants, viscosity modifiers, additional addition promoters, dehydrating agents such as TEOS and orthoformates, oxygen quenchers, or functional materials such as 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.

[0243] Clause 121. A composition according to any one of Clauses 100 to 120, wherein said composition further comprises an organic solvent.

[0244] Clause 122. A composition according to any one of Clauses 100 to 121, wherein the viscosity of said composition is at least >0.1 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 2500 s⁻¹ -1 Measured at the shear rate.

[0245] Clause 123. A cured coating formed from a composition according to any one of Clauses 100 to 122.

[0246] Clause 124. A substrate at least partially coated with a cured coating according to Clause 123, for example, said substrate comprising optical fiber.

[0247] Clause 125. The substrate according to Clause 124 further comprises a sub-coating that contacts and surrounds the cured coating, and optionally an ink layer disposed on the sub-coating.

[0248] Clause 126. The substrate according to Clause 124 or Clause 125, 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.

[0249] Clause 127. A substrate according to any one of Clauses 124 to 126, wherein the cured coating exhibits a peel strength of at least 40 gf / in or at least 55 gf / in after at least 7 days when measured as described in the Examples section of this specification.

[0250] Clause 128. A substrate according to any one of Clauses 124 to 127, wherein the cured coating exhibits at least 35%, for example, at least 50%, elongation at break when measured as described in the Examples section of this specification.

[0251] Clause 129. A method for coating an optical fiber, comprising: (a) providing a glass optical fiber, for example, drawing a glass optical fiber by a drawing tower; (b) applying a primary coating composition to a surface of the glass optical fiber; (c) optionally, applying a UV light dose 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 light to affect the curing of the secondary coating composition and optionally affect the curing of the primary coating composition, wherein the primary coating composition and / or the secondary coating composition comprises a composition according to any one of Clauses 100 to 122.

[0252] Clause 130. A coated optical fiber comprising: (a) a glass core and a cladding layer contacting and surrounding the glass core; and (b) a coating portion at least partially coating the cladding layer, the coating portion comprising: (i) a primary coating layer contacting the cladding layer; and (ii) a secondary coating layer contacting and surrounding the primary coating layer, wherein the primary coating layer and / or the secondary coating layer is a cured product of a composition according to any one of Clauses 100 to 122.

[0253] Clause 131. The coated optical fiber according to Clause 130, wherein the core comprises pure silica glass (SiO2) or silica glass having one or more dopants, such as wherein the dopants comprise GeO2, Al2O3, P2O5, TiO2, ZrO2, Nb2O5, Ta2O5, or any combination of two or more.

[0254] Clause 132. An optical fiber coated according to the method of Clause 129 or according to Clause 130 or Clause 131, wherein the cured master coating has an in-situ glass transition temperature of less than -35°C, less than -40°C, less than -45°C or not greater than -50°C, and / or the cured master 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.

[0255] Clause 133. An optical fiber coated according to the method of Clause 129 or Clause 131 or according to any one of Clauses 131 to 132, wherein the subcoating exhibits an in-situ tensile modulus greater than 800 MPa, greater than 1110 MPa, greater than 1300 MPa, greater than 1400 MPa or greater than 1500 MPa, and / or an in-situ Tg of 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 not greater than 40 μm, 20 to 40 μm or 20 to 30 μm.

[0256] Clause 134. A coated optical fiber according to any one of Clauses 130 to 131, wherein 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 an effective area of ​​20 to 200 μm². 2 .

[0257] The following non-limiting and non-exhaustive examples are intended to further describe various non-limiting and non-exhaustive embodiments, without limiting the scope of the embodiments described in this specification. Example

[0258] Many of the materials used in this paper were prepared by mixing to obtain mixtures with a molecular weight statistical distribution readily identifiable to those skilled in the art. Unless otherwise stated, the structures shown in this section and elsewhere in this paper are only design-average or “ideal” structures.

[0259] Example 1: Synthesis of monoaspartic acid ester precursor IPDA (149 g, 0.87 mol) was added to a four-necked flask (1000 mL), purged with dry air, and cooled to 5°C in an ice bath. Then, diethyl maleate (152 g, 0.88 mol) was added dropwise, keeping the mixture temperature below 10°C. After the addition was complete, the mixture was stirred for 2 hours and heated to 20-25°C to obtain a final product mixture containing structure (A), which was a viscous liquid. This product could be used in subsequent formulations without further purification. Structure (A) is shown below: Example 2: Synthesis of three-day aspartate precursor Jeffamine T-403 (240 g, 0.5 mol) and BHT (0.5 g, 1000 ppm) were added to a four-necked flask (1000 mL) and purged with dry air. Then, diethyl maleate (260 g, 1.5 mol) was added dropwise. After the addition was complete, the mixture was stirred for 6 hours and stored for 6 months to obtain a final product mixture containing structure (B), which was a viscous liquid. This product could be used in subsequent formulations without further purification. Structure (B) is shown below: Example 3: Synthesis of silane precursors KBM-903 (182 g, 1 mol) was placed in a four-necked flask (500 mL) and cooled to 0–5 °C (ice bath) under nitrogen. Then, diethyl maleate (175 g, 1 mol) was added dropwise. The resulting mixture was stirred at 0–10 °C for 3 hours to obtain a final product mixture containing structure (C), which was a viscous liquid. This product could be used in subsequent formulations without further purification. Structure (C) is shown below: Example 4: Synthesis of an olefinically unsaturated silane monomer (ME-01) To prepare ME-01, the silane precursor (70.2 g, 0.2 mol) from Example 3 was placed in a four-necked flask (250 mL) and purged with an air / nitrogen mixture at a volume ratio of 3:1. Then, DBTDL (0.06 g, 600 ppm), BHT (0.10 g, 1000 ppm), and AOI (28.6 g, 0.20 mol) were added sequentially. While continuing to purge with the 3:1 air / nitrogen mixture, the reaction mixture was further stirred at 70°C for 2–4 hours to obtain a final product mixture containing structure (D), which was a viscous liquid. This product could be used in subsequent formulations without further purification. Structure (D) is shown below: Example 5: Synthesis of polysilane compound (ME-02) To prepare ME-02, TMSPI (55 g, 0.27 mol) was placed in a four-necked flask (500 mL), purged with dry air, and stirred. Then, the monoaspartic acid ester precursor from Example 1 (45 g, 0.13 mol) was added dropwise, maintaining the temperature below 45°C. The resulting mixture was stirred at 60°C for 4 hours to obtain a final product mixture containing structure (E), which was a viscous liquid. This product could be used in subsequent formulations without further purification. Structure (E) is shown below: Example 6: Synthesis of polysilane compound (ME-03) To prepare ME-03, NH-1723LF (117 g, 0.2 mol) was placed in a four-necked flask (500 mL), purged with dry air, and stirred. Then, TMSPI (83 g, 0.4 mol) was added, and the resulting mixture was stirred at 60 °C for 16 hours. The mixture was then stirred at 70 °C for 12 hours to obtain a final product mixture containing structure (F), which was a viscous liquid. This product could be used in subsequent formulations without further purification. Structure (F) is shown below: Example 7: Synthesis of polysilane compound (ME-04) To prepare ME-04, TDI (29 g, 0.2 mol) was placed in a four-necked flask (500 mL), purged with dry air, and stirred. Then, the silane precursor from Example 3 (59 g, 0.2 mol) was added dropwise, maintaining the temperature below 45°C. The resulting mixture was stirred for 1 hour. Then, TMSPI (34 g, 0.2 mol) and PPG725 (128 g, 0.2 mol) were added, and the mixture was stirred at 20–25°C for 15 minutes. Then, DBTDL (0.2 g, 600 ppm) was added, and the resulting mixture was stirred at 60°C for 2 hours to obtain a final product mixture containing structure (G), which was a viscous liquid. This product could be used for subsequent formulations without further purification. Structure (G) is shown below: Example 8: Synthesis of polysilane compound (ME-05) To prepare ME-05, TDI (38 g, 0.2 mol) and PPG725 (84 g, 0.1 mol) were placed in a four-necked flask (500 mL), purged with dry air, and stirred for 15 minutes. DBTDL (0.12 g, 600 ppm) was then added under active cooling, and the mixture was stirred at 70°C for 1 hour. The silane precursor from Example 3 (77 g, 0.2 mol) was then added, and the mixture was stirred at 60°C for 1 hour to obtain a final product mixture containing structure (H), which was a viscous liquid. This product could be used in subsequent formulations without further purification. The structure (H) is shown below: Example 9: Synthesis of polysilane compound (ME-06) To prepare ME-06, ME-03 (100 g) was placed in a four-necked flask (500 mL) and purged with dry air. The resulting mixture was then heated to 70-80°C, and acrylic acid (1 g, 1%) was added. The mixture was stirred at 85°C for 1-2 hours to obtain a final product mixture containing structure (I), which was a viscous liquid. This product could be used in subsequent formulations without further purification. Structure (I) is shown below: Example 10: Synthesis of a polysilane compound (ME-07) To prepare ME-07, ME-04 (128 g) was placed in a four-necked flask (500 mL) and purged with dry air. The resulting mixture was then heated to 70-80°C, and acrylic acid (1.2 g, 1%) was added. The mixture was stirred at 85°C for 8 hours to obtain a final product mixture containing structure (J), which was a viscous liquid. This product could be used in subsequent formulations without further purification. Structure (J) is shown below: Example 11: Synthesis of polysilane compound (ME-08) To prepare ME-08, ME-05 (145 g) was placed in a four-necked flask (500 mL) and purged with dry air. The resulting mixture was then heated to 70-80°C, and acrylic acid (1.5 g, 1%) was added. The mixture was stirred at 85°C for 5-6 hours to obtain a final product mixture containing structure (K), which was a viscous liquid. This product could be used in subsequent formulations without further purification. Structure (K) is shown below: Example 12: Synthesis of polysilane compound (ME-09) To prepare ME-09, the three-trispartic acid ester precursor (124 g, 0.12 mol) from Example 2 was placed in a four-necked flask (500 mL) and purged with dry air. Then, TMSPI (77 g, 0.38 mol) was added, and the resulting mixture was stirred at 70°C for 12–14 hours to obtain a final product mixture containing structure (L), which was a viscous liquid. This product could be used in subsequent formulations without further purification. The structure (L) is shown below: Example 13: Synthesis of Oligomer 1 To prepare oligomer 1, a mixture of PPG 4000 (3474 g, 0.9 mol), TDI (313 g, 1.8 mol), and BHT (1000 ppm) was placed in a four-necked flask (5000 mL) and purged with dry air. The resulting mixture was stirred at 20–25 °C for 15 minutes, and then a mixture of DBTDL (400 ppm) was added. The resulting mixture was stirred for 15 minutes without external heating, and then stirred at 60 °C for 1–2 hours. HEA (208 g, 1.8 mol) was then added. While continuing to purge with dry air, the reaction mixture was stirred at 85 °C for another 1–2 hours to obtain a final product mixture containing structure (M), which was a viscous liquid. This product could be used in subsequent formulations without further purification. Structure (E) is shown below: Example 14: Synthesis of oligomer 2 To prepare oligomer 2, PP G4000 (74.3 kg, 19.1 mol), HEA (2.2 kg, 19.1 mol), BHT (1000 ppm), acrylic acid (40 g, 0.56 mol), TDI (3.3 kg, 19.1 mol), and DBTDL (800 ppm) were sequentially added to a batch reactor (180 L). The resulting mixture was stirred at 70 °C for 2–4 hours to obtain a final product mixture containing structure (N), which was a viscous liquid. This product could be used in subsequent formulations without further purification. The structure (N) is shown below: Example 15: Synthesis of oligomer 3 To prepare oligomer 3, TDI (7.22 g, 0.04 mol) and BHT (0.10 g, 1000 ppm) were placed in a four-necked flask (250 mL) and purged with an air / nitrogen mixture at a volume ratio of 3:1. The resulting mixture was stirred at 20–25 °C for 10 minutes, and then DBTDL (0.03 g, 300 ppm), HEA (2.40 g, 0.02 mol), and the silane precursor of Example 3 (7.28 g, 0.02 mol) were added. The resulting mixture was stirred at 60 °C for 1 to 2 hours. Then, DBTDL (0.03 g, 300 ppm) and PPG4000 (82.9 g, 0.02 mol) were added sequentially. The reaction mixture was stirred at 85°C for another 2 hours while being purged with a 3:1 air / nitrogen mixture to obtain a final product mixture with an average structure of (O), which was a viscous liquid. This product could be used in subsequent formulations without further purification. The structure (O) is shown below: .

[0260] Table 3 - Reactants for oligomers 1-3 (expressed in molar ratio) reactants MW (g / mol) 1 2 3 TDI 174.2 2 1 2 HEA 116.1 2 1 1 PPG 4000 ~4000 1 1 1 Silane precursor of Example 3 351.5 -- -- 1 .

[0261] The synthesis of the polysilanes described above, which can be considered as aspartic ester silane components, is expected to be used in coating compositions, such as master coating compositions for optical fibers. To further demonstrate this, a variety of compositions were prepared using subsets of these polysilanes and formulated and evaluated as described below. Such compositions were formulated with appropriate controls using oligomers selected above, which may or may not contain additional silane functional groups or additional aspartic ester functional groups.

[0262] Formula 1-38 SpeedMixer TM The mixture is prepared by mixing in a 100 mL mixing cup. Specifically, the oligomer and monomer components (excluding silane-containing oligomers and / or monomers) are mixed together with the other components specified in Tables 4A-4I. After adding to the cup, the lid is closed and the mixture is mixed in a SpeedMixer. TM Mix at 3000 RPM for 3 minutes in a DAC150FVZ. Afterward, stop mixing, transfer the resulting mixture to a suitable container, and heat in an oven to 60°C and maintain this temperature for approximately 6 hours to ensure all components are completely dissolved. Then remove the sample from the oven and mix again in a SpeedMixer for three minutes using the same method. Add the silane-containing monomer to obtain a total of 100 g. Finally, mix the mixture again in a SpeedMixer for 3 minutes using the same method.

[0263] Next, these formulations were characterized according to their respective total silane and total urea + carbamate contents, as described below. All formulations were then tested according to the methods described below to determine their peel strength, elongation percentage, film modulus, toughness, tensile strength, and viscosity. Unless otherwise specified, total silane content values ​​were rounded to one decimal place, and urea + carbamate content values ​​were rounded to the nearest integer. Meanwhile, film modulus, toughness, and tensile strength values ​​were rounded to two decimal places. Viscosity was expressed in the nearest centipoise. Finally, elongation percentage values ​​were rounded to the nearest 1%. These measured properties are reported in Tables 4A-4I below.

[0264] The “total silane” of a given composition is determined by first calculating the molar number of silane groups (where “silane group” refers to a group of structure Si(X)3, and X represents an alkoxy group or an organic group that is inert to isocyanate groups at 100°C or lower, provided that at least one X represents an alkoxy group) in each silane-containing component (Y) according to the following expression: Where Wt = the weight parts of the corresponding component Y relative to 100g of the total relevant composition; N = the number of silane groups present in one molecule of component Y; MW is the theoretical molecular weight of component Y (g / mol). Total silane content is reported in mmol / 100g. The theoretical molecular weights of the reactants used to prepare the monomers and oligomers (including silane-containing monomers, polysilanes, and oligomers) in the formulations herein are reported in Tables 2-3.

[0265] Then, the total silane number of the entire composition is calculated by summing the molar values ​​of the silane groups of each silane-containing component according to the following expression. The total silane number in this document is reported in mmol / 100g. The total silane number may optionally be expressed as mol / 100g by dividing the sum by 1000, but unless otherwise specified, the values ​​in this document are not reported in this manner. For clarity, when “equivalent” or “milliequivalent” is specified in this document, unless otherwise stated, the value should be interpreted relative to 100g of the composition to which it is associated. The total silane number for each formulation is reported in Tables 4A-4I below.

[0266] It should be noted that if the complete formulation of the composition is not known in advance, the equivalent of the silane moiety can be determined by any suitable analytical method, as will be understood by those skilled in the art, such as size exclusion chromatography (SEC), infrared spectroscopy, HPLC, GC, MALDI-TOF mass spectrometry, or nuclear magnetic resonance (NMR) methods.

[0267] The value of urea + carbamate content is determined by the same method as the above "total silanes", except that instead of evaluating silane groups or silane-containing components, the total number of isocyanate groups that react with isocyanate reactive compounds is calculated.

[0268] Viscosity was measured using an Anton Paar Rheolab QC instrument. Both the Z3 and Z4 systems were used. Samples weighing 14.7 g ± 0.2 g were placed in disposable aluminum cups using the Z3 system, while samples using the Z4 system weighed 3.5 g ± 0.2 g. The samples in the cups were examined; if visual inspection revealed the presence of air bubbles, the sample and cup were centrifuged or allowed to stand for a sufficient time to allow the bubbles to escape from the bulk of the liquid. Bubbles appearing on the top surface of the liquid were considered acceptable. Next, the rotor was gently inserted into the liquid in the measuring cup, and then the cup and rotor were installed in the instrument. Viscosity was measured at 25 °C ± 0.1 °C and 55 °C ± 0.1 °C for 50 seconds. -1 Viscosity was measured at the shear rate, with an equilibration time of five minutes to ensure constant temperature. 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 expressed in millipascal-seconds (mPa·s) and 50 s. -1 The shear rate record.

[0269] To fabricate films capable of testing a variety of physical properties, each sample was cured under a constant nitrogen flow using a conveyor-type DRS-10 / 12 QN 600W UV lamp system at a UV dose of 1 J / cm². The system consisted of a 1600M radiator (600W / inch, equal to 240W / cm, therefore 600W total), equipped with an R500 reflector, one H-bulb UV lamp, and one D-bulb UV lamp, with the D-bulb used for curing the sample. The UV dose was then measured using an International Light IL390 radiometer. Individual test strips, approximately 1.27 cm wide (0.5 inch ± 1 / 32 inch) and 12.7 cm long (5 inch ± 1 / 8 inch), were then cut from the film. The precise thickness of each sample was measured using a calibrated micrometer.

[0270] The method for determining segment modulus used herein is described in paragraphs

[0132] to

[0133] and

[0135] of EP2089333B1, the referenced portion of which is incorporated herein by reference, except that the cured film was conditioned for at least 24 hours prior to testing. Tensile properties (tensile strength, percentage elongation at break, and segment modulus) were determined using an MTS Criterion™ Model 43.104, with test samples being 3-mil thickness test strips of each cured film prepared according to the “Film Sample Preparation” procedure described above. Because these coatings are relatively soft (e.g., modulus less than about 10 MPa), the coatings were applied to and cured on glass plates, and individual samples were cut from the glass plates with a scalpel after a thin layer of talc was applied. The modulus was calculated using a 0.9 kg (2 lb) weighing sensor on an Instron 4442 tensile testing machine at 2.5% elongation by least-squares fitting of the stress-strain curve. The cured films were conditioned for 16 to 24 hours at 23.0℃ ± 0.1℃ and 50.0% ± 0.5% relative humidity before testing. For the test samples, the gauge length was 5.1 cm (2 inches), and the crosshead speed was 25.4 mm / min. All tests were conducted at 23.0℃ ± 0.1℃ and 50.0% ± 0.5% relative humidity. All measurements were determined by averaging at least six test samples. The tensile strength was determined as the maximum stress the sample could withstand before fracture. The toughness was determined as the total area under the stress-strain curve.

[0271] Adhesion properties were determined using an Instron Tensile Tester Model 4442, employing 3-mil thickness test strips of the cured film prepared according to the “Film Sample Preparation” procedure described above. The Instron Tensile Tester Model 4442 was set to a 2-pound load cell, a 20-psi pneumatic clamp, and a crosshead speed of 10.00 inches per minute. The cured film on each plate was cut into four strips using a scalpel and a 1.00-inch wide steel strip, with 6-inch cuts on each side of the strip and a 1 / 4-inch gap between the samples. To minimize the impact of minor sample defects, the sample specimens were cut parallel to the coating direction of the cured film.

[0272] The cured film, cut into four strips, was conditioned for 7 days at 23.0℃ ± 2.0℃ and 50% ± 5% RH. After 7 days, the dry adhesion of two alternating strips (1st and 3rd or 2nd and 4th) was tested. A thin layer of talcum powder was applied using a cotton swab to reduce sticking during the adhesion test. A clamp attached to the braided nylon rope was passed through a pulley, and the nylon rope was clamped in the upper clamp of the Instron testing instrument. The first strip was peeled off the glass plate about one inch and placed horizontally on the table with the peeled sample end facing away from the pulley. A binder was attached to the peeled end of the sample to lay it flat on the sample. The plate was pulled to apply tension to the braided nylon rope until the load reading on the Instron was positive. At this point, the software method was started until the average force value became relatively constant. The test was terminated by clicking the stop button in the software or by releasing the tension on the rope. This process was repeated for two plates, and the reported value was the average of the platform forces of the four samples. After the dry adhesion test, the plates (including unused strips) were placed in a humidity chamber at 23.0℃ ± 2.0℃ and 95% ± 5% RH for 24 hours. After removal from the humidity chamber, a polyethylene slurry was applied to the strips using a synthetic foam brush to prevent drying, and then the wet adhesion was measured using the same instrumental method described for the dry adhesion test. This procedure was repeated for both plates, and the reported value is the average of the platform forces obtained from the four sample runs.

[0273] *Formulas 1, 2, and 5 are comparative examples. For all silane-containing formulations in Table 4A except for Comparative Formulation 1, the total silane content in each formulation was controlled at the same silicon atom level, i.e., 2 mmol per 100 g formulation. The improvement in adhesion was investigated using ME-02 in dry and wet peel strength tests. Three control formulations (Formulations 1, 2, and 5) were used as comparative examples. Comparative Formulation 1 did not contain an adhesion promoter. Comparative Formulation 2 contained the adhesion promoter ME-01, and Comparative Formulation 5 contained the commercially available adhesion promoter acrylated silane TMPSA.

[0274] Comparative formulations 2 and 5, containing adhesion promoters, both exhibited superior peel strength compared to comparative formulation 1. Further improvements in adhesion based on formulations 2 and 5 without increasing the silicon atom level or altering mechanical properties are desirable for optical fiber applications.

[0275] With the invention of novel polysilane adhesion promoters, only ME-02 is used as an adhesion promoter in Formulation 3. ME-02 is also used in the mixture of adhesion promoters in Formulations 4 and 6. To formulate Formulations 4 and 6, 20 mol% of the adhesion promoters in Formulations 2 and 5 were replaced with ME-02, respectively.

[0276] The coating of Formulation 3, which uses ME-02 as the adhesion promoter alone, showed improved dry and wet peel strength compared to the control Formulation 1. Surprisingly, ME-02, which lacks UV-curable functional groups, performed even better in Formulation 3 than commercially available acrylated silane TMPSA (such as Formulation 5). This unexpected result allows polysilane adhesion promoters to be used alone as additive promoters in UV-curable coatings. Furthermore, the coatings of Formulations 4 and 6, which contain a mixture of monofunctional acrylated silane TMPSA and ME-02 in an 80:20 molar ratio, also showed improved dry and wet peel strength at the same total silane content compared to the coatings of Formulations 2 and 5, which contain only monofunctional acrylated silane TMPSA.

[0277] *Formula 5 is a comparative example. Table 4B shows a screening comparison of the aspartic ester polysilane adhesion promoters with control formulation 5 containing the commercially available acrylated silane TMPSA at a silane loading of 2 mmol / 100g. ME-03 contains aspartic ester groups within the two urea bonds, while ME-04 contains one aspartic ester silane, and ME-05 contains two aspartic ester silanes. Surprisingly again, despite lacking UV-curable functional groups, all polysilane adhesion promoters outperformed the commercially available acrylated silane TMPSA in formulation 5.

[0278] *Formula 5 is a comparative example. Table 4C shows a screening comparison of the novel hydantoin polysilanes with control formulation 5 containing the commercially available acrylated silane TMPSA at a silane loading of 2 mmol / 100g. ME-06 and ME-08 contain two hydantoin silane groups, while ME-07 contains only one. Surprisingly again, the coatings prepared using these polysilane adhesion promoters outperformed the commercially available acrylated silane TMPSA in formulation 5, despite lacking UV-curable functional groups. Compared to the coatings prepared with non-hydantoin polysilanes in Table 4B, the coatings prepared with hydantoin polysilanes in Table 4C appear to offer enhanced wet and dry adhesion.

[0279] *Formulas 5, 13, 14, and 15 are comparative examples. Table 4D shows a screening comparison of the novel aspartic ester polysilanes in formulations 16-18 with three commercially available polysilane formulations 13-15. All formulations consisted of an 80:20 molar mixture of monofunctional acrylated silane TMPSA and polysilane, with a silane loading of 2 mmol / 100g. ME-03 contained aspartic ester groups within two urea bonds, while ME-04 contained one aspartic ester silane, and ME-05 contained two aspartic ester silanes. As shown in formulations 13-15, coatings prepared using commercially available polysilanes exhibited similar wet and dry adhesion results to control formulation 5, which did not contain a polysilane adhesion promoter. However, unexpectedly, coatings prepared using the aspartic ester polysilane adhesion promoter in formulations 16-18 showed significantly enhanced wet and dry adhesion results, superior to all four controls.

[0280] *Formulas 5, 13, 14, and 15 are comparative examples. Table 4E shows a screening comparison of the hydantoin polysilanes in formulations 19-21 with three commercially available polysilane formulations 13-15. All formulations consisted of an 80:20 molar mixture of monofunctional acrylated silane TMPSA and polysilane, with a silane loading of 2 mmol / 100g. ME-06 and ME-08 contained two hydantoin silane groups, while ME-07 contained only one hydantoin silane group. As shown in formulations 13-15, coatings prepared using commercially available polysilanes exhibited adhesion results similar to control formulation 5, which did not contain a polysilane adhesion promoter. However, unexpectedly, coatings prepared using the hydantoin polysilane adhesion promoter in formulations 19-21 exhibited enhanced wet and dry adhesion results, superior to all four controls.

[0281] *Formula 22 is a comparative example. Table 4F shows the screening of aspartic ester polysilanes (formulas 23-24) and hydantoin polysilanes (formulas 25-26) in formulations consisting of a mixture of monofunctional acrylate aspartic ester silane monomer 1 and polysilane in an 80:20 molar ratio, with a silane loading of 2 mmol / 100 g. Compared to control formulation 22 containing only monomer 1, the coatings prepared using aspartic ester and hydantoin polysilanes again unexpectedly exhibited enhanced adhesion. Furthermore, the coatings prepared using hydantoin polysilanes in formulations 25-26 showed higher wet and dry adhesion than the coatings prepared using aspartic ester polysilanes in formulations 23-35.

[0282] *Formula 5 is a comparative example. Table 4G shows the gradient study of aspartic ester polysilane ME-03 and acrylated silane TMPSA at different molar ratios (0 to 1). Compared to control formulation 5 containing only acrylated silane TMPSA, the addition of ME-03 did not appear to increase adhesion at molar ratios less than 0.1. However, as the molar ratio increased further, the coatings prepared using aspartic ester polysilane ME-03 exhibited enhanced wet and dry adhesion at molar ratios greater than 0.1. This was unexpected, as ME-03 does not contain any UV-curable functional groups.

[0283] *Formula 22 is a comparative example. Table 4H shows the gradient studies of aspartic ester polysilane ME-03 and acrylate aspartic ester silane ME-01 at different molar ratios (0 to 1). Compared to control formulation 22 containing only ME-01, the addition of ME-03 up to a molar ratio of 0.4 appears to improve both wet and dry adhesion. This is unexpected because ME-03 does not contain any UV-curable functional groups and differs from the case of using acrylated silane TMPSA in Table 4F.

[0284] *Formulas 1, 5, and 36 are comparative examples. Table 4I shows the additional screening of aspartic ester polysilanes. Trifunctional aspartic ester silanes, represented by ME-09, were synthesized and demonstrated in formulation FE-34. The addition of the trifunctional aspartic ester silane ME-09 to formulation FE-34 resulted in increased wet and dry adhesion compared to the control formulation FE-01. This was unexpected, as ME-09 does not contain any UV-curable functional groups. Furthermore, when used in combination with a monofunctional acrylate silane adhesion promoter at an equivalent ratio of 0.33 (EQ ratio in the table), coatings prepared using ME-09 in FE-35 and FE-37 exhibited further increased wet and dry adhesion, superior to the controls FE-05 and FE-36 which contained only the monofunctional acrylate silane adhesion promoter. FE-05 and FE-35 used acrylated silane TMPSA as the monofunctional acrylate silane adhesion promoter, while FE-36 and FE-37 used oligomer 3. In addition to ME-09, the coating prepared in FE-38 using ME-03 in combination with oligomer 3 also showed increased wet and dry adhesion compared to the control FE-36. These aspartic ester polysilane adhesion promoters, when used in combination with monomeric or oligomeric monofunctional acrylate silane adhesion promoters, produced coatings with further enhanced adhesion.

[0285] In any of the formulation groups compared in Tables 4A-4I, the main difference in formulation composition lies only in a small amount of silane adhesive accelerator. This formulation change does not appear to have a significant impact on mechanical properties and viscosity.

[0286] Although the invention has been described in detail above for illustrative purposes, it should be understood that such details are for that purpose only, and that those skilled in the art may make changes therein without departing from the spirit and scope of the invention, unless it may be limited by the claims.

Claims

1. A radiation-curable composition comprising: (I) A polysilane compound comprising: (a) At least two parts of structure (1): and (b1) Part of structure (2): or (b2) Part of structure (3): or (b3) The combination of parts of structure (2) and parts of structure (3), Wherein (i) Y represents a straight-chain or branched linking group containing one or more carbon atoms, (ii) each X may be the same or different, representing an alkoxy group or an organic group that is inert to isocyanate groups at 100°C or lower, provided that at least one X represents an alkoxy group, and (iii) each R 1 They may be the same or different, indicating organic groups that are inert to isocyanate groups at 100°C or lower; (iv) each R 2 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower; and (v) " "Indicates a connection with another part of the polysilane compound; and (II) Free radical photoinitiators.

2. The radiation-curable composition according to claim 1, wherein the sum of the amounts of the polysilane compound (I) and the photoinitiator (II) is 1 to 99 by weight, based on the total weight of the solids in the radiation-curable composition.

3. The radiation-curable composition according to claim 1, wherein each R 2 It is hydrogen.

4. The radiation-curable composition according to claim 1, wherein the polysilane compound further comprises: (c) Chain segments with the following structures: Where G is O, S, or NR, and R represents hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, and each " "" indicates a connection to another part of the polysilane compound.

5. The radiation-curable composition according to claim 1, wherein the polysilane compound has structure (4): Where (i) is each Y 1 They can be the same or different, representing straight-chain or branched linking groups containing one or more carbon atoms, (ii) each R 3 They may be the same or different, indicating organic groups that are inert to isocyanate groups at 100°C or lower, (iii) each R 4 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, (iv) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 (v) Z represents an alkoxy group, (v) Z represents an organic group that is inert to the isocyanate group at 100°C or lower, and (vi) m and n may be the same or different, each being an integer from 1 to 5, for example 1 to 3, or 1.

6. The radiation-curable composition according to claim 1, wherein the polysilane compound has the structure (5): Where (i) is each Y 1 They can be the same or different, representing straight-chain or branched linking groups containing one or more carbon atoms, (ii) each R 3 They may be the same or different, indicating organic groups that are inert to isocyanate groups at 100°C or lower, (iii) each R 4 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, (iv) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 (v) Z represents an alkoxy group, (v) Z represents an organic group that is inert to the isocyanate group at 100°C or lower, and (vi) m and n may be the same or different, each being an integer from 1 to 5, for example 1 to 3, or 1.

7. The radiation-curable composition according to claim 1, wherein the polysilane compound has the structure (6): in: (i) Each Y 1 They can be the same or different, representing straight-chain or branched connecting groups containing one or more carbon atoms, (ii) Y 2 Groups representing the following structures: in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) p is 0 or 1; (iv) each R 3 They may be the same or different, indicating organic groups that are inert to the isocyanate group at 100°C or lower; (v) each R 4 They may be the same or different, representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower; and (vi) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 It represents an alkoxy group.

8. The radiation-curable composition according to claim 1, wherein the polysilane compound has the structure (7): in: (i) Each Y 1 They can be the same or different, representing straight-chain or branched connecting groups containing one or more carbon atoms, (ii) Y 2 Groups representing the following structures: in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) p is 0 or 1; (iv) each R 3 They may be the same or different, indicating organic groups that are inert to the isocyanate group at 100°C or lower; (v) each R 4 They may be the same or different, representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower; and (vi) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 It represents an alkoxy group.

9. The radiation-curable composition according to claim 1, wherein the polysilane compound has the structure (8): in: (i) Each Y 1 They can be the same or different, representing straight-chain or branched connecting groups containing one or more carbon atoms, (ii) each Y 2 The groups can be the same or different, representing the following structures: in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) each p may be the same or different, and may be 0 or 1; (iv) each R 3 Can be the same or different, indicating an organic group that is inert to the isocyanate group at 100°C or lower, (v) each R 4 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, (vi) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 (vii) Z represents an alkoxy group, (vii) Z represents an organic group that is inert to the isocyanate group at 100°C or lower, and (vii) m and n may be the same or different, each being an integer from 1 to 5, for example 1 to 3, or 1.

10. The radiation-curable composition according to claim 1, wherein the polysilane compound has the structure (9): in: (i) Each Y 1 They can be the same or different, representing straight-chain or branched connecting groups containing one or more carbon atoms, (ii) each Y 2 The groups can be the same or different, representing the following structures: in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) each p may be the same or different, and may be 0 or 1; (iv) each R 3 Can be the same or different, indicating an organic group that is inert to the isocyanate group at 100°C or lower, (v) each R 4 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, (vi) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 (vii) Z represents an alkoxy group, (vii) Z represents an organic group that is inert to the isocyanate group at 100°C or lower, and (vii) m and n may be the same or different, each being an integer from 1 to 5, for example 1 to 3, or 1.

11. The radiation-curable composition according to claim 1, wherein the polysilane compound has the structure (10): Where (i) is each Y 1 They can be the same or different, representing straight-chain or branched connecting groups containing one or more carbon atoms, (ii) each Y 2 The groups can be the same or different, representing the following structures: in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) each p may be the same or different, and may be 0 or 1; (iv) each R 3 Can be the same or different, indicating an organic group that is inert to the isocyanate group at 100°C or lower, (v) each R 4 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, (vi) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 (vii) Z represents an alkoxy group, (vii) Z represents an organic group that is inert to the isocyanate group at 100°C or lower, and (vii) m+n is 2 to 10.

12. The radiation-curable composition according to claim 1, wherein the polysilane compound has the structure (11): Where (i) is each Y 1 They can be the same or different, representing straight-chain or branched connecting groups containing one or more carbon atoms, (ii) each Y 2 The groups can be the same or different, representing the following structures: in Indicates Y 1 The connection, The connection to N is indicated, where G is O, S, or NR, where R is hydrogen or an organic group inert to the isocyanate group at 100°C or lower, and Z represents an organic group inert to the isocyanate group at 100°C or lower, for example, optionally containing a hydrocarbon group inert to the isocyanate group, such as oxygen, nitrogen, sulfur, or combinations thereof; (iii) each p may be the same or different, and may be 0 or 1; (iv) each R 3 Can be the same or different, indicating an organic group that is inert to the isocyanate group at 100°C or lower, (v) each R 4 They may be the same or different, each representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower, (vi) each X 1 They may be the same or different, representing an alkoxy group or an organic group that is inert to the isocyanate group at 100°C or lower, provided that at least one X 1 (vii) Z represents an alkoxy group, (vii) Z represents an organic group that is inert to the isocyanate group at 100°C or lower, and (vii) m+n is 2 to 10.

13. The radiation-curable composition according to claim 1, wherein the polysilane compound (I) 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 solids in the composition.

14. The radiation-curable composition according to claim 13, further comprising: (b) Alkene unsaturated oligomers.

15. The radiation-curable composition according to claim 14, wherein the olefinic unsaturated oligomer comprises a urethane (meth)acrylate oligomer comprising a reaction product containing reactants of: (1) a polyol, (2) a polyisocyanate and (3) a hydroxyl-containing (meth)acrylate.

16. The radiation-curable composition of claim 15, wherein the polyol comprises a diol and the polyisocyanate comprises a diisocyanate.

17. The radiation-curable composition according to claim 15, wherein the urethane (meth)acrylate oligomer is present in an amount of 30 to 95% by weight or 65 to 95% by weight, based on the total weight of solids in the composition.

18. The radiation-curable composition according to claim 17, further comprising: (c) A reactive diluent compound comprising one or more olefinic unsaturated groups, wherein the reactive diluent compound is present in an amount of 5 to 90% by weight based on the total weight of solids in the composition.

19. A cured coating formed from the radiation-curable composition of claim 1.

20. A substrate at least partially coated with the cured coating of claim 19, wherein the substrate comprises an optical fiber.

21. A method for coating an optical fiber, comprising: (a) Provide glass optical fiber; (b) Applying the main coating composition to the surface of the glass optical fiber; (c) Optionally, apply a UV light dose sufficient to at least partially cure the main coating composition; (d) Applying the secondary coating composition to the primary coating composition; and (e) Exposing the sub-coating composition to at least one radiation source capable of emitting ultraviolet light to affect the curing of the sub-coating composition, and optionally to affect the curing of the main coating composition. The primary coating composition and / or the secondary coating composition comprise the radiation-curable composition of claim 1.

22. A coated optical fiber comprising: (a) A glass core and a cladding layer that contacts and surrounds the glass core; and (b) A coating portion that at least partially coats the overlay, the coating portion comprising: (i) the main coating layer in contact with the overlay; and (ii) A secondary coating that contacts and surrounds the primary coating. The primary coating and / or the secondary coating are the cured coatings of claim 19.

23. The radiation-curable composition according to claim 1, wherein the polysilane compound (I) comprises a portion of structure 3A: Where X, Y, R 1 R 2 and" "Each is as described with respect to structures (1)-(3), for example, the polysilane compound described therein has 1 to 4 such structural 3A portions." 24. The radiation-curable composition according to claim 1, provided that the polysilane compound (I) has only one portion of structure 3B: Where X, Y, R 1 R 2 and" "Each is as described in terms of structure (1)-(3)." 25. The radiation-curable composition according to claim 1, provided that the polysilane compound (I) has only one portion of structure 2A: Where X, Y, R 1 R 2 and" "Each is as described in terms of structure (1)-(3)." 26. The radiation-curable composition according to claim 1, provided that the polysilane compound (I) has only one portion of structure 2B: Where X, Y and " "Each is as described in terms of structures (1)-(3), and R..." 0 It's not hydrogen.

27. The radiation-curable composition according to claim 26, wherein the portion of structure 2B has structure 2B(i): Where X, Y, R 1 R 2 and" "Each is as described in terms of structure (1)-(3)." 28. A polysilane compound comprising: (a) At least two parts of structure (1): (b1) Part of structure (2): (b2) Part of structure (3): or (b3) The combination of parts of structure (2) and parts of structure (3), The condition is that the polysilane compound has only one part of structure 2A: Wherein (i) Y represents a straight-chain or branched linking group containing one or more carbon atoms, (ii) each X may be the same or different, representing an alkoxy group or an organic group that is inert to isocyanate groups at 100°C or lower, provided that at least one X represents an alkoxy group, and (iii) each R 1 They may be the same or different, indicating organic groups that are inert to isocyanate groups at 100°C or lower; (iv) each R 2 They may be the same or different, representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower; and (v) " "" indicates a connection to another part of the polysilane compound.

29. A polysilane compound comprising: (a) At least two parts of structure (1): (b1) Part of structure (2): or (b2) Part of structure (3): or (b3) The combination of parts of structure (2) and parts of structure (3), The condition is that the polysilane compound has only one structural 2B moiety: Wherein (i) Y represents a straight-chain or branched linking group containing one or more carbon atoms, (ii) each X may be the same or different, representing an alkoxy group or an organic group that is inert to isocyanate groups at 100°C or lower, provided that at least one X represents an alkoxy group, and (iii) R 0 Not hydrogen, (iv) each R 1 They may be the same or different, indicating organic groups that are inert to the isocyanate group at 100°C or lower; (v) each R 2 They may be the same or different, representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower; and (vi) " "" indicates a connection to another part of the polysilane compound.

30. The polysilane compound according to claim 29, wherein the portion of structure 2B has structure 2B(i): 。 31. A polysilane compound comprising: (a) At least two parts of structure (1): (b1) Part of structure (2): or (b2) Part of structure (3): or (b3) The combination of parts of structure (2) and parts of structure (3), The condition is that at least one part of the structure (1) is a part of the structure 3A: Wherein (i) Y represents a straight-chain or branched linking group containing one or more carbon atoms, (ii) each X may be the same or different, representing an alkoxy group or an organic group that is inert to isocyanate groups at 100°C or lower, provided that at least one X represents an alkoxy group, and (iii) each R 1 They may be the same or different, indicating organic groups that are inert to isocyanate groups at 100°C or lower; (iv) each R 2 They may be the same or different, representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower; and (v) " "" indicates a connection to another part of the polysilane compound.

32. A polysilane compound comprising: (a) At least two parts of structure (1): (b1) Part of structure (2): or (b2) Part of structure (3): or (b3) The combination of parts of structure (2) and parts of structure (3), The condition is that the polysilane compound has only one structural 3B moiety: Wherein (i) Y represents a straight-chain or branched linking group containing one or more carbon atoms, (ii) each X may be the same or different, representing an alkoxy group or an organic group that is inert to isocyanate groups at 100°C or lower, provided that at least one X represents an alkoxy group, and (iii) each R 1 They may be the same or different, indicating organic groups that are inert to isocyanate groups at 100°C or lower; (iv) each R 2 They may be the same or different, representing hydrogen or an organic group that is inert to the isocyanate group at 100°C or lower; and (v) " "" indicates a connection to another part of the polysilane compound.

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