BR112020013367B1 - HETEROCHAIN POLYMER COMPOSITION - Google Patents

Abstract

This disclosure relates to polymerizable silicone compositions, methods for polymerizing such compositions, and polymerized silicone compositions formed therefrom. In one embodiment, a polymerizable composition includes one or more first organosiloxanes or organosilanes, each comprising a plurality of silicon hydride functional groups, one or more second organosiloxanes or organosilanes, each comprising a plurality of of reactive heterocycloalkyl functional groups; and one or more third organosiloxanes or organosilanes, each comprising at least about one silicon hydride functional group and at least about one reactive heterocycloalkyl functional group; one or more reactive organic compounds, each comprising at least about one reactive heterocycloalkyl functional group; and an effective amount of a borane catalyst, present, for example, in an amount in the range of 0.0005% by weight to about 10% by weight, wherein the ratio of reactive heterocycloalkyl functional groups to reactive hydride functional groups of silicon in the composition is in the range of 1:5 to 5:1.

Description

CROSS REFERENCE TO RELATED ORDERS

[0001] This application claims the benefit of the priority of Provisional Patent Applications No. 62/612,332, filed on December 30, 2017; No. 62/612336, filed on December 30, 2017; No. 62/612337, filed on December 30, 2017; and No. 62/612338, filed December 30, 2017, each of which is incorporated herein by reference in its entirety.

BACKGROUND TO DISCLOSURE FIELD OF DISCLOSURE

[0002] This disclosure generally relates to heterochain polymer compositions. More specifically, the present disclosure relates to organic compositions based on polymerizable silicone and carbon, methods for polymerizing such compositions, and polymerized compositions formed therefrom, including compositions useful as adhesives (including pressure-sensitive adhesives), sealants, and bonding materials. release.

TECHNICAL BACKGROUND

[0003] Silicones, also known as polysiloxanes, are polymers that include any synthetic, inert compound, formed by repeating units of siloxane, which is a chain of alternating silicon atoms and oxygen atoms, often combined with carbon and hydrogen. Silicones are widely used in applications including electronics, household items, automobiles and cosmetics.

[0004] Although linear silicones of any molecular weight are fluidic due to the flexibility of the silicon-oxygen bonds, silicones can be polymerized or cross-linked (i.e., cured or vulcanized), to provide, for example, liquids, elastomers, gels, plastics hard materials and resins, for use in applications such as sealants, adhesives, lubricants, thermal and electrical insulation, kitchen utensils, etc.

[0005] Silicones are conventionally crosslinked by peroxide curing, addition curing and condensation curing. Peroxide curing, often used to cure molded or extruded high consistency silicone rubber (HCR), involves thermally decomposing peroxides to provide free radicals that initiate cross-linking between silicones. Peroxides such as dia-aralkyl peroxides, alkyl-aralkyl peroxides and dia-alkyl peroxides decompose at relatively low temperatures, but provide radicals capable of forming cross-links between an alkyl group and a vinyl group. Nonspecific vinyl peroxides, such as diacyl peroxides and peroxide esters, provide radicals capable of forming crosslinks between two alkyl groups, but they decompose only at relatively high temperatures. Peroxides are typically included in amounts of about 1% of a composition to achieve effective curing. While some, or even most, of the decomposed peroxide derivatives are consumed during processing and/or post-curing at elevated temperatures, by-products that may be undesirable, for example, in medical or pharmaceutical applications, remain in the silicone composition.

[0006] Addition curing of silicones involves a metal-catalyzed addition reaction between a vinyl group and a silicon hydride group (i.e., hydrosilylation). Addition-cured compositions are conventionally supplied as two-part kits, including a catalyst-vinyl functionalized silicone composition and a vinyl-silicone-silicon hydride functionalized silicone composition. Platinum is the most commonly used hydrosilylation catalyst for addition curing processes. Platinum-catalyzed addition curing, which does not form volatile byproducts, is useful for HCR and liquid silicone rubber (LSR) applications, but requires a sensitive and expensive catalyst material. Platinum is also very sensitive to certain contaminants in epoxy, natural rubber, PVC and moisture-curing silicones, and application to these substrates is limited. Furthermore, the efficiency of the cross-linking reaction requires the use of inhibitors, such as acetylenic alcohols or fumarate- or maleate-based compounds, the inclusion of which increases the temperature required to conduct the cross-linking reaction.

[0007] Condensation curing of silicones involves the reaction of a hydroxyl group and a silane. For example, methyltriacetoxysilane, upon exposure to moisture, hydrolyzes to form hydroxyl groups, which can subsequently form cross-links with other hydroxyl groups, such as those in a hydroxyl-terminated silicone. Such condensation-cured compositions may be provided as one-part kits that cure upon exposure to atmospheric moisture. Because the diffusion of atmospheric moisture through a silicon composition is limited, however, it may be difficult to cure portions of the composition more than, for example, about 10 mm below the surface of the composition. To ensure that condensation-cured silicone compositions are fully crosslinked, an organometallic tin catalyst may be included with the crosslinker, separated from the polymer in a two-part condensation system; however, the toxicity of tin greatly limits the applications for which silicones cured by these means can be used. Furthermore, in all condensation curing processes, the loss of volatile byproducts causes a significant reduction in volume.

[0008] Radiation curing of silicones may involve, for example, the reaction of epoxides (i.e., a cationic curing mechanism), the reaction of acrylates (a free radical curing mechanism), the reaction of an aliphatic group unsaturated (e.g. a vinyl group) and a thiol group, etc. UV light can be used as an energy source for all chemicals, with these reactions requiring the use of a photoinitiator. The electron beam is restricted to free radical chemistry and can be used without a photoinitiator. Radiation curing has advantages in controlling curing, but the photoinitiators used can be very sensitive to ambient humidity. Additionally, the use of electron beam and UV light requires certain safety precautions.

[0009] As would be recognized by one skilled in the art, conventional silicone materials and conventional organic polymers can have a number of desirable properties. However, there are certain ranges of properties such as mechanical properties, surface energies, reactivities and electro-optical properties, especially in combinations that are difficult to achieve using silicone polymers or organic polymers alone.

[0010] Furthermore, the use of curable materials such as adhesives or sealants brings a special set of problems. It is normally desirable for adhesives to have a long shelf life, that is, the time during which the uncured material remains viable, so that it can be dispensed and discarded in the body or bodies to which it is to be adhered. But at the same time, it is desirable for an adhesive or sealant to have a relatively fast curing rate so that once it begins, adhesion does not take a long time. Additionally, adhesives and sealants need to have desirable mechanical and adhesive properties to make them suitable for use.

[0011] Silicone-based pressure-sensitive adhesive compositions are very versatile because they exhibit good adhesion to a variety of substrates, including glass, ceramics, vinyl siding, finished wood, and painted drywall under challenging environmental conditions, including temperature extremes. and humidity. However, pressure-sensitive adhesives require a delicate balance of viscous and elastic properties that affect adhesion, cohesion, stretch and elasticity. Although there are numerous silicone-based pressure-sensitive adhesive compositions, advances in end-use requirements continue to drive the need for new adhesive compositions and tape constructions. In addition to performance properties, environmental regulations and processing costs also influence adhesive production requirements.

[0012] Many silicone-based pressure-sensitive adhesive compositions are covered over a release coating. Release coatings, therefore, provide a variety of functions for pressure-sensitive adhesive compositions, including, for example, preventing contamination of the adhesive layer and facilitating handling of the adhesive or an article covered with adhesive. A release liner is often left in place on a pressure-sensitive adhesive composition and adhered to another substrate. The release liner, therefore, can experience a variety of environmental conditions, including changes in temperature and humidity. As a result, the release liner must function for long periods of time.

[0013] The strength of the adhesive bond formed between a silicone-based pressure-sensitive adhesive composition and a release material (e.g., in the form of a coating) tends to increase over time and after exposure to elevated temperatures. This is known as "adhesion building." If the bond strength between the adhesive composition and the release liner is too high, the release liner and the adhesive composition cannot be separated from each other or can be separated only with difficulty, making the adhesive unsuitable for the intended purpose. which is intended. One method for decreasing the degree of adhesion construction involves altering the surface chemistry of the coating by covering the coating with a surface chemistry modifier such as fluorosilicones. While current methods have reduced adhesion levels, adhesion building continues to occur.

[0014] More generally, providing a material suitable for use as a release material is a special challenge because it is necessary to provide a desirably low release force and at the same time provide other desirable properties to the material (e.g. fast curing, long service life, desirable mechanical strength and thermal properties).

[0015] Therefore, there remains a need for a silicone curing process that does not require a sensitive and/or toxic catalyst, that does not result in significant bulk, does not provide undesirable cross-linking byproducts, and/or provides a curing silicone composition. uniform, especially suitable for use as an adhesive (e.g. pressure-sensitive adhesive), sealant or release material.

DISCLOSURE SUMMARY

[0016] One aspect of the disclosure is a polymerizable composition that includes one or more organosiloxanes or organosilanes, one or more organosiloxanes or organosilanes comprising one or more of one or more organosiloxanes or organosilanes, each comprising a plurality of silicon hydride functional groups, present in an amount within the range of about 0.05% by weight to about 99.95% by weight; one or more second organosiloxanes or organosilane, each comprising a plurality of reactive heterocycloalkyl functional groups, present in an amount within the range of about 0.05% by weight to about 99.95% by weight; and one or more third organosiloxanes or organosilanes, each comprising at least about one silicon hydride functional group and at least about one reactive heterocycloalkyl functional group, present in an amount within the range of about 0.05 % by weight to about 99.95% by weight; one or more reactive organic compounds, each comprising at least about one reactive heterocycloalkyl functional group, present in an amount within the range of about 0.05% by weight to about 99.95% by weight; and an effective amount of a borane catalyst, present, for example, in an amount within the range of 0.0005% by weight to about 10% by weight, wherein the ratio of reactive heterocycloalkyl functional groups to reactive heterocycloalkyl functional groups Reactive silicon hydride in composition is in the range of 1:5 to 5:1.

[0017] In certain further aspects of the disclosure, the polymerizable composition as described above, when polymerized, has a release force no greater than about 200 gf/inch (e.g., no more than about 100 gf/inch, no more than about 75 gf/inch, no more than about 50 gf/inch, no more than about 25 gf/inch, no more than about 10 gf/inch, or no more than about 5 gf/inch), as measured by the PSTC 4 test procedure.

[0018] Another aspect of the disclosure is the use of a polymerized composition of the disclosure as a release material, for example, in the form of a release layer. Such a release material may be formed, for example, as a coating or film on the surface of an article. These release materials can be used, for example, in life science applications, electronic devices such as a microelectronic device, electro-optical devices, and products for retail and consumer applications and industrial applications. The release material may be configured, for example, as a release coating for an adhesive, such as a pressure-sensitive adhesive.

[0019] Another aspect of the disclosure is a polymerized composition that is the polymerization product of a polymerizable composition as described herein.

[0020] Another aspect of the disclosure is the use of a polymerized composition of the disclosure in a product for a life science application, an electronic device such as a microelectronic device or an electro-optical device.

[0021] Another aspect of the disclosure is the use of a polymerized composition of the disclosure in a product for retail and consumer orders (sealants and adhesives) and industrial applications (e.g., construction, fluid system and automotive applications).

[0022] Another aspect of the disclosure is an article comprising: a first surface; a second surface; and a polymerized composition for adhering or sealing the first surface to the second surface, wherein the polymerized composition is a polymerization product of a polymerizable composition as described herein.

[0023] Another aspect of the disclosure is a method for attaching or sealing a first surface to a second surface to prepare the article of the disclosure, the method comprising arranging a polymerizable composition as described herein so that it contacts the first surface and the second surface; and then polymerizing the polymerizable composition to adhere or seal the first surface to the second surface.

[0024] Another aspect of the disclosure is an electro-optical device that includes: an electro-optical array; a matrix attachment material that adheres the electro-optical matrix to a substrate; and an encapsulating material that encapsulates the electro-optical matrix, one or more of the matrix fixing material and the encapsulating material being a polymerized composition as described herein.

[0025] Another aspect of the disclosure is an electro-optical device that includes: an electro-optical array; a matrix attachment material that adheres the electro-optical matrix to a substrate; and an encapsulating material that encapsulates the electro-optical matrix; and an optical material disposed in the encapsulant and configured in an operational optical beam path of the electro-optical array, one or more of the array attachment material, the optical material and the encapsulant material being a polymerized composition as described herein.

[0026] Another aspect of the disclosure is a tubing with a first layer disposed concentrically around a second layer and a layer of a polymerized product of a polymerizable composition according to the disclosure disposed between and in contact with the first layer and the second layer. In certain embodiments, the first layer is formed from a silicone polymer and the second layer is formed from a non-silicone polymer (e.g., a polyolefin or a thermoplastic polyurethane). In certain embodiments, the first layer is formed from a non-silicone polymer (e.g., a polyolefin or a thermoplastic polyurethane) and the second layer is formed from a silicone polymer.

[0027] Another aspect of the disclosure is a polymerizable composition that includes one or more organosiloxanes or organosilanes, one or more organosiloxanes or organosilanes comprising one or more of one or more first organosiloxanes or organosilanes , each comprising a plurality of silicon hydride functional groups, present in an amount ranging from about 0.05% by weight to about 89.95% by weight; one or more second organosiloxanes or organosilanes, each comprising a plurality of reactive heterocycloalkyl functional groups, present in an amount ranging from about 0.05% by weight to about 89.95% by weight; and one or more third organosiloxanes or organosilanes, each comprising at least about one silicon hydride functional group and at least about one reactive heterocycloalkyl functional group, present in an amount in the range of about 0.05% by weight at about 89.95% by weight; one or more reactive organic compounds, each comprising at least about one reactive heterocycloalkyl functional group, present in an amount ranging from about 0.05% by weight to about 89.95% by weight; one or more tackifiers present in an amount ranging from about 10% by weight to about 99.95% by weight; and an effective amount of a borane catalyst, present, for example, in an amount within the range of 0.0005% by weight to about 10% by weight, wherein the ratio of reactive heterocycloalkyl functional groups to reactive heterocycloalkyl functional groups Reactive silicon hydride in composition is in the range of 1:5 to 5:1. In certain embodiments, the tackifier is present in an amount ranging from about 20% by weight to about 75% by weight of the composition.

[0028] Another aspect of the disclosure is a pressure-sensitive adhesive that is the polymerization product of a polymerizable composition, as described herein.

[0029] Another aspect of the disclosure is a pressure-sensitive adhesive that includes a polymerization product of a polymerizable composition comprising one or more organosiloxanes or organosilanes, one or more organosiloxanes or organosilanes comprising one or more of one or more first organosiloxanes or organosilanes, each comprising a plurality of silicon hydride functional groups, present in an amount ranging from about 0.05% by weight to about 89.95% by weight; one or more second organosiloxanes or organosilane, each comprising a plurality of reactive heterocycloalkyl functional groups, present in an amount ranging from about 0.05% by weight to about 89.95% by weight; and one or more third organosiloxanes or organosilanes, each comprising at least about one silicon hydride functional group and at least about one reactive heterocycloalkyl functional group, present in an amount in the range of about 0.05% by weight at about 89.95% by weight; and one or more reactive organic compounds, each comprising at least about one reactive heterocycloalkyl functional group, present in an amount in the range of about 0.05% by weight to about 89.95% by weight; an effective amount of a borane catalyst, present, for example, in an amount within the range of 0.0005% by weight to about 10% by weight, wherein the ratio of reactive heterocycloalkyl functional groups to silicon hydride functional groups reactive in composition is in the range of 1:5 to 5:1; and one or more reactive organic compounds, each comprising at least about one reactive heterocycloalkyl functional group, present in an amount within the range of about 0.05% by weight to about 99.95% by weight; one or more tackifiers, present in an amount within the range of about 10% by weight to about 99.95% by weight. In certain embodiments, the tackifier is present in an amount ranging from about 20% by weight to about 75% by weight of the composition.

[0030] Another aspect of the disclosure is an article comprising: a substrate; and a pressure-sensitive adhesive or release material as described herein disposed on the substrate.

[0031] The articles of the disclosure may further include a release coating, for example, disposed on a layer of pressure-sensitive adhesive opposite the substrate.

BRIEF DESCRIPTION OF FIGURES

[0032] Figure 1 is a schematic cross-sectional view of an article according to one embodiment of the disclosure.

[0033] Figure 2 is a schematic cross-sectional view of an article according to another embodiment of the disclosure.

[0034] Figure 3 is a schematic cross-sectional view of a pipeline according to one embodiment of the disclosure.

[0035] Figure 4 is a schematic cross-sectional view of an electro-optical device according to an embodiment of the disclosure.

[0036] Figure 5 is a schematic cross-sectional view of an article according to one embodiment of the disclosure.

[0037] Figure 6 is a schematic cross-sectional view of an article according to one embodiment of the disclosure.

[0038] Figure 7 is a schematic cross-sectional view of an article according to one embodiment of the disclosure.

[0039] Figure 8 is a schematic cross-sectional view of a structure including a release material in accordance with an embodiment of the disclosure.

[0040] Figure 9 is a schematic cross-sectional view of a structure including a release material in accordance with an embodiment of the disclosure.

[0041] Figure 10 is a photograph of three polymerized compositions obtained by polymerizing the polymerizable compositions of Examples 1 to 3.

[0042] Figure 11 is a graph of the thermogravimetric analysis of the polymerized composition of Example 1 (labeled "silicone-bisphenol A copolymer") compared to two comparative examples.

DETAILED DESCRIPTION

[0043] The information shown here is by way of example only and for purposes of illustrative discussion of preferred embodiments of the present invention and is presented for the sake of providing what is believed to be the most useful and easily understood description of the principles and conceptual aspects of various embodiments of the invention. In this regard, no attempt is made to show structural details of the invention in more detail than is necessary for a fundamental understanding of the invention, the description made with the drawings and/or examples making it apparent to those skilled in the art how the various forms of the invention can be implemented in practice. Thus, before the disclosed processes and devices are described, it should be understood that the aspects described herein are not limited to specific embodiments, apparatus or configurations and, as such, may, of course, vary. It should also be understood that the terminology used here is intended to describe particular aspects only and, unless specifically defined here, is not intended to be limiting.

[0044] The terms "a", "the", and similar referents used in the context of describing the invention (especially in the context of the following claims) should be interpreted to encompass both the singular and the plural, unless as otherwise indicated here or clearly contradicted by the context. The recitation of ranges of values described herein serves only as a shorthand method of individually referring to each separate value within the range. Unless otherwise indicated herein, each individual value is incorporated in the specification as if recited here individually. Ranges may be expressed here as from "about" a particular value and/or to "about" another particular value. When this range is expressed, another aspect includes from a particular value and/or to another particular value. Likewise, when values are expressed as approximations, by the use of the antecedent "about", it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant relative to the other endpoint and independently of the other endpoint.

[0045] All methods described herein can be performed in any suitable order of steps, unless otherwise indicated here or clearly contradicted by the context. The use of any and all examples or exemplary language (e.g., "such as") provided herein is intended only to further illuminate the invention and does not represent a limitation on the scope of the otherwise claimed invention. No language in the specification should be construed as indicating any unclaimed element essential to the practice of the invention.

[0046] Unless the context clearly requires otherwise, throughout the description and claims, the words "comprising", "comprising", and the like are to be construed in an inclusive sense, as opposed to an exclusive or exhaustive sense ; that is, in the sense of "including but not limited to". Words that use the singular or plural number also include the plural and singular number, respectively. Furthermore, the words "described herein", "above" and "below" and words of similar import, when used in this order, shall refer to this order as a whole and not to particular parts of the order.

[0047] As will be understood by one skilled in the art, each embodiment disclosed herein may comprise, consist essentially of, or consist of its particular stated element, step, ingredient, or specific stated component. As used herein, the transitional term "comprise" or "comprises" means to include, but is not limited to, and allows for the inclusion of unspecified elements, steps, ingredients, or components, even in large quantities. The transition phrase "consisting of" excludes any unspecified element, step, ingredient, or component. The transitional phrase "consisting essentially of" limits the scope of the embodiment to the specified elements, steps, ingredients, or components and those that do not materially affect the embodiment.

[0048] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions and so on used in the specification and claims should be understood as modified in all cases by the term "about. " Therefore, unless otherwise indicated, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending on the desired properties to be obtained by the present invention. At a minimum, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter must at least be interpreted in light of the number of significant digits reported and applying common rounding techniques. When more clarity is required, the term "about" has the meaning reasonably assigned to it by one skilled in the art when used in conjunction with a stated numerical value or range, i.e., denoting a little more or a little less than the declared value or range, within a range of ± 20% of the declared value; ± 19% of the declared value; ± 18% of the declared value; ± 17% of the declared value; ± 16% of the declared value; ± 15% of the declared value; ± 14% of the declared value; ± 13% of the declared value; ± 12% of the declared value; ± 11% of the declared value; ± 10% of the declared value; ± 9% of the declared value; ± 8% of the declared value; ± 7% of the declared value; ± 6% of the declared value; ± 5% of the declared value; ± 4% of the declared value; ± 3% of the declared value; ± 2% of the declared value; or ± 1% of the declared value.

[0049] Although the numerical ranges and parameters that establish the broad scope of the invention are approximations, the numerical values established in the specific examples are reported as accurately as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective test measurements.

[0050] Groupings of alternative elements or embodiments of the invention disclosed herein should not be construed as limitations. Each member of the group may be referred to and claimed individually or in any combination with other elements of the group or other elements found herein. It is anticipated that one or more elements of a group may be included or excluded from a group for reasons of convenience and/or patentability. When any inclusion or exclusion occurs, the specification is deemed to contain the modified group, thereby complying with the written description of all Markush groups used in the attached claims.

[0051] Some embodiments of this invention are described here, including the best way known to the inventors to carry out the invention. Obviously, variations in these described embodiments will be apparent to those skilled in the art after reading the previous description. The inventor expects those skilled in the art to employ such variations as appropriate, and the inventors intend for the invention to be practiced other than specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the appended claims, as permitted by applicable law. Furthermore, any combination of the above-described elements in all possible variations is encompassed by the invention unless otherwise indicated here or clearly contradicted by the context.

[0052] Furthermore, numerous references have been made to patents and printed publications throughout this specification. Each cited reference and printed publication is incorporated herein individually by reference in its entirety.

[0053] In closing, it should be understood that the embodiments of the invention disclosed herein are illustrative of the principles of the present invention. Other modifications that may be employed are within the scope of the invention. Thus, by way of example, but not limitation, alternative embodiments of the present invention may be used in accordance with the teachings herein. Therefore, the present invention is not limited to that exactly as shown and described.

[0054] The terms used here may be preceded and/or followed by a single dash, "-", or a double dash, “=”, to indicate the order of bonding between the named substituent and its original portion a single dash indicates a single bond and a double dash indicates a double bond or a pair of single bonds in the case of a spiro substituent. In the absence of a single or double feature, it is understood that a single bond is formed between the substituent and its original moiety; furthermore, substituents must be read "from left to right" unless a dash indicates otherwise. For example, arylalkyl, arylalkyl- and -alkylaryl indicate the same functionality.

[0055] For simplicity, chemical moieties are defined and referred to primarily as univalent chemical moieties (e.g., alkyl, aryl, etc.). However, these terms are also used to convey corresponding multivalent moieties, in appropriate structural circumstances, clear to those skilled in the art. For example, although an "alkyl" moiety may refer to a monovalent radical (e.g., CH3-CH2-), in some circumstances a divalent bond moiety may be "alkyl", in which case those skilled in the art will understand the alkyl as being a divalent radical (e.g. -CH2-CH2-), which is equivalent to the term "alkylene". (Similarly, in circumstances where a divalent moiety is required and is declared to be "aryl", those skilled in the art will understand the term "aryl" to refer to the corresponding divalent moiety, arylene). All atoms have their normal number of valences for bond formation (i.e., 4 for carbon, 3 for N, 2 for O, and 2, 4, or 6 for S, depending on the oxidation state of S). The nitrogens in currently disclosed compounds may be hypervalent, for example, an N-oxide or a tetrasubstituted ammonium salt. On occasion, a portion may be defined, for example, as -B-(A)a, where a is 0 or 1. In such cases, when a is 0, the portion is -B and when a is 1, the portion is -B-A.

[0056] As used herein, the term "hydrocarbon" includes linear hydrocarbons, branched hydrocarbons, acyclic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, including, for example, alkyl (including alkoxyalkyl), alkoxy, alkenyl, alkynyl, aryl, heteroaryl, heterocycloalkyl and cycloalkyl. A "hydrocarbonylene" is a divalent hydrocarbon radical (i.e., with two attachment points). In certain desirable embodiments, each hydrocarbonylene does not include a carbon-carbon double bond. Particular desirable hydrocarbonylene moieties include -(C1-C6alkyl)-, -(C1-C6alkyl)-O-, -O-(C1-C6alkyl)-, and -(C1-C6alkyl)- O-(C1-C6alkyl)- Each alkyl of these moieties may be unsubstituted or in other embodiments may be substituted by one or two =O or -OH groups. In any and all embodiments as described herein that include a hydrocarbonylene moiety, each such hydrocarbonylene moiety may be selected from the moieties described above.

[0057] As used herein, the term "alkyl" includes a saturated hydrocarbon having a projected number of carbon atoms, such as 1 to 10 carbons (i.e., including 1 and 10), 1 to 8 carbons, 1 to 6 carbons, 1 to 3 carbons, or 1, 2, 3, 4, 5 or 6. The alkyl group can be linear or branched and, depending on the context, can be a monovalent radical or a divalent radical (i.e., an alkylene group). For example, the “-(C1-C6alkyl)-O-” moiety means oxygen connection through an alkylene bridge with 1 to 6 carbons and C1-C3 alkyl represents methyl, ethyl and propyl moieties. Examples of "alkyl"; include, for example, methyl, ethyl, propyl, isopropyl, butyl, iso-, sec- and tert-butyl, pentyl and hexyl.

[0058] The term "alkoxy" represents an alkyl group of an indicated number of carbon atoms linked to the original molecular moiety through an oxygen bridge. Examples of "alkoxy" include, for example, methoxy, ethoxy, propoxy and isopropoxy.

[0059] As used herein, the term "alkenyl" includes unsaturated hydrocarbons containing 2 to 10 carbons (i.e., including 2 and 10), 2 to 8 carbons, 2 to 6 carbons, or 2, 3, 4, 5 or 6, unless otherwise indicated, and containing at least one carbon-carbon double bond. An alkenyl group can be linear or branched and, depending on the context, can be a monovalent radical or a divalent radical (i.e., an alkenylene group). For example, the moiety “-(C2-C6alkenyl)-O-” means the connection of an oxygen atom through an alkenylene bridge having from 2 to 6 carbon atoms. Representative examples of alkenyl include, but are not limited to, ethenyl, 2-propenyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, 5-hexenyl, 2-heptenyl, 2-methyl-1-heptenyl, 3-decenyl and 3,7-dimethylocta-2,6-dienyl.

[0060] As used herein, the term "alkynyl" includes unsaturated hydrocarbons containing 2 to 10 carbons (i.e., including 2 and 10), 2 to 8 carbons, 2 to 6 carbons, or 2, 3, 4, 5 or 6, unless otherwise indicated, and containing at least one carbon-carbon triple bond. An alkynyl group can be linear or branched and, depending on the context, can be a monovalent radical or a divalent radical (i.e., an alkynylene group). For example, the moiety “-(C2-C6alkynyl)-O-” means the connection of an oxygen atom through an alkynylene bridge having 2 to 6 carbon atoms. Representative examples of alkynyl include, but are not limited to, acetylenyl, 1-propynyl, 2-propynyl, 3-butynyl, 2-pentynyl and 1-butynyl.

[0061] The term "aryl" represents an aromatic ring system with a single ring (e.g., phenyl) that is optionally fused with other aromatic hydrocarbon rings or non-aromatic hydrocarbon rings or heterocycles. "Aryl" includes ring systems having multiple condensed rings and in which at least one is carbocyclic and aromatic (e.g., 1,2,3,4-tetrahydronaphthyl, naphthyl). Examples of aryl groups include phenyl, 1-naphthyl, 2-naphthyl, indanyl, indenyl, dihydronaphthyl, fluorenyl, tetralinyl and 6,7,8,9-tetrahydro-5H-benzo[a]cycloheptenyl. "Aryl" also includes ring systems with a first carbocyclic aromatic ring fused to a non-aromatic heterocycle, for example, 1H-2,3-dihydrobenzofuran and tetrahydroisoquinolinyl. Aryl groups herein are unsubstituted or, when specified as "optionally substituted", may, unless otherwise indicated, be substituted at one or more positions substitutable by various groups as indicated.

[0062] The terms "halogen" or "halo" indicate fluorine, chlorine, bromine and iodine.

[0063] The term "heteroaryl" refers to a system of aromatic rings containing at least one heteroatom selected from nitrogen, oxygen and sulfur. Most commonly, heteroaryl groups will have 1, 2, 3, or 4 heteroatoms. Heteroaryl may be fused with one or more non-aromatic rings, for example, cycloalkyl or heterocycloalkyl rings, wherein cycloalkyl and heterocycloalkyl rings are described herein. In one embodiment of the present compounds, the heteroaryl group is linked to the remainder of the structure through an atom in an aromatic ring of the heteroaryl group. In another embodiment, the heteroaryl group is linked to the rest of the structure through a non-aromatic ring atom. Examples of heteroaryl groups include, for example, pyridyl, pyrimidinyl, quinolinyl, benzothienyl, indolyl, indolinyl, pyridazinyl, pyrazinyl, isoindolyl, isoquinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, imidazolyl, isoxazolyl, pyrazolyl, oxazolyl, thiazolyl, indolizinyl, indazolyl, benzothiazolyl , benzimidazolyl, benzofuranyl, furanyl, thienyl, pyrrolyl, oxadiazolyl, thiadiazolyl, benzo[1,4] oxazinyl, triazolyl, tetrazolyl, isothiazolyl, naphthyridinyl, isochromanyl, cromanyl, isoindolinyl, isobenzotienyl, benzoxazolyl, pyridopyridinyl, purinyl, benzodioxolyl, il, pteridinyl , benzothiazolyl, imidazopyridinyl, imidazothiazolyl, benzisoxazinyl, benzoxazinyl, benzopyranyl, benzothiopyryl, benzopyril, cromonyl, chromanonyl, -N- pyridinyl oxide, isoindolinonyl, benzodioxanyl, benzoxazolinonyl, pyrrolyl N-oxide, pyrimidinyl N-oxide, N-oxide pyridazinyl, pyrazinyl N-oxide, quinolinyl N-oxide, indolyl N-oxide, indolinyl N-oxide, isoquinolyl N-oxide, quinazolinyl N-oxide, quinoxalinyl N-oxide, phthalazinyl N-oxide, Imidazolyl N-oxide, Isoxazolyl N-oxide, Oxazolyl N-oxide, Thiazolyl N-oxide, Indolizinyl N-oxide, Indazolyl N-oxide, Benzothiazolyl N-oxide, Benzimidazolyl N-oxide, N- pyrrolyl oxide, oxadiazolyl N-oxide, thiadiazolyl N-oxide, triazolyl N-oxide, tetrazolyl N-oxide, benzothiopyranyl S-oxide, S,S- benzothiopyranyl dioxide. Preferred heteroaryl groups include pyridyl, pyrimidyl, quinolinyl, indolyl, pyrrolyl, furanyl, thienyl and imidazolyl, pyrazolyl, indazolyl, thiazolyl and benzothiazolyl. In certain embodiments, each heteroaryl is selected from pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, imidazolyl, isoxazolyl, pyrazolyl, oxazolyl, thiazolyl, furanyl, thienyl, pyrrolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, isothiazolyl, pyridinyl-N-oxide, Pyrrolyl N-oxide, Pyrimidinyl N-oxide, Pyridazinyl N-oxide, Pyrazinyl N-oxide, Imidazolyl N-oxide, Isoxazolyl N-oxide, Oxazolyl N-oxide, Thiazolyl N-oxide, N- pyrrolyl oxide, oxadiazolyl N-oxide, thiadiazolyl N-oxide, triazolyl N-oxide and tetrazolyl N-oxide. Preferred heteroaryl groups include pyridyl, pyrimidyl, quinolinyl, indolyl, pyrrolyl, furanyl, thienyl, imidazolyl, pyrazolyl, indazolyl, thiazolyl and benzothiazolyl. The heteroaryl groups mentioned herein are unsubstituted or, when specified as "optionally substituted" may, unless otherwise indicated, be substituted at one or more positions substitutable by various groups as indicated.

[0064] The term "heterocycloalkyl" refers to a non-aromatic ring or ring system containing at least one heteroatom that is selected from nitrogen, oxygen and sulfur, wherein said heteroatom is in a non-aromatic ring . Heterocycloalkyl can have 1, 2, 3 or 4 heteroatoms. The heterocycloalkyl may be saturated (i.e., a heterocycloalkyl) or partially unsaturated (i.e., a heterocycloalkenyl). Heterocycloalkyl includes monocyclic groups of 3 to 8 ring atoms, as well as bicyclic and polycyclic ring systems, including bridged and fused systems, wherein each ring includes 3 to 8 ring atoms. The heterocycloalkyl ring is optionally fused with other heterocycloalkyl rings and/or non-aromatic hydrocarbon rings. In certain embodiments, heterocycloalkyl groups have 3 to 7 elements in a single ring. In other embodiments, heterocycloalkyl groups have 5 or 6 elements in a single ring. In some embodiments, heterocycloalkyl groups have 3, 4, 5, 6 or 7 elements in a single ring. Examples of heterocycloalkyl groups include, for example, azabicyclo[2.2.2]octyl, azabicyclo[3.2.1]octyl, 2,5-diazabicyclo[2.2.1]heptyl, morpholinyl, thiomorpholinyl, thiomorpholinyl S-oxide, S dioxide, S- of thiomorpholinyl, 2-oxazolidonyl, piperazinyl, homopiperazinyl, piperazinonyl, pyrrolidinyl, azepanil, azetidinyl, pyrrolinyl, tetrahydropyranyl, piperidinyl, tetrahydrofuranyl, tetrahydrothienyl, 3,4-dihydroisoquinolin-2(1H)- yl, isoindolindionyl, homopiperidinyl, homomorpholyl, homothiomorpholyl, homothiomorpholyl S,S- dioxide, oxazolidinonyl, dihydropyrazolyl, dihydropyrrolyl, dihydropyrazinyl, dihydropyridinyl, dihydropyrimidinyl, dihydrofuryl, dihydropyranyl, imidazolidinyl, S- tetrahydrothienyl oxide, S,S- tetrahydrothienyl dioxide and S- homothiomorpholinyl oxide. Heterocycloalkyl groups include morpholinyl, 3,4-dihydroisoquinolin-2(1H)-yl, tetrahydropyranyl, piperidinyl, aza-bicyclo[2.2.2]octyl, Y—butyrolactonyl (i.e., a tetrahydrofuranyl substituted by - oxos), Y-butyrolactamyl (i.e., an oxo-substituted pyrrolidine), pyrrolidinyl, piperazinyl, azepanil, azetidinyl, thiomorpholinyl, S,S- thiomorpholinyl dioxide, 2-oxazolidonyl, imidazolidonyl, isoindolindionyl, piperazinonionyl. The heterocycloalkyl groups mentioned herein are unsubstituted or, when specified as "optionally substituted" may, unless otherwise indicated, be substituted at one or more positions substitutable by various groups as indicated.

[0065] Specifically, "reactive heterocycloalkyl" refers to heterocycloalkyl groups that are reactive to borane-catalyzed hydrosilylation. Reactive heterocycloalkyl groups include cyclic ethers, such as epoxides and oxetanes, and cyclic thioethers, such as episulfide groups. In certain embodiments as disclosed herein, "reactive heterocycloalkyl" refers herein to epoxide functional groups.

[0066] The term "cycloalkyl" refers to a non-aromatic carbocyclic ring or ring system, which may be saturated (i.e., a cycloalkyl) or partially unsaturated (i.e., a cycloalkenyl). The cycloalkyl ring may optionally be fused to or otherwise attached (e.g., bridged systems) to other cycloalkyl rings. Certain examples of cycloalkyl groups present in the disclosed compounds have 3 to 7 elements in a single ring, such as having 5 or 6 elements in a single ring. In some embodiments, the cycloalkyl groups have 3, 4, 5, 6, or 7 elements in a single ring. Examples of cycloalkyl groups include, for example, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, tetrahydronaphthyl and bicyclo[2.2.1] heptane. The cycloalkyl groups mentioned herein are unsubstituted or, when specified as "optionally substituted", may be substituted at one or more positions substitutable by various groups, as indicated.

[0067] The term "siloxane" refers to the Si-O-Si functional group. The term "siloxane" may refer to disiloxane, i.e., R3Si-O-SiR3, or polysiloxane, i.e., R3Si-O-[SiR2-O]n-SiR3, where n is at least one. As used herein, the term "siloxane" includes cyclic polysiloxanes. The term "siloxane repeat unit" refers to repeat units - [SiR2-O] - comprising a polysiloxane.

[0068] The term “organosiloxane” refers to compounds including the functional siloxane group, i.e. Si-O-Si, in which one or more silicon atoms are bonded to carbon and/or hydrogen, i.e. R3Si-O-Si-R3 or R3Si-O-[SiR2-O]n-SiR3, where at least one R includes carbon and/or hydrogen. For example, hexamethyldisiloxane, poly(dimethylsiloxane), and methylhydrosiloxane-dimethylsiloxane copolymer are organosiloxanes.

[0069] The term "silane" refers to saturated chemical compounds, including one or multiple atoms of silicon bonded together or one or multiple atoms of other chemical elements as tetrahedral centers of multiple single bonds. The skilled artisan will appreciate that certain siloxanes, for example, tetrakis (dimethylsilyl) orthosilicate, may also be referred to as silanes.

[0070] The term "organosilane" refers to silanes, in which one or more silicon atoms are bonded to carbon and/or hydrogen. For example, tetrakis (dimethylsilyl) orthosilicate and tetramethylsilane are organosilanes.

[0071] The term "hydride" refers to a hydrogen functional group linked to a more electropositive element or group. For example, calcium hydride and sodium hydride comprise hydride functional groups. In another example, hydride-terminated trimethylsilane and poly(dimethylsiloxane) comprise hydride functional groups.

[0072] The term "epoxide" refers to a three-element ring with two carbon atoms and one oxygen atom. For example, 3-(2,3-epoxypropoxy)-propyl and 3,4-epoxycyclohexylethyl groups include an epoxide functional group. The term "oxetane" refers to a four-element ring with three carbon atoms and one oxygen atom. For example, 2-ethyloxane groups include an oxetane functional group.

[0073] The term "ring system" encompasses monocyclics, as well as fused and/or bridged polycyclics.

[0074] The term "oxo" means a doubly bonded oxygen, sometimes designated as =O or, for example, describing a carbonyl, "C(O)" can be used to show a substituted oxo carbon.

[0075] The term "substituted", when used to modify a specified group or radical, means that one or more hydrogen atoms of the specified group or radical are, independently of each other, replaced by the same or different substituent groups, as defined below , unless otherwise specified.

[0076] The terms "polymerizable" and "polymerized" refer to one or more compounds that can be reacted to provide a larger compound and to one or more compounds that have been reacted to provide a larger compound, respectively. For example, a composition of a single compound may be polymerizable (i.e., a monomer) and, upon polymerization, may provide a polymerized compound comprising repeating monomer units. Polymerizable or polymerized compositions may also include "curable" or "cured" compositions, or "cross-linkable" or "cross-linked" compositions, in which compositions comprising polymers and, optionally, monomers and/or cross-linkers, can be, or have been, reacted to provide a composition of larger compounds.

[0077] The present inventors have determined that the hydrosilylation of reactive heterocycloalkanes, such as epoxides, can be advantageously used to form polymers, for example, when catalyzed by borane catalysts. Therefore, the disclosure relates to polymerizable compositions that include one or more organosiloxane(s) or organosilane(s) that include silicon hydrides and reactive alkyl heterocycles and organic molecules that include reactive alkyl heterocycles in a suitable configuration. to provide polymeric material when reacted and a borane catalyst. The disclosure demonstrates that these compositions, which may be free of sensitive and/or toxic catalysts, can be polymerized uniformly, in a controlled manner, without forming undesirable byproducts. The compositions of the disclosure may also be less sensitive to contaminants, such as thiol and tin, compared to metal-catalyzed formulations. The compositions of the disclosure may also have a desirable long shelf life. For example, in certain embodiments, the compositions of the disclosure have working times of 2 hours to a few days, while conventional metal-catalyzed formulations typically have working times of up to 90 minutes. Furthermore, the time and temperature at which the compositions of the disclosure can be cured can be adjusted depending on the desired application. In several particular embodiments, the compositions of the disclosure can be cured in times ranging from, for example, 1 minute to up to 10 days, depending on the polymerization temperature.

[0078] The present inventors have observed that silicones can have numerous desirable properties as a high-performance material, in various cases, including one or more of flexibility, thermal stability, optical transparency and biocompatibility, but that silicones can suffer from a variety of disadvantages. , for example, low tear strength; and poor miscibility and general compatibility with most other polymers. The present inventors have observed that the chemistry detailed here may allow the formation of copolymers of silicones with organic monomers, which may lead to materials that may, in many embodiments, essentially have miscibility between silicone and organic at the molecular level. Such a copolymer can be used to provide materials with desired properties from siloxane and organic monomers, or as the compatibilizer for silicone and organic polymer.

[0079] One aspect of the disclosure is a polymerizable composition that includes one or more organosiloxanes or organosilanes, one or more organosiloxanes or organosilanes comprising one or more of one or more first organosiloxanes or organosilanes , each comprising a plurality of silicon hydride functional groups, present in an amount within the range of about 0.05% by weight to about 99.95% by weight; one or more second organosiloxanes or organosilanes, each comprising a plurality of reactive heterocycloalkyl functional groups, present in an amount ranging from about 0.05% by weight to about 99.95% by weight; and one or more third organosiloxanes or organosilanes, each comprising at least about one silicon hydride functional group and at least about one reactive heterocycloalkyl functional group, present in an amount within the range of about 0.05 % by weight to about 99.95% by weight; one or more reactive organic compounds, each comprising at least about one reactive heterocycloalkyl functional group, present in an amount within the range of about 0.05% by weight to about 99.95% by weight; and an effective amount of a borane catalyst, present, for example, in an amount within the range of 0.0005% by weight to about 10% by weight, wherein the ratio of reactive heterocycloalkyl functional groups to reactive heterocycloalkyl functional groups Reactive silicon hydride in composition is in the range of 1:5 to 5:1.

[0080] As described above, the polymerizable composition includes one or more organosiloxanes or organosilanes, the one or more organosiloxanes or organosilanes comprising one or more of: one or more first organosiloxanes or organosilane, a or more second organosiloxanes or organosilane and one or more third organosiloxanes or organosilanes. That is, any combination of "first", "second" and/or "third" materials can be used to provide a composition with a ratio of reactive heterocycloalkyl functional groups to reactive silicon hydride functional groups in the composition that is in the range from 1:5 to 5:1 (or some other desired range, e.g. as described in this document).

[0081] In certain embodiments, the polymerizable composition includes one or more first organosiloxanes or organosilanes and one or more second organosiloxanes or organosilanes. In certain embodiments, the polymerizable composition is substantially free of (e.g., less than 1% of) the one or more third organosiloxanes or organosilanes. In such embodiments, a polyfunctional silicon hydride-containing material may be reacted with a polyfunctional reactive alkyl heterocycle-containing material to form a polymer, for example, using borane catalysis.

[0082] In other embodiments, the polymerizable composition includes one or more third organosiloxanes. In certain embodiments, the polymerizable composition is substantially free of (e.g., less than 1% of) the one or more first organosiloxanes or organosilanes and the one or more second organosiloxanes or organosilanes. In such embodiments, an organosiloxane or organosilane containing at least one silicon hydride and at least one reactive heterocycloalkyl may be polymerized, for example, using borane catalysis.

[0083] And in still other embodiments, the polymerizable composition includes one or more first organosiloxanes and organosolanes and one or more reactive organic compounds. In certain embodiments, the polymerizable composition is substantially free of (e.g., less than 1% of) the one or more second organosiloxanes or organosilanes and the one or more third organosiloxanes or organosilanes. In such embodiments, a polyfunctional silicon hydride-containing material may be reacted with a polyfunctional reactive alkyl heterocycle-containing material to form a polymer, for example, using borane catalysis.

[0084] The person skilled in the art will appreciate that one or more of the first, second and/or third organosiloxanes or organosilanes and one or more reactive organic compounds can be combined in various ways to provide polymerizable compositions in which the proportion of groups reactive heterocycloalkyl functionals to reactive silicon hydride functional groups in the composition is in the range of 1:5 to 5:1.

[0085] The person skilled in the art will appreciate that the various organosiloxanes and organosilanes described herein can be supplied in a variety of molecular weights. Molecular weights can help provide a desired viscosity to the material, for example, a higher viscosity for some conventional coating and molding technologies or a lower viscosity for certain 3D printing technologies. One skilled in the art will appreciate that a particular organosiloxane or organosilane, reactive organic compound or other component (e.g. tackifier) will often be in the form of an oligomer and therefore may have a variety of weights and molecular structures. in a given sample. Unless otherwise indicated, a "molecular weight", as used throughout, is the "weighted average" MW molecular weight. M W can be calculated using the equation: ∑M2ni/∑Mini, where n is the number of molecules of molecular weight Mz. MW is determined for purposes of the disclosure herein using gel permeation chromatography by comparison with an appropriate standard. The structures provided here represent a weight average structure over the sample of organosiloxane or other oligomeric or polymeric material. The person skilled in the art will be able to distinguish between different materials, such as having substantially different average molecular weights or substantially different structures.

[0086] As described above, the polymerizable compositions of the disclosure may comprise one or more first organosiloxanes or organosilanes in an amount ranging from about 0.05% by weight to about 99.95% by weight based on in the total weight of the polymerizable composition. All weight % values described in this disclosure are based on the dry weight of the total weight of the polymerizable composition, excluding any evaporable solvents under polymerization conditions, unless otherwise clarified by the context. For example, in certain embodiments of the compositions as described herein, the first organosiloxane or organosilane is present in an amount within the range of about 0.05% by weight to about 99% by weight, or about 0.05% by weight to about 95% by weight, or about 0.05% by weight to about 90% by weight, or about 0.05% by weight to about 85% by weight, or about 0.05% by weight to about 80% by weight, or about 0.05% by weight to about 75% by weight, or about 0.05% by weight to about 70% by weight, or about 0.05% by weight to about 65% by weight, or about 0.05% by weight to about 60% by weight or about 0.05% by weight to about 55% by weight or about from 0.05% by weight to about 50% by weight, or about 0.05% by weight to about 45% by weight, or about 0.05% by weight to about 50% by weight, or about 0.05% by weight to about 45% by weight, or about 0.05% by weight to about 40% by weight or about 0.05% by weight to about 35% by weight or about from 0.05% by weight to about 30% by weight, or about 0.5% by weight to about 99.95% by weight, or about 1% by weight to about 99.95% by weight , or about 1% by weight to about 99% by weight, or about 1% by weight to about 95% by weight, or about 1% by weight to about 90% by weight, or about 1% by weight to about 85% by weight, or about 1% by weight to about 80% by weight, or about 1% by weight to about 75% by weight, or about 1% by weight to about 70% by weight, or about 1% by weight to about 65% by weight, or about 1% by weight to about 60% by weight, or about 1% by weight to about 55% by weight, or about 1% by weight to about 50% by weight, or about 1% by weight to about 45% by weight, or about 1% by weight to about 50% by weight, or about 1% by weight weight to about 45% by weight, or about 1% by weight to about 40% by weight, or about 1% by weight to about 35% by weight, or about 1% by weight to about 30% by weight or about 5% by weight to about 99.95% by weight, or about 45% by weight to about 99.95% by weight, or about 50% by weight to about 99.95% by weight, or about 55% by weight to about 99.95% by weight, or about 60% by weight to about 99.95% by weight, or about 65% by weight to about 99.95% by weight, or about 70% by weight to about 99.95% by weight, or about 5% by weight to about 95% by weight, or about 10% by weight to about 89.95% by weight , or about 15% by weight to about 89.95% by weight, or about 20% by weight to about 89.95% by weight, or about 25% by weight to about 89.95% by weight weight or about 30% by weight to about 89.95% by weight, or about 35% by weight to about 89.95% by weight, or about 40% by weight to about 89.95% by weight weight, or about 45% by weight to about 89.95% by weight, or about 50% by weight to about 89.95% by weight, or about 55% by weight to about 89.95% by weight or about 60% by weight to about 89.95% by weight, or about 65% by weight to about 89.95% by weight, or about 70% by weight to about 89.95% by weight, or about 10% by weight to about 90% by weight, or about 15% by weight to about 85% by weight, or about 20% by weight to about 80% by weight, or about from 25% by weight to about 75% by weight or from about 30% by weight to about 70% by weight based on the total weight of the polymerizable composition. But in other embodiments, there is substantially no first organosiloxane or organosilane (e.g., less than 1% by weight or even less than 0.5% by weight).

[0087] A first organosiloxane or organosilane comprises a plurality of silicon hydride functional groups. In certain embodiments of the compositions as described herein, one or more (e.g., each) first organosiloxane or organosilane comprises at least about two (e.g., about two) silicon hydride functional groups (i.e., , per molecule, on average over the sample), for example, 1.7 to 2.3 silicon hydride functional groups per molecule. For example, in certain embodiments of the compositions as described herein, one or more (e.g., each) first organosiloxane comprises hydride-terminated tetramethyldisiloxane or poly(dimethylsiloxane). In certain embodiments of the compositions as described herein, one or more (e.g., each) first organosiloxane or organosilane comprises about three or more silicon hydride functional groups. For example, in certain embodiments of the compositions as described herein, a first organosiloxane comprises trimethylsiloxane-terminated poly(methylhydrosiloxane) copolymer or trimethylsiloxane-terminated poly(methylhydrosiloxane)-poly(dimethylsiloxane) copolymer. with trimethylsiloxane. In certain embodiments of the compositions as described herein, a first organosiloxane or organosilane comprises a number of silicon hydride functional groups in the range of about 2 to about 1,000, or about 4 to about 1,000, or about 5 to about 1,000, or about 10 to about 1,000, or about 50 to about 1,000, or about 100 to about 1,000, or about 5 to about 500, or about 10 to about from 500, or about 50 to about 500, or about 100 to about 500, or about 5 to about 100, or about 10 to about 100, or about 50 to about 100, or about from 3 to about 100, or about 3 to about 50, or about 3 to about 20 (i.e., per molecule, averaged over the sample).

[0088] In certain embodiments of the compositions as described herein, one or more of the first organosiloxanes or organosilanes is an organosiloxane that includes about two or more siloxane repeat units. In certain embodiments, the number of siloxane repeating units comprising a silicon hydride functional group is in the range of about 0.01% to about 100%, or about 0.1% to about 100%, or about 0.5% to about 20% of the total number of siloxane repeating units of the organosiloxane. For example, in certain embodiments of the compositions as described herein, the amount of siloxane repeat units comprising a silicon hydride functional group is in the range of about 0.5% to about 10%, or about 0. 5% to about 5%, or about 2% to about 20%, or about 2% to about 10%, or about 2% to about 5%, or about 5% to about 20 %, or about 5% to about 10%, or about 10% to about 20% of the total number of siloxane repeat units of the organosiloxane (i.e., per molecule, averaged over the sample) . In certain embodiments, the number of siloxane repeat units comprising a silicon hydride functional group is in the range of about 20% to about 60% of the total number of siloxane repeat units of the organosiloxane. For example, in certain embodiments of the compositions as described herein, the amount of siloxane repeating units comprising a silicon hydride functional group is in the range of about 20% to about 40%, or about 30% to about from 60%, or about 30% to about 50%, or about 0.1% to 100%, or about 0.1% to about 30%, or about 60% to about 80%, or about 70% to 100% of the total number of siloxane repeating units of the organosiloxane (i.e., per molecule, averaged over the sample).

[0089] In certain embodiments of the compositions as described herein, one or more of (e.g., each) of the first organosiloxane or organosilanes is an organosiloxane in which each non-terminal siloxane repeat comprises a functional group silicon hydride. For example, in certain embodiments of the compositions as described herein, a first organosiloxane comprises poly(methylhydrosiloxane) terminated with trimethylsiloxane. In certain embodiments of the compositions as described herein, each silicon atom of a disiloxane comprises a silicon hydride functional group. For example, in certain embodiments of the compositions as described herein, the organosiloxane comprises tetramethyldisiloxane.

[0090] The person skilled in the art will appreciate that a wide variety of first organosiloxanes or organosilanes can be used in the compositions and methods described in this document. In certain embodiments of the compositions as described herein, at least one of (e.g., each) of the first organosiloxane or organosilanes is a compound of Formula IA: wherein: each of R1, R2, and R3 is independently hydrogen, C1-C60 (e.g., C1-C6 or C1-C3) hydrocarbon; each of R4, R5, and R6 is independently C1C60 hydrocarbon (e.g., C1-C6 or C1-C3); each of R7, R9, R10, and R12 independently hydrogen or hydrocarbon C1-C60 (e.g., C1-C6 or C1-C3); R8 is hydrogen, O, or hydrocarbon C1-C60 (e.g., C1-C6 or C1-C3); R11 is a covalent bond to R8, if R8 is O and is otherwise hydrogen or C1-C60 hydrocarbon (e.g. C1-C6 or C1-C3); and each of X, Y and Z is independently from 0 to 20,000, provided that at least one of

[0091] For example, in certain embodiments of the compositions as described herein, one or more of the first organosiloxanes or organosilanes is a compound of Formula I-A in which R8 and R11 are hydrogen, and each of R7, R9, R10, and R12 is independently C1-C60 hydrocarbon (e.g., C1-C6 or C1-C3). In certain embodiments, each C1-C60 hydrocarbon is independently C1-C6 linear or branched alkyl. In certain embodiments, each of R1, R2, and R3 is independently C1-C60 hydrocarbon (e.g., C1-C6 or C1-C3). In certain embodiments, each of X, Y and Z are 0 (i.e., the first organosiloxane is a disiloxane).

[0092] In certain embodiments of the compositions as described herein, one or more of the first organosiloxanes or organosilanes is a compound of Formula I-A in which R1 is C1-C60 (e.g., C1-C6 or C1-C3) hydrocarbon, independently C1-C60 hydrocarbons (e.g. C1-C6 or C1C3). In certain embodiments, each C1-C60 hydrocarbon is independently C1-C6 linear or branched alkyl.

[0093] In certain embodiments of the compositions, as described herein, one or more of the first organosiloxanes or organosilanes is a compound of Formula I-A in which one or more of one or more of R1, R2 and R3 is hydrogen. In certain embodiments, R8 and R11 are not hydrogen. For example, in certain embodiments, R8 is O and R11 is a covalent bond of R8.

[0094] In certain embodiments of the compositions, as described herein, one or more of the first organosiloxanes or organosilanes is a compound of Formula I-A in which each of R1 and R3 is, independently, C1-C60 hydrocarbon, R2 hydrogen , each of X and Z is independently 0-1000 (e.g. 0-500) and Y is 1-2000 (e.g. 1-500). In certain embodiments, R8 and R11 are hydrogens, and each of R7, R9, R10, and R12 is independently C1-C60 hydrocarbon. But in other embodiments, neither R8 nor R11 is hydrogen. In certain embodiments, the ratio of Y to the total of X and Z is within the range of 1:199 to 1:4. In certain embodiments of the compositions as described herein, the ratio of Y to the total of X and Z is within the range of 1:150 to 1:4 or 1:100 to 1:4 or 1:50 to 1:4 or 1:199 to 1:10, or 1:199 to 1:25, or 1:199 to 1:50, or 1:199 to 1:100 or 1:199 to 1:50 or 1:150 to 1:10 or 1:100 to 1:25. In other embodiments, the ratio of Y to the total of X and Z is within the range of 1:4 to 3:2. In certain embodiments of the compositions as described herein, the ratio of Y to the total of X and Z is within the range of 1:3 to 3:2 or 1:2 to 3:2 or 1:1 to 3:2 or 1:4 to 1:1 or 1:4 to 1:2 or 1:4 to 1:3 or 1:3 to 1:1. In certain embodiments, each C1-C60 hydrocarbon is independently C1-C6 linear or branched alkyl.

[0095] In certain embodiments of the compositions, as described herein, one or more of (e.g., each) of the first organosiloxanes or organosilanes is a compound of Formula IB: wherein: each of R13, R14, R15, and R16 is independently hydrogen, hydrocarbon C1-C60 (e.g., C1-C6 or C1-C3), or RL; and RL is , wherein each of R17 and R18 is independently C1-C4 hydrocarbon, provided that the compound has at least two reactive silicon hydride groups.

[0096] Therefore, in various embodiments described herein, the one or more first organosiloxanes or organosilanes may comprise a hydride-terminated polysiloxane, or a polysiloxane with silicon hydrides along its polysiloxane backbone. , or a silane or disiloxane containing two silicon hydrides.

[0097] In certain embodiments of the compositions, as described herein, the one or more first organosiloxanes or organosilanes include one or more hydride-terminated PDMS; methylhydrosiloxanedimethylsiloxane copolymer; polymethylhydrosililoxanes; methyl hydrogen silicone fluid (side chain type); 2,4,6,8-tetramethylcyclotetrasiloxane; and methylhydrosiloxane-phenylmethylsiloxane copolymer.

[0098] The person skilled in the art will appreciate that the various organosiloxanes and organosilanes described herein can be supplied in a variety of molecular weights. Unless otherwise specified herein, all molecular weights are given as weight average molecular weights. Molecular weights can help provide a desired viscosity to the material, for example, a higher viscosity for some conventional coating and molding technologies or a lower viscosity for certain 3D printing technologies.

[0099] In certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) of the first organosiloxanes or organosilanes is within the range of about 88 Da to about 1 MDa, for example, about 88 Da to about 10 kDa, or about 130 Da to about 10 kDa. In certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) the first organosiloxanes or organosilanes is in the range of about 250 Da to about 10 kDa, or about from 500 Da to about 500 kDa, or about 500 Da to about 10 kDa, or about 1 kDa to about 100 kDa, or about 1 kDa to about 10 kDa, or about 2 kDa to about 10 kDa, or about 2 kDa to about 10 kDa, or about 3 kDa to about 10 kDa, or about 4 kDa to about 10 kDa, or about 5 kDa to about 10 kDa, or about 6 kDa to about 10 kDa, or about 7 kDa to about 10 kDa, or about 130 Da to about 9 kDa, or about 130 Da to about 8 kDa, or about 130 Da to about 7 kDa, or about 130 Da to about 6 kDa, or about 130 Da to about 5 kDa, or about 130 Da to about 4 kDa, or about 130 Da to about 3 kDa, or about 130 Da to about of 2 kDa, or about 130 Da to about 1 kDa, or about 130 Da to about 750 Da, or about 400 Da to about 500 Da, or about 0.9 kDa to about 1.2 kDa, or about 1 kDa to about 1.1 kDa, or about 1.4 kDa to about 1.8 kDa, or about 1.8 kDa to about 2.1 kDa, or about 1. 9 kDa to about 2 kDa, or about 2.1 kDa to about 2.4 kDa, or about 2.1 kDa to about 2.4 kDa, or about 4 kDa to about 5 kDa, or about 5.5 kDa to about 6.5 kDa. In certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) of the first organosiloxanes or organosilanes is within the range of about 10 kDa to about 65 kDa. In certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) of the first organosiloxanes or organosilanes is within the range of about 10 kDa to about 55 kDa or about from 10 kDa to about 45 kDa, or about 10 kDa to about 40 kDa, or about 10 kDa to about 35 kDa, or about 10 kDa to about 30 kDa, or about 10 kDa to about 25 kDa, or about 20 kDa to about 65 kDa, or about 30 kDa to about 65 kDa, or about 35 kDa to about 65 kDa, or about 40 kDa to about 65 kDa, or about 45 kDa to about 65 kDa or about 50 kDa to about 65 kDa or about 15 kDa to about 20 kDa or , or about 20 kDa to about 25 kDa, or about 25 kDa to about 30 kDa , or about 45 kDa to about 60 kDa, or about 50 kDa to about 50 kDa, or about 60 kDa to about 65 kDa. In certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) the first organosiloxanes or organosilanes is within the range of about 25 kDa to about 1 MDa. For example, in certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) the first organosiloxanes or organosilanes is within the range of about 50 kDa to about 1 MDa, or about 75 kDa to about 1 MDa, or about 100 kDa to about 1 MDa, or about 150 kDa to about 1 MDa, or about 200 kDa to about 1 MDa, or about 300 kDa to about 1 MDa, or about 400 kDa to about 1 MDa, or about 500 kDa to about 1 MDa, or about 600 kDa to about 1 MDa, or about 700 kDa to about 1 MDa, or about 25 kDa to about 900 kDa, or about 25 kDa to about 800 kDa, or about 25 kDa to about 700 kDa, or about 25 kDa to about 600 kDa, or about 25 kDa to about of 500 kDa, or about 25 kDa to about 400 kDa, or about 25 kDa to about 300 kDa, or about 25 kDa to about 250 kDa, or about 25 kDa to about 200 kDa, or about from 25 kDa to about 150 kDa, or about 25 kDa to about 100 kDa, or about 50 kDa to about 900 kDa, or about 100 kDa to about 800 kDa, or about 200 kDa to about 700 kDa, or about 300 kDa to about 600 kDa.

[0100] The person skilled in the art will appreciate that the values of X, Y and Z can be selected in conjunction with the identities of the siloxane components to provide such molecular weights.

[0101] For example, in certain embodiments of the compositions, as described herein, in one or more of (e.g., each) organosiloxanes of formula IA, X is in the range of 0 to 10000, 0 to 2000, 0 to 1000, 0 to 500, 0 to 100, 0 to 50, 5 to 10000, 5 to 2000, 5 to 1000, 5 to 500, 5 to 100, 5 to 50, 10 to 10000, 10 to 2000, 10 to 1000, 10 to 500, 10 to 100, 50 to 10000, 50 to 2000, 50 to 1000 or 50 to 500.

[0102] Likewise, in certain embodiments of the compositions, as described herein, in one or more of (for example, each) of the organosiloxanes of formula IA, Y is in the range of 0 to 10000, 0 to 2000, 0 to 1000, 0 to 500, 0 to 100, 0 to 50, 5 to 10000, 5 to 2000, 5 to 1000, 5 to 500, 5 to 100, 5 to 50, 10 to 10000, 10 to 2000, 10 to 1000, 10 to 500, 10 to 100, 50 to 10000, 50 to 2000, 50 to 1000 or 50 to 500.

[0103] For example, in certain embodiments of the compositions, as described herein, in one or more of (e.g., each) of the organosiloxanes of formula IA, Z is in the range of 0 to 10000, 0 to 2000, 0 to 1000, 0 to 500, 0 to 100, 0 to 50, 5 to 10000, 5 to 2000, 5 to 1000, 5 to 500, 5 to 100, 5 to 50, 10 to 10000, 10 to 2000, 10 to 1000 , 10 to 500, 10 to 100 , 50 to 10000, 50 to 2000, 50 to 1000 or 50 to 500.

[0104] As described above, the polymerizable compositions of the disclosure may comprise one or more second organosiloxanes or organosilanes in an amount within the range of about 0.05% by weight to about 99.95% by weight with based on the total weight of the polymerizable composition. For example, in certain embodiments of the compositions as described herein, the second organosiloxane or organosilane is present in an amount ranging from about 0.05% by weight to about 99.5% by weight, or about from 0.05% by weight to about 99%, or about 0.05% by weight to about 95% by weight, or about 0.05% by weight to about 90% by weight, or about 0.05% by weight to about 85% by weight, or about 0.05% by weight to about 80% by weight, or about 0.05% by weight to about 75% by weight, or about 0.05% by weight to about 70% by weight, or about 0.05% by weight to about 65% by weight, or about 0.05% by weight to about 60% by weight, or about 0.05% by weight to about 55% by weight, or about 0.05% by weight to about 50% by weight, or about 0.05% by weight to about 45% by weight, or about from 0.05% by weight to about 40% by weight, or about 0.05% by weight to about 35% by weight, or about 0.05% by weight to about 30% by weight, or about 1% by weight to about 99.95% by weight, or about 1% by weight to about 99% by weight, or about 1% by weight to about 95% by weight, or about 1 % by weight to about 90% by weight, or about 1% by weight to about 85% by weight, or about 1% by weight to about 80% by weight, or about 1% by weight to about 75% by weight, or about 1% by weight to about 70% by weight, or about 1% by weight to about 65% by weight, or about 1% by weight to about 60% by weight, or about 1% by weight to 55% by weight, or about 1% by weight to about 50% by weight, or about 1% by weight to about 45% by weight, or about 1% by weight to about from 40% by weight, or about 1% by weight to about 35% by weight, or about 1% by weight to about 30% by weight, or about 5% by weight to about 99.95% by weight or about 5% by weight to about 89.95% by weight, or about 10% by weight to about 89.95% by weight, or about 15% by weight to about 89.95% by weight, or about 20% by weight to about 89.95% by weight, or about 25% by weight to about 89.95% by weight, or about 30% by weight to about 89.95 % by weight, or about 35% by weight to about 89.95% by weight, or about 40% by weight to about 89.95% by weight, or about 45% by weight to about 89, 95% by weight or about 50% by weight to about 89.95% by weight, or about 55% by weight to about 89.95% by weight, or about 60% by weight to about 89, 95% by weight, or about 65% by weight to about 89.95% by weight, or about 70% by weight to about 89.95% by weight, or about 10% by weight to about 99 .95% by weight, or about 15% by weight to about 99.95% by weight, or about 20% by weight to about 99.95% by weight, or about 25% by weight to about 99.95% by weight or about 30% by weight to about 99.95% by weight or about 35% by weight to about 99.95% by weight or about 40% by weight to about 99 .95% by weight, or about 45% by weight to about 99.95% by weight, or about 50% by weight to about 99.95% by weight or about 55% by weight to about 99 95% by weight, or about 60% by weight to about 99.95% by weight, or about 65% by weight to about 99.95% by weight, or about 70% by weight to about 99.95% by weight, or about 5% by weight to about 95% by weight or about 15% by weight to about 85% by weight, or about 20% by weight to about 80% by weight , or about 25% by weight to about 75% by weight, or about 30% by weight to about 70% by weight, based on the total weight of the polymerizable composition. But in other embodiments, there is substantially no second organosiloxane or organosilane (e.g., less than 1% by weight or even less than 0.5% by weight).

[0105] A second organosiloxane or organosilane comprises a plurality of reactive heterocycloalkyl functional groups. In certain embodiments of the compositions as described herein, each reactive heterocylcoalkyl functional group is a cyclic ether. For example, in certain embodiments of the compositions as described herein, each reactive functional group is an epoxide functional group or an oxetane functional group. In certain embodiments of the compositions as described herein, a second organosiloxane or organosilane comprises about two (e.g., 1.7 to 2.3) reactive heterocycloalkyl functional groups (i.e., per molecule, on average, on the sample). For example, in certain embodiments of the compositions as described herein, one or more (e.g., each) second organosiloxane comprises 1,3-bis(3-(2,3-epoxypropoxy)propyl)tetramethyldisiloxane or 3-(2 .3 poly(dimethylsiloxane) terminated in -epoxypropoxy) propyl. In certain embodiments of the compositions as described herein, a second organosiloxane or organosilane comprises about three or more heterocycloalkyl functional groups. For example, in certain embodiments of the compositions as described herein, one or more (e.g., each) second organosiloxane comprises poly((3-(2,3-epoxypropoxy)propyl)methylsiloxane)-pol(dimethylsiloxane) copolymer finished with trimethylsiloxane. In certain embodiments of the compositions as described herein, a second organosiloxane or organosilane comprises a number of reactive heterocycloalkyl functional groups within the range of about 5 to about 500, or about 10 to about 500, about 50 to about 500, or about 100 to about 500, or about 5 to about 100, or about 10 to about 100, or 20 to about 100, or about 3 to about 50, or about 5 to about 50, or about 10 to about 50, or about 3 to about 20, or about 5 to about 20, or about 100 to about 500, or about 2 to about 1000 (i.e. per molecule, averaged over the sample).

[0106] In certain embodiments of the compositions as described herein, one or more of the second organosiloxane or organosilanes is an organosiloxane that includes about two or more siloxane repeat units. In certain embodiments, the number of siloxane repeat units comprising a reactive heterocycloalkyl functional group is within the range of about 0.5% to about 20% of the total number of siloxane repeat units of the organosiloxane. For example, in certain embodiments of the compositions as described herein, the amount of siloxane repeat units comprising a reactive heterocycloalkyl functional group is within the range of about 0.5% to about 10%, or about 0.5%. % to about 5%, or about 0.5% to about 3%, or about 2% to about 20%, or about 2% to about 10%, or about 2% to about 5%, or about 5% to about 20%, or about 0.5% to about 15%, or about 5% to about 10%, or about 10% to about 20% of the number total siloxane repeat units of the organosiloxane (i.e., per molecule, averaged over the sample). For example, in certain embodiments of the compositions as described herein, the amount of siloxane repeat units comprising a reactive heterocycloalkyl functional group is within the range of about 0.5% to about 10%, or about 0.5%. % to about 5%, or about 0.5% to about 3%, or about 2% to about 20%, or about 2% to about 10%, or about 2% to about 5%, or about 5% to about 20%, or about 0.5% to about 15%, or about 5% to about 10%, or about 10% to about 20% of the number total siloxane repeat units of the organosiloxane (i.e., per molecule, averaged over the sample).

[0107] In certain embodiments of the compositions, as described herein, one or more of the second organosiloxane or organosilanes is a disiloxane in which each silicon atom has a heterocycloalkyl functional group. For example, in certain embodiments of the compositions as described herein, the second organosiloxane comprises 1,3-bis (3-(2,3-epoxypropoxy) propyl) tetramethyldisiloxane.

[0108] The person skilled in the art will appreciate that a wide variety of second organosiloxanes or organosilanes can be used in the compositions and methods described in this document. In certain embodiments of the compositions as described herein, at least one of the second organosiloxanes or organosilanes is a compound of Formula II-A: wherein: each of R21, R22, R23, R27, and R30 is independently C1-C60 hydrocarbon (e.g., C1-C6 or C1-C3), RA, or RB; RA is in which each of Q 1 and T 1 is, independently, O, or S; RC is C1-C20 hydrocarbonylene; each of RD and RE is independently C1-C6 hydrocarbylene or a covalent bond; r is 0 or 1; and RF is C1-C6 hydrocarbonylene; RB is in which each of Q 2 and T 2 is, independently, O, or S; RL is C1-C20 hydrocarbonylene; each of RH and RJ is independently C1-C5 hydrocarbonylene; r is 0 or 1; RK is C1-C6 hydrocarbonylene and r is 1; and RK is C1-C6 hydrocarbonylene; or a covalent bond when r is 0; each of R24, R25, and R26 is independently C1-C60 (e.g., C1-C6 or C1-C3) hydrocarbon; each of R29 and R32 is independently hydrogen or C1-C60 (e.g., C1-C6 or C1-C3) hydrocarbon; R28 is O, or C1-C60 hydrocarbon; R31 is a covalent bond to R28 if R28 is O or otherwise is C1-C60 (e.g. C1-C6 or C1-C3) hydrocarbon; each of A, B, and C is independently 0 to 20,000, provided that at least one of A, B, and C is nonzero and that the molecule has at least two reactive heterocycloalkyl groups.

[0109] For example, in certain embodiments of the compositions as described herein, one or more of the second organosiloxanes is a compound of Formula II-A in which each of R21, R23, R27, and R30 is independently C1-C60 hydrocarbon (e.g. C1-C6 or C1-C3); R22 is RA or RB, each of A and C is independently 0-1000, and B is 12000. In certain embodiments, the ratio of B to the sum of A and C is within the range of 1:99 to 1: 9. In certain embodiments, the ratio of B to the sum of A and C is within the range of 1:199 to 1:9. For example in certain embodiments of the compositions as described herein, the ratio of B to the total of A and C is within the range of 1:150 to 1:9 or 1:100 to 1:9 or 1:50 to 1: 9 or 1:199 to 1:15, or 1:199 to 1:25, or 1:199 to 1:50, or 1:199 to 1:100 or 1:199 to 1:50 or 1:150 to 1 :10 or 1:100 to 1:25.

[0110] In certain embodiments of compounds of general formula II-A, R28 is O and R31 is a covalent bond to R28.

[0111] In certain embodiments of the compositions, as described herein, one or more of the second organosiloxanes or organosilanes is a compound of Formula II-B: wherein: each of R33, R34, R35, and R36 is independently hydrocarbon C1-C60 (e.g., C1-C6 or C1-C3), RA, RB, or RM; RM is wherein each of R37 and R38 is independently C1-C60 hydrocarbon (e.g., C1-C6 or C1-C3); and R39 is from RA or RB; RA is in which each of Q 1 and T 1 is, independently, O, or S; RC is C1-C20 hydrocarbonylene; each of RD and RE is independently C1-C6 hydrocarbylene or a covalent bond; r is 0 or 1; and RF is C1-C6 hydrocarbonylene; RB is in which each of Q 2 and T 2 is, independently, O, or S; RL is C1-C20 hydrocarbonylene; each of RH and RJ is independently C1-C5 hydrocarbonylene; r is 0 or 1; RK is C1-C6 hydrocarbonylene and r is 1; and RK is C1-C6 hydrocarbonylene or a covalent bond, if r is 0, provided that the compounds have at least two reactive heterocycloalkyl functional groups.

[0112] Therefore, in various embodiments described herein, the one or more second organosiloxanes or organosilanes may comprise a reactive polysiloxane terminated with heterocycloalkyl (e.g., epoxy) or a polysiloxane with reactive heterocycloalkyls (e.g., epoxides) along its polysiloxane backbone or a silane or disiloxane containing two reactive heterocycloalkyls (e.g., epoxides).

[0113] In certain embodiments of the compositions, as described herein, the one or more second organosiloxanes or organosilanes include one or more epoxide-terminated polysiloxanes; epoxycyclohexylethylmethylsiloxane-dimethylsioxane copolymer; 2,4,6,8-tetramethyl-2,4,6,8-tetrakis (propyl glycidyl ether) cyclotetrasiloxane; and epoxy-modified side-chain type silicone fluids (e.g., epoxypropoxypropyl)methylsiloxane-siloxane copolymer).

[0114] In certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) of the second organosiloxanes or organosilanes is within the range of about 200 Da to about 1 MDa, or about 350 Da to about 5 kDa, or about 1 kDa to about 50 kDa. For example, in certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) of the second organosiloxanes or organosilanes is within the range of about 500 kDa to about 5 kDa. , or about 750 Da to about 5 kDa, or about 1 kDa to about 5 kDa, or about 1.5 kDa to about 5 kDa, or about 2 kDa to about 5 kDa, or about 2.5 kDa to about 5 kDa, or about 3 kDa to about 5 kDa, or about 3.5 kDa to about 5 kDa, or about 350 Da to about 4.5 kDa, or about 350 Da to about 4 kDa, or about 350 Da to about 3.5 kDa, or about 350 Da to about 3 kDa, or about 350 Da to about 2.5 kDa, or about 350 Da to about 2 kDa, or about 350 Da to about 1.5 kDa, or about 350 Da to about 1 kDa, or about 350 kDa to about 500 Da, or about 500 Da to about 600 Da, or about 1 kDa to about 1.4 kDa, or about 4.5 kDa to about 5 kDa. In certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) of the second organosiloxanes or organosilanes is within the range of about 5 kDa to about 25 kDa. For example, in certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) of the second organosiloxanes or organosilanes is within the range of about 7.5 kDa to about 25 kDa, or about 10 kDa to about 25 kDa, or about 12.5 kDa to about 25 kDa, or about 15 kDa to about 25 kDa, or about 17.5 kDa to about 25 kDa, or about 20 kDa to about 25 kDa, or about 5 kDa to about 22.5 kDa, or about 5 kDa to about 20 kDa, or about 5 kDa to about 17.5 kDa, or about 5 kDa to about 15 kDa, or about 5 kDa to about 12.5 kDa, or about 5 kDa to about 10 kDa, or about 5 kDa to about 5.5 kDa, or about 7 kDa to about 9 kDa, or about 10 kDa to about 12 kDa, or about 12 kDa to about 15 kDa, or about 18 kDa to about 20 kDa. In certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) of the second organosiloxanes or organosilanes is within the range of about 25 kDa to about 1 MDa. For example, in certain embodiments of the compositions as described herein, the molecular weight of one or more (e.g., each) of the second organosiloxanes or organosilanes is within the range of about 50 kDa to about 1 MDa, or about 75 kDa to about 1 MDa, or about 100 kDa to about 1 MDa, or about 150 kDa to about 1 MDa, or about 200 kDa to about 1 MDa, or about 300 kDa to about 1 MDa, or about 400 kDa to about 1 MDa, or about 500 kDa to about 1 MDa, or about 600 kDa to about 1 MDa, or about 700 kDa to about 1 MDa, or about 25 kDa to about 900 kDa, or about 25 kDa to about 800 kDa, or about 25 kDa to about 700 kDa, or about 25 kDa to about 600 kDa, or about 25 kDa to about of 500 kDa, or about 25 kDa to about 400 kDa, or about 25 kDa to about 300 kDa, or about 25 kDa to about 250 kDa, or about 25 kDa to about 200 kDa, or about from 25 kDa to about 150 kDa, or about 25 kDa to about 100 kDa, or about 50 kDa to about 900 kDa, or either about 100 kDa to about 800 kDa or about 200 kDa to about 700 kDa, or about 300 kDa to about 600 kDa.

[0115] The person skilled in the art will appreciate that the values of A, B and C can be selected in conjunction with the identities of the siloxane components to provide such molecular weights.

[0116] For example, in certain embodiments as described herein, in one or more of (e.g., each) the organosiloxanes of formula II-A, A are in the range of 0 to 10000, 0 to 2000, 0 to 1000, 0 to 500, 0 to 100, 0 to 50, 5 to 10000, 5 to 2000, 5 to 1000, 5 to 500, 5 to 100, 5 to 50, 10 to 10000, 10 to 2000, 10 to 1000, 10 to 500, 10 to 100, 50 to 10000, 50 to 2000, 50 to 1000 or 50 to 500.

[0117] Likewise, in certain embodiments of the compositions as described herein, in one or more of (for example, each) of the organosiloxanes of formula II-A, Z is in the range of 0 to 10000, 0 to 2000 , 0 to 1000, 0 to 500, 0 to 100, 0 to 50, 5 to 10000, 5 to 2000, 5 to 1000, 5 to 500, 5 to 100, 5 to 50, 10 to 10000, 10 to 2000, 10 to 1000, 10 to 500, 10 to 100, 50 to 10000, 50 to 2000, 50 to 1000 or 50 to 500.

[0118] Likewise, in certain embodiments of the compositions, as described herein, in one or more of (for example, each) of the organosiloxanes of formula II-A, C is in the range of 0 to 10000, 0 to 2000, 0 to 1000, 0 to 500, 0 to 100, 0 to 50, 5 to 10000, 5 to 2000, 5 to 1000, 5 to 500, 5 to 100, 5 to 50, 10 to 10000, 10 to 2000, 10 to 1000, 10 to 500, 10 to 100, 50 to 10000, 50 to 2000, 50 to 1000 or 50 to 500.

[0119] As described above, the polymerizable compositions of the disclosure may comprise one or more third organosiloxanes or organosilanes in an amount ranging from about 0.05% by weight to about 99.95% by weight based on in the total weight of the polymerizable composition. For example, in certain embodiments of the compositions as described herein, the third organosiloxane or organosilane is present in an amount ranging from about 0.05% by weight to about 99.5% by weight, or about from 0.05% by weight to about 99%, or about 0.05% by weight to about 95% by weight, or about 0.05% by weight to about 90% by weight, or about 0.05% by weight to about 85% by weight, or about 0.05% by weight to about 80% by weight, or about 0.05% by weight to about 75% by weight, or about 0.05% by weight to about 70% by weight, or about 0.05% by weight to about 65% by weight, or about 0.05% by weight to about 60% by weight, or about 0.05% by weight to about 55% by weight, or about 0.05% by weight to about 50% by weight, or about 0.05% by weight to about 45% by weight, or about from 0.05% by weight to about 40% by weight, or about 0.05% by weight to about 35% by weight, or about 0.05% by weight to about 30% by weight, or about 1% by weight to about 99.95% by weight, or about 1% by weight to about 99% by weight, or about 1% by weight to about 95% by weight, or about 1 % by weight to about 90% by weight, or about 1% by weight to about 85% by weight, or about 1% by weight to about 80% by weight, or about 1% by weight to about 75% by weight, or about 1% by weight to about 70% by weight, or about 1% by weight to about 65% by weight, or about 1% by weight to about 60% by weight, or about 1% by weight to 55% by weight, or about 1% by weight to about 50% by weight, or about 1% by weight to about 45% by weight, or about 1% by weight to about from 40% by weight, or about 1% by weight to about 35% by weight, or about 1% by weight to about 30% by weight, or about 5% by weight to about 99.95% by weight or about 5% by weight to about 89.95% by weight, or about 10% by weight to about 89.95% by weight, or about 15% by weight to about 89.95% by weight, or about 20% by weight to about 89.95% by weight, or about 25% by weight to about 89.95% by weight, or about 30% by weight to about 89.95 % by weight, or about 35% by weight to about 89.95% by weight, or about 40% by weight to about 89.95% by weight, or about 45% by weight to about 89, 95% by weight or about 50% by weight to about 89.95% by weight, or about 55% by weight to about 89.95% by weight, or about 60% by weight to about 89, 95% by weight, or about 65% by weight to about 89.95% by weight, or about 70% by weight to about 89.95% by weight, or about 10% by weight to about 99 .95% by weight, or about 15% by weight to about 99.95% by weight, or about 20% by weight to about 99.95% by weight, or about 25% by weight to about 99.95% by weight or about 30% by weight to about 99.95% by weight or about 35% by weight to about 99.95% by weight or about 40% by weight to about 99 .95% by weight, or about 45% by weight to about 99.95% by weight, or about 50% by weight to about 99.95% by weight or about 55% by weight to about 99 95% by weight, or about 60% by weight to about 99.95% by weight, or about 65% by weight to about 99.95% by weight, or about 70% by weight to about 99.95% by weight, or about 5% by weight to about 95% by weight or about 15% by weight to about 85% by weight, or about 20% by weight to about 80% by weight , or about 25% by weight to about 75% by weight, or about 30% by weight to about 70% by weight, based on the total weight of the polymerizable composition. But in other embodiments, there is substantially no third organosiloxane or organosilane (e.g., less than 1% by weight or even less than 0.5% by weight).

[0120] A third organosiloxane or organosilane comprises at least about one silicon hydride functional group and at least about one reactive heterocycloalkyl functional group. In certain embodiments of the compositions as described herein, each reactive heterocylcoalkyl functional group is a cyclic ether. For example, in certain embodiments of the compositions as described herein, each reactive functional group is an epoxide functional group or an oxetane functional group. In certain embodiments of the compositions as described herein, one or more (e.g., each) third organosiloxane or organosilane includes about one (e.g., 0.7 to 1.3) silicon hydride and about one (e.g., 0.7 to 1.3) reactive heterocycloalkyl functional group (e.g., per molecule, averaged over the sample). For example, in certain embodiments of the compositions as described herein, one or more (e.g., each) third organosiloxane or organosilane is a poly(dimethylsiloxane) having a first end and a second end terminated at the first end by a group silicon hydride functional and terminated at the second end by a reactive heterocycloalkyl functional group (e.g., a 3-(2,3-epoxypropoxy)propyl group). In other embodiments the third organosiloxane or organosilane includes about two or more silicon hydrides and/or about two or more reactive heterocycloalkyl functional groups (i.e., per molecule, on average, over the sample). For example, in certain embodiments of the compositions as described herein, a third organosiloxane or organosilane is a polysiloxane with about two or more epoxy-functional siloxane subunits and about two or more monoalkylsiloxane subunits (i.e., per molecule, on average, over the sample).

[0121] In certain embodiments of the compositions as described herein, one or more of the third organosiloxane or organosilanes is an organosiloxane that includes about two or more siloxane repeat units. In certain embodiments, the number of siloxane units comprising a heterocycloalkyl functional group or a silicon hydride functional group is within the range of about 0.01% to about 100% (e.g., about 0.5% to about 50%) of the total number of siloxane units of the total number of siloxane repeating units of the organosiloxane. For example, in certain embodiments of the compositions as described herein, the amount of siloxane repeat units comprising a reactive heterocycloalkyl functional group or a silicon hydride functional group is within the range of about 0.5% to about 20%. % or about 0.5% to about 10%, or about 0.5% to about 5%, or about 2% to about 50%, or about 2% to about 20%, or about 2% to about 10%, or about 5% to about 50%, or about 5% to about 20%, or about 5% to about 10%, or about 10% to about from 50% or about 10% to about 20% of the total number of siloxane repeating units of the organosiloxane (i.e., per molecule averaged over the sample).

[0122] The person skilled in the art will appreciate that a wide variety of third-party organosiloxanes or organosilanes can be used in the compositions and methods described herein. In certain embodiments of the compositions as described herein, at least one of the third organosiloxanes or organosilanes is a compound of Formula III-A: wherein: each of R41, R42, R43, R47, and R50 is independently hydrocarbons C1-C60 (e.g., hydrogen C1-C6 or C1-C3), RA or RB; each of Q 1 and T 1 is, independently, O, or S; RA is RC is C1-C20 hydrocarbonylene; each of RD and RE is independently C1-C6 hydrocarbylene or a covalent bond; r is 0 or 1; and RF is C1-C6 hydrocarbonylene; RB is in which each of Q 2 and T 2 is, independently, O, or S; RL is C1-C20 hydrocarbonylene; each of RH and RJ is independently C1-C5 hydrocarbonylene; r is 0 or 1; RK is C1-C6 hydrocarbonylene and r is 1; and RK is C1-C6 hydrocarbonylene; or a covalent bond when r is 0; each of R44, R45 and R46 is independently C1-C60 hydrocarbon (e.g., C1-C6 or C1-C3); each of R49 and R52 is independently C1-C60 hydrocarbon (e.g., C1-C6 or C1-C3); R48 is O, or C1-C60 hydrocarbon; R51 is a covalent bond to R48 if R48 is O or otherwise is C1-C60 hydrocarbon (e.g. C1-C6 or C1-C3); each of D, E and F is independently from 0 to 20,000, provided that at least one of D, E and F is non-zero and that the molecule has at least one reactive silicon hydride and at least one reactive heterocycloalkyl group.

[0123] For example, in certain embodiments of the compositions as described herein, one or more of the third organosiloxane or organosilanes is a compound of Formula III-A in which each of R43, R47 and R50 is independently C1- C60 (e.g. C1-C6 or C1-C3) hydrocarbon; R41 is H; R42 is from RA or RB; D is 1 to 2000, E is 1 to 2000; and F is 0 to 2000. In certain embodiments, the ratio of E to the sum of D and F is within the range of 1:199 to 1:9, and the ratio of D to the sum of E and F is within the range of range from 1:199 to 1:9. For example, in certain embodiments of the compositions as described herein, each of the ratios of E to the sum of D and F and the ratio of D to the sum of E and F are independently within the range of 1:199 to 1: 9 or 1:150 to 1:9 or 1:100 to 1:9 or 1:50 to 1:9 or 1:199 to 1:15 or 1:199 to 1:25 or 1:199 to 1:50, or 1:199 to 1:100, or 1:199 to 1:50, or 1:150 to 1:10, or 1:100 to 1:25.

[0124] In certain embodiments of compounds of formula III-A, R48 is O and R51 is a covalent bond to R48.

[0125] In certain embodiments of the compositions, as described herein, one or more of the third organosiloxanes or organosilanes is a compound of Formula III-B: wherein: each of R53, R54, R55, and R56 is independently C1-C60 hydrocarbon, H, RA, RB, or RM; RM is in which independently C1-C60 hydrocarbon; R59 is from RA or RB; RA is in which each of Q 1 and T 1 is, independently, O, or S; RC is C1-C20 hydrocarbonylene; each of RD and RE is independently C1-C6 hydrocarbylene or a covalent bond; r is 0 or 1; and RF is C1-C6 hydrocarbonylene; RB is in which each of Q 2 and T 2 is, independently, O, or S; RL is C1-C20 hydrocarbonylene; each of RH and RJ is independently C1-C5 hydrocarbonylene; r is 0 or 1; RK is C1-C6 hydrocarbonylene and r is 1; and RK is C1-C6 hydrocarbonylene or a covalent bond, if r is 0, provided that the molecule has at least one silicon hydride and at least one reactive heterocycloalkyl group.

[0126] In certain embodiments, the RA and RB groups of compounds II-A, II-B, III-A and III-B are generally described above. The skilled artisan will appreciate that a variety of RA and RB groups can be used in the compounds described herein. Each of the RA and RB groups can be defined independently as described in the other embodiments below. In certain embodiments, each group RA and RB is as defined in one of the additional embodiments below.

[0127] For example, in certain embodiments as described herein, in one or more compounds (e.g., each of compounds) II-A, II-B, III-A and IIIB, each of RD and RE is a bond covalent. In other embodiments of the compositions as described herein, in one or more compounds (e.g., each of compounds) II-A, II-B, III-A and IIIB, each of RD and RE is independently C1-C2 alkylene .

[0128] In certain embodiments, as described herein, in one or more compounds (e.g., each of compounds) II-A, II-B, III-A and IIIB, RF is linear or branched C1-C4 alkylene, e.g. example, methylene.

[0129] In certain embodiments, as described herein, in one or more compounds (e.g., each of the compounds) II-A, II-B, III-A and IIIB, each Q1 and T1 of RA are O.

[0130] In certain embodiments, as described herein, in one or more compounds (e.g., each of the compounds) II-A, II-B, III-A and III-B, r of RA is 0.

[0131] In certain embodiments, as described herein, in one or more compounds (e.g., each of compounds) II-A, II-B, III-A and III-B, RA is:

[0132] In certain embodiments, as described herein, in one or more compounds (e.g., each of the compounds) II-A, II-B, III-A and III-B, RC is linear or branched C1-C6 heteroalkylene . For example, in certain embodiments, as described herein, in one or more compounds (e.g., each of compounds) II-A, II-B, III-A and III-B, RC is:

[0133] In certain embodiments, as described herein, in one or more compounds (for example, each of the compounds) II-A, II-B, III-A and III-B, RH is C1-C2 alkylene.

[0134] In certain embodiments, as described herein, in one or more compounds (e.g., each of compounds) II-A, II-B, III-A and III-B, RJ is a methylene group.

[0135] In certain embodiments, as described herein, in one or more compounds (e.g., each of compounds) II-A, II-B, III-A and III-B, RK is methylene.

[0136] In certain embodiments, as described herein, in one or more compounds (e.g., each of compounds) II-A, II-B, III-A and III-B, each of Q2 and T2 of RB is O.

[0137] In certain embodiments, as described herein, in one or more compounds (e.g., each of the compounds) II-A, II-B, III-A and III-B, r of RB is 0. In certain embodiments , RK is a covalent bond.

[0138] In certain embodiments, as described herein, in one or more compounds (e.g., each of compounds) II-A, II-B, III-A and III-B, RB is:

[0139] In certain embodiments, as described herein, in one or more compounds (e.g., each of the compounds) II-A, II-B, III-A and III-B, RG is linear or branched C1-C6 alkylene .

[0140] In certain embodiments, as described herein, in one or more compounds (e.g., each of compounds) II-A, II-B, III-A and III-B, each C 1 -C 60 hydrocarbon is independently linear or branched C 1 - C 6 alkyl.

[0141] Therefore, in various embodiments described herein, the one or more third organosiloxanes or organosilanes may comprise one or more of a polysiloxane terminated with one or more reactive heterocycloalkyls (e.g., epoxides) and with one or more silicon hydrides along its backbone, a polysiloxane terminated with one or more silicon hydrides and with one or more reactive heterocycloalkyls (e.g., epoxides) along its backbone; a polysiloxane terminated with a silicon hydride and a reactive heterocycloalkyl (e.g., epoxy); or a polysiloxane with one or more silicon hydrides and one or more reactive heterocycloalkyls (e.g., epoxides) along its polysiloxane backbone.

[0142] In certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) of the third organosiloxanes or organosilanes is within the range of about 120 Da to about 1 MDa; or about 1 kDa to about 100 kDa, or about 350 Da to about 5 kDa. In certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) of the third organosiloxanes or organosilanes is within the range of about 500 kDa to about 5 kDa, or about 750 Da to about 5 kDa, or about 1 kDa to about 5 kDa, or about 1.5 kDa to about 5 kDa, or about 2 kDa to about 5 kDa, or about 2, 5 kDa to about 5 kDa, or about 3 kDa to about 5 kDa, or about 3.5 kDa to about 5 kDa, or about 350 Da to about 4.5 kDa, or about 350 Da to about 4 kDa, or about 350 Da to about 3.5 kDa, or about 350 Da to about 3 kDa, or about 350 Da to about 2.5 kDa, or about 350 Da to about from 2 kDa, or about 350 Da to about 1.5 kDa, or about 350 Da to about 1 kDa, or about 350 kDa to about 500 Da, or about 500 Da to about 600 Da, or about 1 kDa to about 1.4 kDa, or about 4.5 kDa to about 5 kDa. In certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) of the third organosiloxanes or organosilanes is within the range of about 5 kDa to about 25 kDa. In certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) the third organosiloxanes or organosilanes is within the range of about 7.5 kDa to about 25 kDa. or about 10 kDa to about 25 kDa, or about 12.5 kDa to about 25 kDa, or about 15 kDa to about 25 kDa, or about 17.5 kDa to about 25 kDa, or about from 20 kDa to about 25 kDa, or about 20 kDa to about 25 kDa, or about 5 kDa to about 25 kDa, or about 5 kDa to about 25 kDa, or about 5 kDa to about 20 kDa, or about 5 kDa to about 17.5 kDa, or about 5 kDa to about 15 kDa or about 5 kDa to about 12.5 kDa or about 5 kDa to about 10 kDa or about 5 kDa to about 10 kDa, or about 5 kDa to about 5.5 kDa, or about 7 kDa to about 9 kDa, or about 10 kDa to about 12 kDa, or about 12 kDa to about 15 kDa, or about 18 kDa to about 20 kDa.

[0143] In certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) of the third organosiloxanes or organosilanes is within the range of about 25 kDa to about 1 MDa. For example, in certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) the third organosiloxanes or organosilanes is within the range of about 50 kDa to about 1 MDa, or about 75 kDa to about 1 MDa, or about 100 kDa to about 1 MDa, or about 150 kDa to about 1 MDa, or about 200 kDa to about 1 MDa, or about 300 kDa to about 1 MDa, or about 400 kDa to about 1 MDa, or about 500 kDa to about 1 MDa, or about 600 kDa to about 1 MDa, or about 700 kDa to about 1 MDa, or about 25 kDa to about 900 kDa, or about 25 kDa to about 800 kDa, or about 25 kDa to about 700 kDa, or about 25 kDa to about 600 kDa, or about 25 kDa to about of 500 kDa, or about 25 kDa to about 400 kDa, or about 25 kDa to about 300 kDa, or about 25 kDa to about 250 kDa, or about 25 kDa to about 200 kDa, or about from 25 kDa to about 150 kDa, or about 25 kDa to about 100 kDa, or about 50 kDa to about 900 kDa, or about 100 kDa to about 800 kDa, or about 200 kDa to about 700 kDa, or about 300 kDa to about 600 kDa.

[0144] The person skilled in the art will appreciate that the values of D, E and F can be selected in conjunction with the identities of the siloxane components to provide such molecular weights.

[0145] For example, in certain embodiments, as described herein, in one or more of (e.g., each) the organosiloxanes of formula II-A, D are in the range of 0 to 10000, 0 to 2000, 0 to 1000, 0 to 500, 0 to 100, 0 to 50, 5 to 10000, 5 to 2000, 5 to 1000, 5 to 500, 5 to 100, 5 to 50, 10 to 10000, 10 to 2000, 10 to 1000, 10 to 500, 10 to 100, 50 to 10000, 50 to 2000, 50 to 1000 or 50 to 500.

[0146] Likewise, in certain embodiments of the compositions, as described herein, in one or more of (for example, each) of the organosiloxanes of formula II-A, E is in the range of 0 to 10000, 0 to 2000, 0 to 1000, 0 to 500, 0 to 100, 0 to 50, 5 to 10000, 5 to 2000, 5 to 1000, 5 to 500, 5 to 100, 5 to 50, 10 to 10000, 10 to 2000, 10 to 1000, 10 to 500, 10 to 100, 50 to 10000, 50 to 2000, 50 to 1000 or 50 to 500.

[0147] Likewise, in certain embodiments, as described herein, in one or more of (e.g., each) of the organosiloxanes of formula II-A, F is in the range of 0 to 10000, 0 to 2000, 0 to 1000, 0 to 500, 0 to 100, 0 to 50, 5 to 10000, 5 to 2000, 5 to 1000, 5 to 500, 5 to 100, 5 to 50, 10 to 10000, 10 to 2000, 10 to 1000, 10 to 500, 10 to 100, 50 to 10000, 50 to 2000, 50 to 1000 or 50 to 500.

[0148] As described above, the polymerizable compositions of the disclosure include one or more reactive organic compounds. The one or more reactive organic compounds are present in an amount within the range of about 0.05% by weight to about 99.95% by weight, based on the total weight of the polymerizable composition. For example, in certain embodiments of the compositions as described herein, one or more reactive organic compounds is present in an amount within the range of about 0.05% by weight to about 99.5% by weight, or about 0. .05% by weight to about 99% by weight, or about 0.05% by weight to about 95% by weight, or about 0.05% by weight to about 90% by weight, or about 0.05% by weight to about 85% by weight, or about 0.05% by weight to about 80% by weight, or about 0.05% by weight to about 75% by weight, or about 0.05% by weight to about 70% by weight, or about 0.05% by weight to about 65% by weight, or about 0.05% by weight to about 60% by weight, or about 0.05% by weight to about 55% by weight, or about 0.05% by weight to about 50% by weight, or about 0.05% by weight to about 45% by weight, or about from 0.05% by weight to about 40% by weight, or about 0.05% by weight to about 35% by weight, or about 0.05% by weight to about 30% by weight, or about 1% by weight to about 99.95% by weight, or about 1% by weight to about 99% by weight, or about 1% by weight to about 95% by weight, or about 1 % by weight to about 90% by weight, or about 1% by weight to about 85% by weight, or about 1% by weight to about 80% by weight, or about 1% by weight to about 75% by weight, or about 1% by weight to about 70% by weight, or about 1% by weight to about 65% by weight, or about 1% by weight to about 60% by weight, or about 1% by weight to 55% by weight, or about 1% by weight to about 50% by weight, or about 1% by weight to about 45% by weight, or about 1% by weight to about from 40% by weight, or about 1% by weight to about 35% by weight, or about 1% by weight to about 30% by weight, or or about 5% by weight to about 99.95 % by weight, or about 10% by weight to about 99.95% by weight, or about 15% by weight to about 99.95% by weight, or about 20% by weight to about 99, 95% by weight, or about 25% by weight to about 99.95% by weight, or about 30% by weight to about 99.95% by weight, or about 35% by weight to about 99, 95% by weight, or about 40% by weight to about 99.95% by weight, or about 45% by weight to about 99.95% by weight or about 50% by weight to about 99, 95% by weight, or about 55% by weight to about 99.95% by weight, or about 60% by weight to about 99.95% by weight, or about 65% by weight to about 99 .95% by weight, or about 70% by weight to about 99.95% by weight, or about 5% by weight to about 95% by weight, or about 10% by weight to about 90% by weight, or about 15% by weight to about 85% by weight, or about 20% by weight to about 80% by weight, or about 25% by weight to about 75% by weight, or about 30% by weight to about 70% by weight, based on the total weight of the polymerizable composition.

[0149] A reactive organic compound comprises about one or more reactive heterocycloalkyl functional groups. In certain embodiments of the compositions as described herein, each reactive heterocylcoalkyl functional group is a cyclic ether. For example, in certain embodiments of the compositions as described herein, each reactive functional group is an epoxide functional group or an oxetane functional group. In certain embodiments of the compositions as described herein, the reactive organic compound comprises at least about two (e.g., about two, e.g., 1.7 to 2.3) reactive heterocycloalkyl functional groups (i.e., per molecule , on average, over the sample). In certain embodiments of the compositions as described herein, a reactive organic compound comprises about one reactive heterocycloalkyl functional group (i.e., per molecule, on average, over the sample). In certain embodiments of the compositions as described herein a reactive organic compound comprises a number of reactive heterocycloalkyl functional groups within the range of about 2 to about 10,000, or about 2 to about 20, or about 3 to about 20 or about 5 to about 20, or about 2 to about 10, or about 3 to about 10, or about 5 to about 10, or about 3 to about 100, or about 5 to about 100, or about 10 to about 500, or about 10 to about 100, or about 2 to about 5, or about 2 to about 500, or about 2 to about 50 ( i.e. per molecule, averaged over the sample). The reactive organic compound can be a small molecule, an oligomer, or a polymer.

[0150] The person skilled in the art will appreciate that a wide variety of reactive organic compounds can be used in the compositions and methods described herein. Therefore, in various embodiments described herein, the reactive organic compounds may comprise a reactive heterocycloalkyl moiety (e.g., epoxy), or a heterocycloalkyl moiety (e.g., epoxies) along their backbone.

[0151] In some embodiments, the one or more reactive organic compounds comprises an aliphatic hydrocarbon, an aromatic hydrocarbon or a polymer. In certain embodiments, the one or more reactive organic compounds is , or , or wherein Re is an aliphatic hydrocarbon (e.g., optionally substituted C1-C24 alkyl, C1-C24 alkenyl, C1-C24 alkynyl), an aromatic hydrocarbon, or a polymer (such as, without limitation, polyethylene, polypropylene, polyethylene glycol, polyacrylate, polymethacrylate , polyolefin, etc.) In some embodiments, when R is an aliphatic hydrocarbon or an aromatic hydrocarbon, one or more carbon atoms in the hydrocarbon may be independently replaced by a heteroatom (e.g., O, NH, S). In various embodiments, R includes a halogenated moiety, such as a halogenated alkyl group (e.g., fluoroalkyl) or a halogenated aryl group (e.g., chloroaryl, fluoroaryl, or bromoaryl).

[0152] In some embodiments, the one or more reactive organic compounds comprises an epoxy derivative of a fatty acid, such as linoleic acid, α-linolenic acid, oleic acid, stearic acid, palmitic acid and combinations thereof. Epoxidized oils such as epoxidized soybean oils may also be suitable for use. In some embodiments, the one or more reactive organic compounds comprises bisphenol A diglycidyl ether or an ethoxylated and/or propoxylated version thereof, 2,2,4,4-tetramethyl-1,3-cyclobutanediol diglycidyl ether and 1,4-cyclo -hexanedimethanol diglycidyl ether, bis[4-(glycidyloxy)phenyl] methane, 1,3-butanedieoxide, 1,4-butanediol diycidylidyl ether, an alkyl or aromatic glycidyl ether, 4-chlorophenyl glycidyl ether, 1,4-cyclo diglycidyl ether -hexanedimethanol, diglycidyl ether dioxide, 1,2,5,6-diepoxycyclooctane, 1,2,7,8-diepoxyoctane, tris(4-hydroxyphenyl) triglycidyl methane ether, tris(2,3-epoxypropyl) isocyanurate, triss ether (2,3- epoxypropyl), resorcinol diglycidyl ether, fluoroalkyl glycidyl ether such as glycidyl 2,2,3,3,4,4,5,5-octafluoropentyl ether, tetraphenylolethane glycidyl ether, resorcinol diglycidyl ether, a poly(alkylene oxide ) glycidyl, such as poly(ethylene glycol) digylcidyl ether or poly(propylene glycol) diglycidyl ether, or an epoxy-functional polymer or resin, or or an epoxy-functionalized ethylene-propylene-diene rubber. The person skilled in the art will appreciate, based on the disclosure described herein, that a wide variety of reactive organic compounds can be used, depending on the particular reactivity and properties desired.

[0153] In certain embodiments of the compositions, as described here, the reactive organic compound is a polymer. In certain embodiments, the reactive organic compound has a molecular weight in the range of about 100 Da to about 1MDa. In some embodiments, the molecular weight of the reactive organic compound is within the range of about 350 Da to about 25 kDa. For example, in certain embodiments of the compositions as described herein, the molecular weight of one or more of (e.g., each) the second organosiloxanes or organosilanes is within the range of about 500 kDa to about 5 kDa. kDa, or about 750 Da to about 5 kDa, or about 1 kDa to about 5 kDa, or about 1.5 kDa to about 5 kDa, or about 2 kDa to about 5 kDa, or about from 2.5 kDa to about 5 kDa, or about 2.5 kDa to about 5 kDa, or about 3 kDa to about 5 kDa, or about 3.5 kDa to about 5 kDa, or about from 350 Da to about 4.5 kDa, or about 350 Da to about 4 kDa, or about 350 Da to about 3.5 kDa, or about 350 Da to about 3 kDa, or about 350 Da to about 2.5 kDa, or about 350 Da to about 2 kDa, or about 350 Da to about 1.5 kDa, or about 350 Da to about 1 kDa, or about 350 kDa to about 500 Da, or about 500 Da to about 500 Da, or about 500 Da to about 600 Da, or about 1 kDa to about 1.4 kDa, or about 4.5 kDa to about 5 kDa, or about 7.5 kDa to about 25 kDa, or about 10 kDa to about 25 kDa, or about 12.5 kDa to about 25 kDa, or about 15 kDa to about 25 kDa, or about 17.5 kDa to about 25 kDa, or about 20 kDa to about 25 kDa, or about 5 kDa to about 22.5 kDa, or about 5 kDa to about 20 kDa, about 5 kDa to about 17.5 kDa, or about 5 kDa to about 15 kDa, or about 5 kDa to about 12.5 kDa, or about 5 kDa to about 10 kDa, or about 5 kDa to about 5.5 kDa or about 7 kDa to about 9 kDa or about 10 kDa to about 12 kDa, or about 12 kDa to about 15 kDa, or about 18 kDa to about 20 kDa, or about 20 kDa to about 100 kDa, or about 50 kDa to about 500 kDa, or about 200 kDa to about 1 MDa.

[0154] The person skilled in the art will appreciate that the first, second and/or third organosiloxanes or organosilanes and the reactive organic compound can be combined in various combinations and amounts. For example, in certain embodiments as described herein, the composition includes one or more first organosiloxanes or organosilanes present in an amount within the range of about 0.05% by weight to about 30% by weight; one or more second organosiloxanes or organosilanes present in an amount within the range of about 70% by weight to about 99.9% by weight; and one or more reactive organic compounds in an amount ranging from about 0.05% by weight to about 30% by weight. In other embodiments, as described herein, the composition includes one or more first organosiloxanes or organosilanes present in an amount in the range of about 1% by weight to about 30% by weight, about 5% by weight to about 30% by weight, or about 10% by weight to about 30% by weight; one or more second organosiloxanes or organosilanes present in an amount in the range of about 70% by weight to about 99% by weight, about 70% by weight to about 95% by weight, or about 70% by weight at about 90% by weight; and one or more reactive organic compounds present in an amount in the range of about 1% by weight to about 30% by weight, about 5% by weight to about 30% by weight, or about 10% by weight to about 30% by weight. In other embodiments, as described herein, the composition includes one or more first organosiloxanes or organosilanes present in an amount within the range of about 30% by weight to about 70% by weight; one or more second organosiloxanes or organosilanes present in an amount within the range of about 15% by weight to about 55% by weight; and one or more reactive organic compounds present in an amount ranging from about 15% by weight to about 55% by weight. In other embodiments, as described herein, the composition includes one or more first organosiloxanes or organosilanes present in an amount within the range of about 40% by weight to about 59.95% by weight; one or more second organosiloxanes or organosilanes present in an amount within the range of about 0.05% by weight to about 30% by weight; and one or more reactive organic compounds present in an amount ranging from about 40% by weight to about 59.9% by weight. In certain embodiments, substantially no third organosiloxane or organosilane is present (e.g., no more than 0.5% by weight or no more than 0.1% by weight).

[0155] In other embodiments, as described herein, the composition includes one or more third organosiloxanes or organosilanes present in an amount ranging from about 30% by weight to about 99.95% by weight; and one or more reactive organic compounds in an amount ranging from about 0.05% by weight to about 60% by weight. For example, in certain embodiments, the one or more third organosiloxanes or organosilanes are present in an amount within the range of about 50% by weight to about 99.95% by weight, or about 70% by weight. weight to about 99.95% by weight. In certain embodiments, substantially no first organosiloxane or organosilane or second organosiloxane or organosilane is present (e.g., no more than 0.5% by weight or no more than 0.1% by weight of each).

[0156] In other embodiments, as described herein, substantial amounts of each of the first organosiloxanes or organosilanes, the second organosiloxane or organosilane and the third organosiloxane or organosilane are present. For example, in certain embodiments, a composition includes one or more first organosiloxanes or organosilanes in an amount within the range of about 5% by weight to about 80% by weight; one or more second organosiloxanes or organosilanes in an amount within the range of about 5% by weight to about 80% by weight; and one or more third organosiloxanes or organosilanes in an amount within the range of about 5% by weight to about 80% by weight.

[0157] In other embodiments, as described herein, the polymerizable composition includes one or more first organosiloxanes or organosilanes in an amount ranging from about 10% by weight to about 95% by weight; and one or more reactive organic compounds in an amount within the range of about 5% by weight to about 90% by weight. In certain embodiments, substantially no second or third organosiloxane or organosilane is present.

[0158] The person skilled in the art will appreciate that the hydrosilylation reaction has a stoichiometry of a silicon hydride to a reactive heterocycloalkyl. Therefore, as described above, in various compositions as described herein, the ratio of silicon hydride functional groups to reactive heterocycloalkyl functional groups in the overall composition (i.e., including all first, second and/or third organosiloxanes or organo -silanes and reactive organic compounds) is in the range of 1:5 to 5:1. For example, in certain embodiments of the compositions as described herein, the ratio of silicon hydride functional groups to heterocycloalkyl functional groups is within the range of 1:5 to 4:1 or 1:5 to 3:1 or 1: 5 to 2:1 or 1:5 to 1:1 or 1:4 to 5:1 or 1:3 to 5:1 or 1:2 to 5:1 or 1:1 to 5:1 or 1:4 to 4:1 or 1:3 to 3:1 or 1:2 to 2:1, 1:1.25 to 1.25:1 or 1:1.2 to 1.2:1 or 1:1.15 to 1.15:1 or 1:1.1 to 1.1:1. In some embodiments, there is an excess of heterocycloalkyl functional groups; heterocycloalkyl functional groups (especially epoxy groups) can react with each other (i.e. in addition to being hydrosilylated). Accordingly, in certain embodiments, the ratio of silicon hydride functional groups to heterocycloalkyl functional groups is in the range of 1:5 to 1:1, or 1:4 to 1:1, or 1:3 to 1:1 , or 1:2 to 1:1, or 1.5:1 to 1:1, or 1.25:1 to 1:1.

[0159] In certain embodiments of the compositions, as described herein, the polymerizable composition is substantially free of ethylenic unsaturations subject to hydrosilylation, including, for example, vinyl functional groups. The present inventors have determined that hydrosilylation of epoxides can form polymers without the need to hydrosilylate ethylenic unsaturations as is conventional. For example, in certain embodiments of the compositions, as described herein, the atoms comprising ethylenic unsaturations capable of hydrosilylation present in the polymerizable composition comprise less than 0.5 at.% (atomic percentage), less than 0.4 at.% (atomic percentage). atomic), less than 0.3 at. % (atomic percentage), less than 0.2 at. % (atomic percentage), less than 0.1 at. % (atomic percentage), less than 0.05 at. % (atomic percentage) or less than 0.01 at. % (atomic percentage) of the polymerizable composition. In certain embodiments of the compositions, as described herein, the proportion of ethylenic unsaturations capable of hydrosilylation to silicon hydride functional groups is less than 0.05, less than 0.01, less than 0.005 or even less than 0.001.

[0160] The present inventors have determined that borane catalysts may be useful for catalyzing the hydrosilylation of reactive heterocycloalkyl groups to provide a cross-linked silicone material. Accordingly, the compositions described herein in connection with the first aspect of the disclosure have an effective amount of a borane catalyst. As used herein, an "effective amount" is an amount effective to cause hydrosilylation of reactive heterocycloalkyl groups to provide a substantially polymerized material. In certain embodiments of the compositions of the disclosure, the borane catalyst is present in an amount ranging from about 0.0005% by weight to about 10% by weight, based on the total weight of the polymerizable composition. For example, in certain embodiments of the compositions as described herein, the borane catalyst is present in an amount within the range of about 0.0005% by weight to about 7% by weight, or about 0.0005% by weight. weight to about 5% by weight, or about 0.0005% by weight to about 3% by weight, or about 0.0005% by weight to about 2% by weight, or about 0.0005% by weight to about 1% by weight, or about 0.05% by weight to about 10% by weight, or about 0.01% by weight to about 7% by weight, or about 0. 01% by weight to about 5% by weight, or about 0.01% by weight to about 3% by weight, or about 0.01% by weight to about 2% by weight, or about 0 .01 wt% to about 1 wt%, or about 0.1 wt% to about 10 wt%, or about 0.1 wt% to about 7 wt%, or about from 0.1% by weight to about 5% by weight, or about 0.1% by weight to about 3% by weight, or about 0.1% by weight to about 2% by weight, or about from 0.1% by weight to about 1% by weight, based on the total weight of the polymerizable composition. In certain embodiments, the borane catalyst is present in an amount of at least about 0.005% by weight, e.g., at least about 0.05% by weight, at least about 0.5% by weight, or at least about 5% by weight of the composition. Obviously, one skilled in the art will appreciate that in some cases the effective amount of borane catalyst will be outside these ranges.

[0161] As described above, the polymerizable composition includes an effective amount of a borane catalyst. In certain embodiments of the compositions as described herein, the borane catalyst comprises or is a compound of the formula B(RC)q(RD)r wherein each RC is independently C6-C14 aryl, optionally substituted with one or more groups which are independently fluoroalkyl, halogen, nitro, or CN C1-C3; each RD is independently halogen; q is 1-3; r is 0-2; and the sum of q and r is 3. For example, in certain embodiments of the compositions as described herein, the borane catalyst comprises or is a compound of the formula B(RC)q(RD)r wherein aryl RC is C6, optionally substituted with one or more groups that are independently C1-C3 fluoroalkyl, halogen, nitro, or CN, q is 3 and r is 0.

[0162] In certain embodiments of the compositions, as described herein, the borane catalyst comprises B(C6F5)3 3 or a tetra (pentafluorophenyl) borate salt, such as [(C6F5)3PF][B(C6F5)4].

[0163] In certain embodiments of the compositions, as described herein, the borane catalyst comprises or is a borate complex. For example, in certain embodiments of the compositions as described herein, the borane catalyst comprises a borate carbamate such as, for example, a carbazole-based compound, such as

[0164] Although the polymerizable compositions described herein may include various additional components, such as additives and/or fillers, they may be in substantial part formed from the materials described herein. For example, in certain embodiments of the compositions as described herein, the total amount of first, second and/or third organosiloxanes or organosilanes, the reactive organic compound and borane catalyst is at least about 20%, e.g. example, at least about 30% by weight of the composition. For example, in certain embodiments of the compositions as described herein, the total amount of first, second and/or third organosiloxanes or organosilanes, the reactive organic compound and borane catalyst is at least about 40% by weight or at least about 50% by weight, or at least about 60% by weight, or at least about 70% by weight, or at least about 80% by weight, or at least about 85% by weight, or at least about at least about 90% by weight, or at least about 95% by weight, or at least about 98% by weight, or at least about 99% by weight of the composition.

[0165] In certain embodiments, the polymerizable composition is substantially free of (e.g., less than 0.1% by weight, or less than 0.01% by weight, or less than 0.001% by weight) metal hydrosilylation catalysts transitions, such as platinum-based catalysts, ruthenium-based catalysts, palladium-based catalysts, osmium-based catalysts, iridium-based catalysts, titanium-based catalysts, tin-based catalysts, and tin-based catalysts. rhodium. In certain embodiments, the polymerizable composition is substantially free of (e.g., less than 0.1% by weight or less than 0.01% by weight or less than 0.001% by weight) a condensation catalyst, a free radical initiator and/or an acid or base catalyst.

[0166] However, in alternative embodiments, one or more other catalysts are present in the polymerizable composition.

[0167] As noted above, the polymerizable compositions described herein can include a variety of other components.

[0168] For example, in certain embodiments as described herein, the polymerizable composition further includes one or more adhesion promoters. A variety of adhesion promoters are known in the art, such as silanes, silicones, etc. Typically, the adhesion promoter is a silicon-based adhesion promoter such as silane or silicone. Suitable silicone-based adhesion promoters may differ from other silicone-based ingredients of the polymerizable composition composition of the disclosure (e.g., the first organosiloxanes or organosilanes, the second organosiloxanes or organosilanes and/or or the third organosiloxanes or organosilanes) in: structure, viscosity, average molecular weight, siloxane units and/or sequence of units. Suitable silicone-based adhesion promoters include, but are not limited to, (aminoalkyl)alkoxysilane, (aminoalkyl)trialkoxysilane, (aminoalkyl)alkyl-dialkoxysilane, bis(trialkoxysilylalkyl)amine, tris(trialkoxysilylalkyl)amine, tris(trialkoxysilylalkyl)amine amine, tris(trialkoxysilylalkyl) amine, tris(trialkoxysilylalkyl) isocyanurate, (epoxyalkyl)alkoxysilane, (epoxyalkyl)-alkyalldialkoxysilane, (epoxyalkyl)trialkoxysilane and (mercaptoalkyl)alkoxysilane, as well as various (meth)acryl-, alkyl-, aryl -, vinyl-alkoxysilanes functionalized with epoxy. The person skilled in the art will select an adhesion promoter appropriate for a desired substrate and a polymerizable composition. Additionally, organically functional silicon hydrides can, in some embodiments, help improve adhesion to a substrate.

[0169] In certain embodiments of the compositions as described herein, the polymerizable composition comprises one or more adhesion promoters in a total amount within the range of up to about 10% by weight of the composition, for example, within the range of about 0 .1 wt% to about 10 wt% based on the total weight of the polymerizable composition. For example, in certain embodiments of the compositions as described herein, the polymerizable composition further comprises one or more adhesion promoters in a total amount within the range of about 0% by weight to about 10% by weight, or about 0%. by weight to about 8% by weight, or about 0% by weight to about 5% by weight, or about 0% by weight to about 2% by weight, or about 0.1% by weight to about 8% by weight, or about 0.1% by weight to about 5% by weight, or about 0.1% by weight to about 2% by weight, or about 1% by weight to about from 10% by weight, or about 1% by weight to about 8% by weight, or about 1% by weight to about 5% by weight, or about 2% by weight to about 10% by weight %, or about 2% by weight to about 8% by weight, or about 2% by weight to about 5% by weight, or about 5% by weight to about 10% by weight, or about 8% by weight to about 10% by weight. In certain embodiments, the total amount of first, second, and third organosiloxanes or organosilanes, one or more adhesion promoters, and borane catalyst is at least about 20% by weight, e.g., at least about 30% by weight. % by weight, at least about 50% by weight, at least about 70% by weight, at least about 80% by weight, at least about 90% by weight or at least about 95% by weight of the composition . However, in other embodiments, substantially no adhesion promoter is present.

[0170] In certain embodiments of the compositions as described herein, the polymerizable composition further comprises one or more fillers. A variety of fillers are known in the art, made from materials such as, for example, silicone resin, other polymers, silica, glasses, minerals and metal oxides, nitrides, carbonates or carbides. Such fillers may be in the form of, for example, powder, flakes or fibers. For example, in certain embodiments of the compositions as described herein, the polymerizable composition further comprises silica as a filler.

[0171] In certain embodiments of the compositions as described herein, the polymerizable composition comprises one or more fillers in a total amount within the range of up to about 75% by weight, based on the total weight of the polymerizable composition, e.g., up to about 40% by weight of the composition, or about 15% by weight to about 75% by weight, or within the range of about 0.1% by weight to about 40% by weight of the composition. For example, in certain embodiments of the compositions as described herein, the polymerizable composition further comprises one or more fillers in a total amount within the range of about 15% by weight to about 55% by weight, or about 15% by weight. to about 50 wt%, or about 15 wt% to about 45 wt%, or about 15 wt% to about 40 wt%, or about 15 wt% to about 35 % by weight, or about 15% by weight to about 30% by weight or about 15% by weight % to about 25% by weight, or about 20% by weight to about 60% by weight, or about 25% by weight to about 60% by weight, or about 30% by weight to about 60% by weight, or about 35% by weight to about 60% by weight, or about 40% by weight weight to about 60% by weight, or about 20% by weight to about 55% by weight, or about 25% by weight to about 50% by weight, or about 30% by weight to about 45 % by weight. In certain embodiments, the total amount of first, second, third organosiloxanes or organosilanes, filler catalyst and borane is at least about 20% by weight, for example, at least about 30% by weight, at least about 50% by weight, at least about 70% by weight, at least about 80% by weight, at least about 90% by weight or at least about 95% by weight of the composition.

[0172] The currently disclosed polymerizable compositions can, in certain embodiments, be used as substantially solvent-free formulations. Therefore, in certain embodiments, a polymerizable composition as described herein has less than 5% by weight, less than 2% by weight, or even less than 1% by weight of solvent.

[0173] But the present inventors have also noted that the currently disclosed polymerizable compositions can be dispersed (e.g., dissolved or suspended) in a solvent to be used in coating formation, for example, by spray coating, dip coating or coating. by centrifugation. Accordingly, another aspect of the disclosure is a solvent-based coating composition, comprising a polymerizable composition as described herein, dispersed in a solvent. In certain embodiments, the total amount of the first, second and/or third organosiloxanes or organosilanes, reactive organic compound, tackifier (if present) and borane catalyst is at least about 0.5% by weight. , for example, at least about 0.05% by weight, or at least about 0.1% by weight of the coating composition, or in the range of 0.05% by weight to 10% by weight, or 0. 05% by weight to 2% by weight, or 0.05% by weight to 0.8% by weight or 0.1% by weight to 0.5% by weight of the coating composition (i.e., including solvent). And, in certain embodiments, the total amount of the first, second and/or third organosiloxanes or organosilanes, the reactive organic compound, tackifier (if present), the borane catalyst and the solvent in the composition is at least at least about 70% by weight, at least about 80% by weight, at least about 90% by weight, at least about 95% by weight, or even at least about 99% by weight. In certain embodiments, the solvent has a boiling point not exceeding 250 °C, for example, not exceeding 200 °C or even not exceeding 175 °C, at atmospheric pressure. A variety of solvents can be used, including water and a variety of conventional organic solvents. The solvent need not itself be a dissolving solvent for the polymerizable composition, as long as the polymerizable composition is otherwise dispersed in the solvent. The choice of solvent will depend on the desired application. Suitable solvents include, but are not limited to, water, hydrocarbon solvent (e.g., pentane, hexane, xylene, toluene, etc.), ethyl acetate, hexamethyldisiloxane, dimethylformamide, ether and any combination thereof.

[0174] The use of organosiloxane or organosilane materials, as claimed, allows the person skilled in the art to provide the polymerizable composition with a desired viscosity while maintaining desirable properties for the polymerized product, for example, for use as an adhesive or sealant. In certain embodiments, as described herein, the polymerizable composition has a viscosity of less than about 10,000 cP at 25 ° C. In certain embodiments, as described herein, the polymerizable composition has a viscosity of up to about 1,000,000 cP at 25 ° C. The viscosity is measured with a DHR1 rheometer using the shear rate sweep experiment. For example, the shear rate can range from 0.01/s to 1000/s. In certain embodiments, the polymerizable compositions of the disclosure may exhibit Newtonian fluidic behavior (i.e., viscosity substantially invariant with shear rate). For example, in various embodiments as described herein, the photocurable composition has a viscosity at 25°C of less than 5,000 cP , or less than 4,000 cP, or even less than 2,500 cP. In various other embodiments, as described herein, the photocurable composition has a viscosity at 25 °C of up to about 100,000 cP, or up to about 500,000 cP, or up to about 1,000,000 cP. In certain embodiments as described herein, the photocurable composition has a viscosity at 25°C of about 50 cP to about 10,000 cP, or about 50 cP to about 5,000 cP, or about 50 cP to about 2,500 cP. , or about 50 cP to about 1,000 cP, or about 100 cP to about 10,000 cP, or about 100 cP to about 5,000 cP, or about 100 cP to about 2,500 cP, or about 100 cP to about 1,000 cP, or about 1,000 cP to about 10,000 cP, or about 1,000 cP to about 5,000 cP, or about 1,000 cP to about 2,500 cP, or about 10,000 cP to about 1,000,000 cP, or about 10,000 cP to about 500,000 cP, or about 10,000 cP to about 250,000 cP or about 10,000 cP to about 100,000 cP or about 50,000 cP to about 1,000,000 cP, or about 50,000 cP to about 500,000 cP, or about 50,000 cP to about 250,000 cP, or about 50,000 cP to about 100,000 cP, or about 100,000 cP to about 1,000,000 cP or about 100,000 cP to about 500,000 cP, or about 100,000 cP to about 250,000 cP, or about 500,000 cP to about 1,000,000 cP. But the person skilled in the art will appreciate that formulations of other viscosities can be used.

[0175] When used as an adhesive (e.g., pressure-sensitive adhesive), sealant or release material, the person skilled in the art can use conventional additives used in such materials.

[0176] When used as a release material, the person skilled in the art can use conventional additives used in such materials. For example, an adhesion inhibitor, such as a polymeric adhesion inhibitor, can be used to provide materials with desirable low levels of adhesion after curing. The adhesion inhibitor may be, for example, a fluoropolymer or a silicone polymer, for example, bearing fluorinated or phenyl-containing side groups.

[0177] The present inventors have determined that the polymerizable compositions of the disclosure can have longer working times compared to conventional metal-catalyzed compositions. As used herein, "working time" is quantified as the time after which the initial viscosity of the polymerizable composition has quadrupled when maintained at 25 ° C and 50% relative humidity. The compositions disclosed herein can be made to be relatively stable at room temperature, allowing for long working times and pot life. In certain embodiments, as described herein, the polymerizable composition has a working time of at least 5 minutes, at least 20 minutes, at least 2 hours, at least 12 hours, at least 2 days, e.g., at least 7 days or even in at least 10 days, as measured for a % inch diameter bead at 25°C, 50% relative humidity. The working time can be adjusted by those skilled in the art, depending on the desired application, for example, by adjusting the polymerization temperature.

[0178] In certain embodiments, the polymerizable compositions of the disclosure have service temperatures within the range of about -65°C to about 300°C, e.g., in the range of about -20°C to about 300° C or about -40°C to about 250°C, or about -55°C to about 180°C.

[0179] Another aspect of the disclosure is a method of preparing a silicone material. The method includes providing a polymerizable composition comprising a polymerizable composition as described herein, then polymerizing the polymerizable composition. The amounts and identities of the various components of the polymerizable composition may be as described above.

[0180] As described above, the method includes polymerizing the polymerizable composition. In certain embodiments of the methods described herein, polymerizing the polymerizable composition comprises exposing (e.g., heating) the polymerizable composition to a temperature within the range of about -20°C to about 250°C for a time sufficient for polymerization. to occur. For example, in certain embodiments of the methods described herein, polymerizing the polymerizable composition comprises exposing the polymerizable composition to a temperature in the range of about 0°C to about 250°C, or 30°C to about 250°C, or 50°C to about 250°C, or about 90°C to about 250°C, or about 100°C to about 250°C, or about 125°C to about 250°C, or about 150°C to about 250°C, or about 180°C to about 250°C, or about 0°C to about 200°C, or about 0°C to about 180°C , or about 0°C to about 150°C, or about 0°C to about 100°C, or about 0°C to about 90°C, or about 0°C to about 30°C °C, or about 20 °C to about 225 °C, or about 20 °C to about 200 °C, or about 20 °C to about 175 °C, or about 20 °C to about 150°C, or about 20°C to about 125°C, or about 20°C to about 100°C, or about 30°C to about 225°C, or about 30°C to about 200°C, or about 30°C to about 180°C, or about 30°C to about 150°C, or about 30°C to about 100°C or about 30°C to about 90°C, or about 40°C to about 200°C, or about 50°C to about 180°C, or about 90°C to about 180°C, or about 60 °C to about 170 °C, or about 70 °C to about 160 °C

[0181] In certain embodiments of the methods, as described herein, polymerizing the polymerizable composition comprises irradiating the polymerizable composition. For example, in certain embodiments of the methods as described herein, polymerizing the polymerizable composition comprises irradiating the polymerizable composition with light having a wavelength of less than about 400 nm, such as, for example, less than about 350 nm or less. at about 300 nm.

[0182] In certain embodiments of the methods, as described herein, polymerization of the polymerizable composition is carried out within the range of about 1 minute to about 10 days, or about 10 minutes to about 10 days, or about 90 minutes about 10 days, or 2 hours about 10 days, or about 3 minutes about 7 days, or about 10 minutes about 7 days, or about 90 minutes about 7 days, or 2 hours to about 7 days, or about 1 minute to about 2 days, or about 3 minutes to about 2 days, or about 10 minutes to about 2 days, or about 90 minutes to about 2 days , or 2 hours to about 2 days, or about 1 minute to about 24 hours, or about 3 minutes to about 24 hours, or about 10 minutes to about 24 hours, or about 90 minutes to about from 24 hours or 2 hours to about 24 hours. The polymerization time can be adjusted by those skilled in the art depending on the desired application, for example, by adjusting the polymerization temperature or the irradiation wavelength.

[0183] For example, in certain embodiments of the methods described herein, the polymerizable composition comprises a borane catalyst comprising a borate complex such as, for example, a carbazole-based compound of Formula IV, and polymerizing the polymerizable composition comprises irradiating the composition polymerizable with light having a wavelength of about 254 nm. In certain embodiments, irradiation causes the borate complex to react to form a triarylborane, such as, for example, B(C6F5)3.

[0184] In certain embodiments of the methods, as described herein, irradiation of the polymerizable composition comprises the use of standardized radiation, thus providing a polymerized material having a shape. In certain embodiments, patterned radiation is formed using a photomask. In other embodiments, patterned radiation is formed using diffractive optics. In other embodiments, the patterned radiation is formed by rasterization. In certain embodiments, the polymerizable composition is in the form of a thin film. In certain embodiments, patterned radiation is delivered to the surface of a body of the polymerizable composition and operates to polymerize only an upper portion of the polymerizable composition.

[0185] Another aspect of the disclosure is a polymerized composition, prepared in accordance with the methods as described herein. Advantageously, the present inventors have determined that at least one silicon hydride functional group of the first organosiloxane or organosilane and at least one heterocycloalkyl functional group of the second organosiloxane or organosilane or reactive organic compound react, in the presence of the borane catalyst, to form a crosslink comprising a heterocycloalkylhydrosilyl addition product. Desirably, the formation of the heterocycloalkylhydrosilyl addition product does not produce undesirable byproducts. For example, in certain embodiments of the methods described herein, polymerization of the polymerizable composition involves one or more of the crosslinking reactions of Scheme I:

[0186] An analogous reaction can occur between a heterocycloalkyl group of a second organosiloxane or silane and the hydride of a first or third organosiloxane or silane.

[0187] In another example, in certain embodiments of the methods as described herein, polymerizing the polymerizable composition involves the reaction of Scheme II:

[0188] Analogous reactions can occur with the heterocycloalkyl groups of a reactive organic compound and a hydride of a first or third organosiloxane or silane.

[0189] Therefore, another aspect of the disclosure is a polymerized composition that is the polymerized product of a polymerizable composition, as described herein. In certain embodiments of the compositions as described herein, the molar ratio of a total of heterocycloalkylhydrosilyl addition products to a total of heterocycloalkyl-heterocycloalkyl addition products is at least 1.5:1. For example, in certain embodiments of the compositions as described herein, the molar ratio of total heterocycloalkylhydrosilyl addition products to total heterocycloalkyl-heterocycloalkyl addition products is at least 2:1 or at least 2. 5:1 or at least 3:1.

[0190] In certain embodiments of the polymerized compositions, as described herein, the molar ratio of a total of heterocycloalkylhydrosilyl addition products to a total of unreacted heterocycloalkyl functional groups is at least 10:1. For example, in certain embodiments of the compositions as described herein, the molar ratio of total heterocycloalkylhydrosilyl addition products to total unreacted heterocycloalkyl functional groups is at least 25:1 or at least 50:1 or at least about 75:1 or at least 100:1 or at least about 250:1 or at least about 500:1, at least about 750:1 or at least about 1000:1. will appreciate that even if a heterocycloalkyl functional group is not hydrosilylated, it can nevertheless undergo addition between heterocycloalkyl groups.

[0191] In certain embodiments, the polymerized composition can be substantially completely polymerized. However, as one skilled in the art will appreciate, polymerized compositions do not need to be fully polymerized; Polymerized compositions that retain some degree of unreacted silicon hydride functional groups and/or unreacted reactive heterocycloalkyl functional groups can still provide desirable properties to a material, for example, adhesive or sealing properties. For example, the polymerized composition may have, in certain embodiments, up to 50 mol%, up to 20 mol%, up to 10 mol%, up to 5 mol%, or up to 1 mol% silicon hydride functional groups that unreacted and/or unreacted reactive heterocycloalkyl functional groups.

[0192] The polymerized product of a polymerizable composition, as described herein, can be further characterized by its tensile properties, such as tensile strength and elongation at break. Tensile properties are measured using the ASTM D 412 test method, with average peak stress values recorded in pounds per square inch (psi) for tensile strength and peak stress values recorded as percentage elongation at break. For example, the polymerized product may have an elongation greater than about 25%, e.g., greater than about 50%, or greater than about 100%, or greater than 500%, or greater than 800%, or up to 1200 %, or within the range of about 25% to about 800%, or about 50% to about 800%, or about 100% to about 800%, or about 250% to about 800%, or about 500% to about 800%, or about 25% to about 500%, or about 50% to about 500%, or about 100% to about 500%, or about 250% to about 500%, or about 100% to about 800%, or about 250% to about 800% or about 500% to about 800%. The polymerized product may have a tensile strength of about 425 psi, for example, up to about 400 psi, or up to 300 psi, or up to 200 psi, or within the range of about 95 psi to about 400 psi, or about from 95 psi to about 300 psi, or about 95 psi to about 200 psi, or about 125 psi to about 400 psi, or about 125 psi to about 300 psi, or about 125 psi to about 200 psi, or about 150 psi to about 200 psi, or about 150 psi to about 300 psi, or about 150 psi to about 200 psi, or about 200 psi to about 400 psi, or about 300 psi to about 400 psi.

[0193] Polymerizable compositions and polymerized products, as described herein, can be further characterized by their peel bond strength. Peel bond strength is measured using the ASTM C 794 test method, on a polymerized product of the polymerized composition of the disclosure. For example, in certain embodiments, the polymerized product may have a peel bond strength within the range of about 25 to about 55 pounds/inch.

[0194] Polymerizable compositions and polymerized products as described herein may have a variety of hardnesses, for example, in some embodiments, a Shore A hardness of up to 65. Shore hardness is determined in accordance with ASTM C 661 in a polymerized product of the polymerizable composition of the disclosure. For example, in certain embodiments, the polymerized product of a polymerizable composition as described herein may otherwise have Shore A hardness within the range of from about 4 to about 65, from about 9 to about 65, or about from 4 to 55 or about 9 to about 55, or about 20 to about 50, such as about 30 to about 50 or about 40 to about 50. But in other embodiments, the material has a harder hardness appropriately measured on the Shore D scale.

[0195] The person skilled in the art will appreciate that the compositions described herein can be used in a wide variety of applications. They can be formulated as one- or two-part systems and the properties can be selected by the person skilled in the art to be useful in a variety of processes, e.g. injection molding, transfer molding, reactive extrusion, continuous printing, batch printing , adhesive techniques, sealing techniques, coating techniques, encapsulation techniques, photolithography and 3D printing, to name a few. A wide variety of articles can be formed using the compositions and methods described herein, including those suitable for life science applications (e.g., medical devices or biopharma), retail and consumer applications, and various industrial applications (e.g., electronic devices , such as microelectronic devices), electro-optical devices and optical devices and in construction, fluid system and automotive applications).

[0196] For example, one embodiment of the disclosure is an article in which the adhesive is in the form of a thin film. In certain embodiments, the thin film may have a thickness of about 1 μm to about 200 μm, or about 5 μm to about 180 μm, or about 30 μm to 150 μm.

[0197] Another aspect of the disclosure is an article comprising a first surface; a second surface; and a polymerized composition for adhering or sealing the first surface to the second surface, wherein the adhesive is a polymerization product of a polymerizable composition according to the disclosure. An embodiment of such an article is shown in Figure 1. Here, a first component 110 has a first surface 115 and a second component has a second surface 125. The polymerized composition 130 adheres the first surface 115 to the second surface 125. Another embodiment of such article is shown in Figure 2. Here, a first component 210 has a first surface 115 and a second component has a second surface 225. The polymerized composition 230 seals the first surface 215 to the second surface 225.

[0198] In certain embodiments of the article of disclosure, the first surface is a silicone polymer surface; and the second surface is a non-silicone polymer surface (e.g., a polyolefin or thermoplastic polyurethane surface). In certain embodiments of the article of the disclosure, the first surface is a non-silicone polymer surface (e.g., a polyolefin or thermoplastic polyurethane surface); and the second surface is a silicone polymer surface.

[0199] The polymerized composition can take various forms. For example, in certain embodiments of the disclosure, the polymerized composition is in the form of a thin film. In certain embodiments, the thin film may have a thickness of about 1 μm to about 200 μm, or about 5 μm to about 180 μm, or about 30 μm to 150 μm. Obviously, in other embodiments, depending on the specific application, the polymerized composition may be provided as a thicker layer or as a body of any desired shape.

[0200] Various articles of the disclosure may be prepared by sealing or affixing a first surface to a second surface. Certain methods include arranging a polymerizable composition as described herein so that it contacts the first surface and the second surface; and then polymerizing the polymerizable composition to adhere or seal the first surface to the second surface.

[0201] Another aspect of the disclosure is a tubing with a first layer disposed concentrically around a second layer and a layer of a polymerized product of a polymerizable composition according to the disclosure disposed between and in contact with the first layer and the second layer. In certain embodiments, the first layer is formed from a silicone polymer and the second layer is formed from a non-silicone polymer (e.g., a polyolefin). In certain embodiments, the first layer is formed from a non-silicone polymer (e.g., a polyolefin) and the second layer is formed from a silicone polymer. The compositions of the disclosure may act as a bonding layer to aid adhesion between materials other than the first layer and the second layer.

[0202] An embodiment of a pipeline is shown in schematic view in Figure 3. Here, the pipeline 300 includes a layer 306, which is a polymerized product of a polymerizable composition according to the disclosure. The layer 306 is pressed between the first layer 302 and the second layer 304, for example, so that the layer 306 is in direct contact with the inner surface 310 of the first layer 302 and in direct contact with the outer surface 308 of the second layer 304.

[0203] Another embodiment of the disclosure is an electro-optical device that includes an electro-optical die; a matrix attachment material that adheres the electro-optical matrix to a substrate; and an encapsulating material that encapsulates the electro-optical matrix, in which one or more of the matrix fixing material and the encapsulating material are a polymerized composition of a polymerizable composition, as described herein. In certain embodiments, the encapsulating material itself is shaped like a lens or a mirror. Another embodiment of the disclosure is an electro-optical device that includes an electro-optical die; a matrix attachment material that adheres the electro-optical matrix to a substrate; an encapsulating material that encapsulates the electro-optical matrix; and an optical material disposed in the encapsulant and configured in an operational optical beam path of the electro-optical array, wherein one or more of the array attachment material, the optical material and the encapsulant material is a polymerized composition of a polymerizable composition, as described here. In certain embodiments, the optical material is shaped like a lens or a mirror. The electro-optical device may be, for example, in the form of a light-emitting diode or a photodetector. An embodiment of an electro-optical device is shown in schematic cross-sectional view in Figure 4. Here, the electro-optical device 400 (in the form of a light-emitting diode) includes an electro-optical array 415 adhered to a substrate 405 by the matrix fixing material 420; an encapsulating material 410; and a lens-shaped optical material 430. Any or all of the matrix fixing material, encapsulating material and optical material can be formed from a polymerized composition of a polymerizable composition, as described herein.

[0204] The materials described herein can be molded into a variety of shapes. Accordingly, another aspect of the disclosure is a molded body of a polymer, as described herein.

[0205] Another aspect of the disclosure is a polymerizable composition that includes one or more organosiloxanes or organosilanes, one or more organosiloxanes or organosilanes comprising one or more of one or more first organosiloxanes or organosilanes , each comprising a plurality of silicon hydride functional groups, present in an amount ranging from about 0.05% by weight to about 89.95% by weight; one or more second organosiloxanes or organosilanes, each comprising a plurality of reactive heterocycloalkyl functional groups, present in an amount ranging from about 0.05% by weight to about 89.95% by weight; and one or more third organosiloxanes or organosilanes, each comprising at least about one silicon hydride functional group and at least about one reactive heterocycloalkyl functional group, present in an amount in the range of about 0.05% by weight at about 89.95% by weight; one or more reactive organic compounds, each comprising at least about one reactive heterocycloalkyl functional group, present in an amount within the range of about 0.05% by weight to about 99.95% by weight; one or more tackifiers present in an amount ranging from about 10% by weight to about 99.95% by weight; and an effective amount of a borane catalyst, present, for example, in an amount within the range of 0.0005% by weight to about 10% by weight, wherein the ratio of reactive heterocycloalkyl functional groups to reactive heterocycloalkyl functional groups Reactive silicon hydride in composition is in the range of 1:5 to 5:1. In certain embodiments, the tackifier is present in an amount ranging from about 20% by weight to about 75% by weight of the composition.

[0206] Such compositions can be formulated and cured, for example, as described above.

[0207] In certain embodiments (i.e., to make a pressure-sensitive adhesive), the polymerizable compositions of the disclosure include one or more tackifiers. The one or more tackifiers are present in an amount ranging from about 10% by weight to about 99.95% by weight, based on the total weight of the polymerizable composition. For example, in certain embodiments of the compositions as described herein, one or more tackifiers are present in an amount within the range of about 10% by weight to about 99% by weight, or about 10% by weight to about 95% by weight, or about 10% by weight to about 90% by weight, or about 10% by weight to about 85% by weight, or about 10% by weight to about 80% by weight weight, or about 10% by weight to about 75% by weight, or about 10% by weight to about 70% by weight, or about 10% by weight to about 65% by weight, or about 10% by weight to about 60% by weight, or about 10% by weight to about 55% by weight, or about 10% by weight to about 50% by weight, or about 10% by weight to about 45% by weight, or about 10% by weight to about 40% by weight, or about 10% by weight to about 35% by weight, or about 10% by weight to about 30% by weight weight, or about 15% by weight to about 99.95% by weight, or about 20% by weight to about 99.95% by weight, or about 20% by weight to about 99% by weight , or about 20% by weight to about 95% by weight, or about 20% by weight to about 90% by weight, or about 20% by weight to about 85% by weight, or about 20 % by weight to about 80% by weight, or about 2% by weight to about 75% by weight, or about 20% by weight to about 70% by weight, or about 20% by weight to about from 65% by weight, or about 20% by weight to about 60% by weight, or about 20% by weight to about 55% by weight, or about 20% by weight to about 50% by weight , or about 20% by weight to about 45% by weight, or about 20% by weight to about 50% by weight, or about 20% by weight to about 45% by weight, or about 20 % by weight to about 40% by weight, or about 20% by weight to about 35% by weight, or about 20% by weight to about 30% by weight, or about 15% by weight to about from 99.95% by weight, or about 20% by weight to about 99.95% by weight, or about 25% by weight to about 99.95% by weight, or about 30% by weight to about 99.95% by weight, or about 35% by weight to about 99.95% by weight, or about 40% by weight to about 99.95% by weight, or about 45% by weight to about 99.95% by weight, or about 50% by weight to about 99.95% by weight, or about 55% by weight to about 99.95% by weight, or about 60% by weight weight to about 99.95% by weight, or about 65% by weight to about 99.95% by weight, or about 70% by weight to about 99.95% by weight, or about 50% by weight to about 95% by weight, or about 50% by weight to about 90% by weight, or about 50% by weight to about 85% by weight, or about 50% by weight to about 80% by weight, or about 25% by weight to about 75% by weight, or about 30% by weight to about 70% by weight, based on the total weight of the polymerizable composition.

[0208] The tackifier can be any that is known in the art suitable for use in pressure-sensitive adhesives and includes solid and liquid tackifiers. The tackifier may include, but is not limited to, amorphous tackifier resins of all types known for tackifier adhesives, including silicone-based (including dendrimeric silicones), resin-based, and resin-based. hydrogenated, hydrogenated resin based, hydrocarbon resin based and hydrogenated hydrocarbon resin types of liquid resin based on phenolic resin, based on terpene resin, based on phenolic terpene resin, based on styrenated terpene resin, hydrogenated terpene resin-based, hydrogenated terpene resin-based, polyester resin-based, pure aromatic-based monomer, aromatic acrylic-based, liquid resin types, and functionalized types thereof. These sticky agents can also be in hydrogenated form.

[0209] In certain embodiments of the compositions, as described herein, one or more sticky agents include terpene resins, petroleum hydrocarbon resins, piperylene and isoprene resins, hydrogenated resins and silicone resins.

[0210] The person skilled in the art will appreciate that the first, second and/or third organosiloxanes or organosilanes, the reactive organic compound and the tackifying agent can be combined in various combinations and amounts. For example, in certain embodiments as described herein, the composition includes one or more first organosiloxanes or organosilanes present in an amount within the range of about 0.05% by weight to about 30% by weight; one or more second organosiloxanes or organosilanes present in an amount within the range of about 70% by weight to about 89% by weight; and one or more tackifiers in an amount within the range of about 10% by weight to about 30% by weight. In other embodiments, as described herein, the composition includes one or more first organosiloxanes or organosilanes present in an amount within the range of about 1% by weight to about 30% by weight, about 5% by weight. to about 30% by weight, or about 10% by weight; to about 30% by weight; one or more second organosiloxanes or organosilanes present in an amount within the range of about 70% by weight to about 89% by weight, about 70% by weight to about 85% by weight or about 70 % by weight to about 80% by weight; and one or more tackifiers present in an amount within the range of about 10% by weight to about 30% by weight, about 15% by weight to about 30% by weight, or about 20% by weight to about 30% by weight. In other embodiments, as described herein, the composition includes one or more first organosiloxanes or organosilanes present in an amount within the range of about 30% by weight to about 70% by weight; one or more second organosiloxanes or organosilanes present in an amount within the range of about 15% by weight to about 55% by weight; and one or more tackifiers present in an amount within the range of about 15% by weight to about 55% by weight. In other embodiments, as described herein, the composition includes one or more first organosiloxanes or organosilanes present in an amount within the range of about 40% by weight to about 59.95% by weight; one or more second organosiloxanes or organosilanes present in an amount within the range of about 0.05% by weight to about 30% by weight; and one or more tackifiers present in an amount within the range of about 40% by weight to about 59.9% by weight. In certain embodiments, substantially no third organosiloxane or organosilane is present (e.g., no more than 0.5% by weight or no more than 0.1% by weight). In these embodiments, the reactive organic compound may be present in any desirable amount, as described above.

[0211] In other embodiments, as described herein, the composition includes one or more third organosiloxanes or organosilanes present in an amount within the range of about 30% by weight to about 89% by weight; and one or more tackifiers in an amount within the range of about 10% by weight to about 70% by weight. For example, in certain embodiments, the one or more third organosiloxanes or organosilanes are present in an amount within the range of about 50% by weight to about 89% by weight, or about 70% by weight to about 89% by weight. In certain embodiments, substantially no first organosiloxane or organosilane or second organosiloxane or organosilane is present (e.g., no more than 0.5% by weight or no more than 0.1% by weight of each). In these embodiments, the reactive organic compound may be present in any desirable amount, as described above.

[0212] In other embodiments, as described herein, a polymerizable composition includes one or more first organosiloxanes or organosilanes in an amount within the range of about 5% by weight to about 75% by weight; one or more second organosiloxanes or organosilanes in an amount of up to about 75% by weight; one or more third organosiloxanes or organosilanes in an amount of up to about 75% by weight; and one or more tackifiers in an amount within the range of about 10% by weight to about 85% by weight. In these embodiments, the reactive organic compound may be present in any desirable amount, as described above.

[0213] In other embodiments, as described herein, the one or more tackifiers are present in a total amount ranging from about 20% by weight to about 80% by weight, and the total amount of any first organo- siloxanes or organosilanes, any second organosiloxanes or organosilanes and any third organosiloxanes or organosilanes are in the range of about 15% by weight to about 85% by weight. In these embodiments, the reactive organic compound may be present in any desirable amount, as described above.

[0214] In other embodiments, as described herein, the one or more tackifiers are present in a total amount ranging from about 20% by weight to about 80% by weight, and the total amount of any first organo- siloxanes or organosilanes, any second organosiloxanes or organosilanes, and any third organosiloxanes or organosilanes are in the range of about 15% by weight to about 85% by weight. In these embodiments, the reactive organic compound may be present in any desirable amount, as described above.

[0215] Another aspect of the disclosure is an article comprising a substrate; and an adhesive disposed on a first surface of the substrate, wherein the adhesive is a polymerized product of a polymerizable composition according to the disclosure.

[0216] An embodiment of an article of the disclosure is illustrated in Figure 5. Here, the article 500 includes a substrate 510 and the adhesive 520 (e.g., a polymerized product of a polymerizable composition according to the disclosure) in contact with the surface of substrate 530. The surface of substrate 530 may comprise a coating of initiators (not shown).

[0217] In certain embodiments of the article of the disclosure, the substrate is a back layer liner. A standard backsheet coating may be used, such as cellulosic material (e.g. paper), silicone-free film (e.g. thermoplastic or polymer material, polymer blends or polymer-filled films), cardboard, stock board, woven fabrics and non-woven fabrics, glass (e.g. uncoated or PTFE/silicone rubber coated fabrics), glass sheets, foams, foams composed of films, metal sheets, metal sheets, glass, ceramics etc. The back layer coating may include a single layer or consist of multiple layers, including a layer that provides the desired rheological and surface properties and another layer that provides the desired physical properties, such as tearing, elongation, and tensile properties. Single or multiple back layer coating can be produced in conventional ways, such as by molding, calendering and extrusion. Other lamination and coextrusion techniques can be used to form multiple layers of backsheet liners. In certain embodiments, the back layer covering may be paper, such as kraft paper. Exact paper weight may vary, and illustrative weights include, but are not limited to, about 25 pounds to about 96 pounds per thousand square feet, e.g., about 96 pounds per thousand square feet or about 75 pounds per thousand feet squares, or about 60 pounds per thousand square feet, or about 42 pounds per thousand square feet. In certain embodiments, the back layer coating may be polymer film, such as polyethylene terephthalate (PET), polyethylene (PE), high-density polyethylene (HDPE), polypropylene (PP), polytetrafluoroethylene (PTFE), polyester, polyamide and polyolefin. The exact thickness of the polymer film may vary and illustrative thicknesses include, but are not limited to, about 0.4 mils to about 20 mils, e.g., about 1 mils or about 2 mils or about 3 mils or about 4 mils, or about 1 mil to about 4 mils, or about 0.4 mils to about 40 mils, or about 1 mils to about 40 mils, or about 2 mils to about 40 mils or about 5 mils to about 40 mils or about 10 mils to about 40 mils, or about 20 mils to about 40 mils, or about 1 mils to about 20 mils, or about 2 mils to about 20 mils, or about 5 mils to about 20 mils or about 10 mils to about 20 mils.

[0218] In certain embodiments, the substrate is a release coating. In other embodiments, a separate release coating is used in conjunction with adhesive disposed on a substrate. A release liner is configured to allow the adhesive to be released cleanly so that it can be peeled off to expose the adhesive surface. The release liner may be coated with a suitable release liner or may be formed from a material that provides suitable release properties. Coatings and release materials are known and include materials such as, for example, silicone (such as fluorosilicone), fluoropolymers, polyethylene, polycarbamate, polyacrylics and the like. In certain embodiments, the release coating may be coated on the release coating to form a release layer with a dry layer weight of 0.5 to 6 g/m2, for example, 2 to 3 g/m2.

[0219] An embodiment of the article of the disclosure comprising a release coating is illustrated in Figure 6. Here, the article 600 includes a substrate 610 that is in contact with the first surface of the adhesive 620 (e.g., a polymerized product of a composition polymerizable according to disclosure). The surface of the substrate 610 that is in contact with the adhesive may comprise a coating of initiators (not shown). The article also comprises a release liner 650 covered with a release liner 640 in contact with the second surface of the adhesive 620.

[0220] In certain embodiments, such as those for single-sided tape applications, the side of the release coating surface opposite the surface in contact with the adhesive may be covered with a suitable release coating. This embodiment of the article of the disclosure is illustrated in Figure 7. Here, the article 700 in the form of a roll includes a substrate 710 and the adhesive 720 (e.g., a polymerized product of a polymerizable composition according to the disclosure) in contact with the first surface 730 of the substrate. Surface 730 may comprise a coating of initiators (not shown). The substrate 710 also comprises a release liner 740 in contact with the second surface 760 of the substrate. When the article 700 is rolled up, the adhesive 720 comes into contact with the release liner 740.

[0221] The release liner may also be coated with a suitable release initiator, which acts to improve the anchoring of the adhesive to the release liner. Suitable initiators include, but are not limited to, aqueous or solvent-based acrylic polymers, ethylene-vinyl acetate copolymers, fluorinated polymers, ethylene-vinyl acetate-acrylic copolymers, styrene-butadiene copolymers and styrene-butadiene copolymers and styrene-butadiene-acrylonitrile copolymers. In certain embodiments, the primer may be coated onto the release coating to form an initial coating with a dry coating weight of 0.5 to 6 g/m2, for example, 2 to 3 g/m2. The adhesive layer as described herein is then applied to the primer coating.

[0222] The release force properties of the release coating vary depending on the use of the article. Release force is measured using the PSTC 4 ("Relative Performance of Release Coatings") test procedure as set forth in the Pressure Sensitive Tape Council Test Methods. For example, the release liner may have a release force of about 1 gf/inch to about 150 gf/inch, e.g., about 1 gf/inch to about 100 gf/inch, or about 1 gf/inch /inch to about 50 gf/inch, or about 1 gf/inch to about 10 gf/inch, or about 10 gf/inch to about 150 gf/inch, or about 10 gf/inch to about 100 gf/inch, or about 10 gf/inch to about 50 gf/inch/inch, or about 50 gf/inch to about 150 gf/inch, or about 50 gf/inch to about 100 gf /in, or about 100 gf/in to about 150 gf/in.

[0223] In one embodiment of the article of disclosure, the adhesive is in the form of a thin film. In certain embodiments, the thin film may have a thickness of about 0.01 μm to about 500 μm, about 0.01 μm to about 200 μm, about 0.01 μm to about 1 μm, or about 0.01μm to about 0.5μm, or about 0.01μm to 0.1μm, or about 0.01μm to 0.07μm, or about 0.04μm to 0.07μm, or about 1 μm to about 200 μm, or about 5 μm to about 180 μm, or about 30 μm to 150 μm.

[0224] One skilled in the art can select adhesive with specific adhesion properties depending on the desired use, generally ranging from about 0.01 N/dm to about 100 N/dm, e.g., about 0.1 N /dm to about 100 N/dm, or about 1 N/dm to about 100 N/dm, or about 10 N/dm to about 100 N/dm, or about 50 N/dm to about 100 N/dm, or about 0.01 N/dm to about 80 N/dm, or about 0.1 N/dm to about 80 N/dm, or about 1 N/dm to about 80 N/dm, or about 10 N/dm to about 80 N/dm, or about 50 N/dm to about 80 N/dm, or about 0.01 N/dm to about 50 N/dm , or about 0.1 N/dm to about 50 N/dm, or about 1 N/dm to about 50 N/dm, or about 10 N/dm to about 50 N/dm, at a peeling angle of 180°, measured according to PSTC-1 and PSTC-3 at a peeling rate of 12.7 cm/min. Adhesives with higher levels of peel adhesion generally require back-layer coating with higher tensile strength.

[0225] In certain embodiments, the articles of the disclosure have service temperatures in the range of -80 °C to about 300 °C.

[0226] The article of the disclosure may be prepared by disposing a polymerizable composition of the disclosure on a substrate; and polymerizing the polymerizable composition to provide an adhesive disposed on the substrate.

[0227] Private experiments can be performed as described below:

[0228] One or more organosiloxanes and the tackifier are added to a glass container. Solvent is optionally added to provide a homogeneous mixture. A mechanical mixer is then used to stir the mixture. The borane catalyst is then added dropwise to the mixture and mixing is continued for an additional 30 minutes. The mixture is then applied to the back layer liner and, after removing any solvent by evaporation and appropriate curing, the article of the disclosure is obtained.

[0229] A disclosure article is prepared in accordance with the general procedure provided above, with the appropriate materials described in the table below.

[0230] In certain embodiments, polymerizable compositions as described herein have, when polymerized, a release force of no more than 200 gf/inch (e.g., no more than 100 gf/inch or no more than 50 gf/inch inch), as measured by PSTC 4 test procedure.

[0231] The term "release force" refers to the force required to remove a unit width of pressure-sensitive adhesive tape, which has been in contact with a release liner for a given period of time, from a test panel standard, as measured by the PSTC 4 test procedure ("Relative Performance of Release Coatings"), as set forth in the Pressure Sensitive Tape Council Test Methods, incorporated herein by reference in its entirety. Notably, the polymerized products of the compositions of the disclosure have release forces of no more than about 200 gf/inch, e.g., no more than about 100 gf/inch, no more than about 75 gf/inch, no more than about about 50 gf/inch, no more than about 25 gf/inch, no more than about 10 gf/inch or even no more than about 5 gf/inch; these release forces can make materials specifically suitable as release materials. In certain embodiments, the polymerized products have a release force in the range of about 1 gf/inch to about 200 gf/inch, or about 1 gf/inch to about 100 gf/inch, or about 1 g/inch. inch to about 75 gf/inch, or about 1 gf/inch to about 50 gf/inch, or about 1 gf/inch to about 25 gf/inch, or about 1 gf/inch to about 10 gf/inch, or about 5 gf/inch to about 150 gf/inch, or about 5 gf/inch to about 100 gf/inch, or about 5 gf/inch to about 75 gf/inch, or about 5 gf/inch to about 50 gf/inch, or about 5 gf/inch to about 25 gf/inch, or about 10 gf/inch to about 150 gf/inch, or about 10 gf/inch inch to about 100 gf/inch, or about 10 gf/inch to about 75 gf/inch, or about 10 gf/inch to about 50 gf/inch, or about 25 gf/inch to about 150 gf/inch, or about 25 gf/inch to about 100 gf/inch, or about 25 gf/inch to about 75 gf/inch, or about 25 gf/inch to about 50 gf/inch. Based on the disclosure described herein, one skilled in the art will provide a material with the desired release force.

[0232] In certain desirable embodiments, the first organosiloxane or organosilane includes one or more aryl groups (e.g., phenyl or substituted phenyl, such as fluorophenyl or alkylphenyl) and/or one or more fluorinated groups (e.g., fluoroaryl or fluoroalkyl). The use of these materials in appropriate amounts, as determined by one skilled in the art based on the present disclosure, can help provide a lower release force.

[0233] Second organosiloxanes or organosilanes that include, for example, aryl groups (e.g., phenyl or substituted phenyl, such as fluorophenyl or alkylphenyl) and/or fluorinated groups (e.g., fluorinated alkyl or fluorinated aryl) can help provide desirably low release forces.

[0234] Likewise, third organosiloxanes or organosilanes, including fluorinated groups or aryl groups, can help provide a desirably low release force.

[0235] Another aspect of the disclosure is a release layer disposed on a first surface; the release layer being a polymerization product of a polymerized product of a polymerizable composition, as described herein.

[0236] One embodiment of a release layer of the disclosure is illustrated in Figure 8, here configured as a release liner. The release liner 800 includes a back layer coating 810, with a first surface 815, with a release layer 820 disposed thereon. The release layer 820 has a coating release surface 830. The coating release surface of the release layer can provide a low release force, as described above, and therefore can provide the desired release characteristics to the coating.

[0237] In certain embodiments of the release coating of the disclosure, the first surface is a back coating layer. The standard backing layer may be used, such as cellulosic material such as paper, non-silicone film (e.g. thermoplastic or polymer material, polymer blends or filled polymer films), cardboard, stock board, woven fabrics and non-woven fabrics, foams, composite foams, metal sheets, metal sheets, glass, ceramics, etc. The backcoat layer may include a single layer or consist of multiple layers, including a layer that provides the desired rheological and surface properties and another layer that provides the desired physical properties, such as tearing, elongation, and tensile properties. The single or multi-layer coating back layer can be produced in conventional ways, such as by molding, calendering and extrusion. Additional lamination and coextrusion techniques can be used to form multilayer coating backsheet. In certain embodiments, the backing layer may be paper, such as kraft paper. Exact paper weight may vary, and illustrative weights include, but are not limited to, about 25 pounds to about 96 pounds per thousand square feet, e.g., about 96 pounds per thousand square feet or about 75 pounds per thousand feet squares, or about 60 pounds per thousand square feet, or about 42 pounds per thousand square feet. In certain embodiments, the backing layer may be polymer film, such as polyethylene terephthalate (PET), polyethylene (PE), high-density polyethylene (HDPE), polypropylene (PP), and polyolefin. The exact thickness of the polymer film may vary and illustrative thicknesses include, but are not limited to, about 0.4 mils to about 20 mils, e.g., about 1 mils or about 2 mils or about 3 mils or about 4 mils, or about 1 mil to about 4 mils.

[0238] Another embodiment is shown in the schematic cross-sectional view in Figure 9. A release liner 900 (including the backcoat layer 910 and the release layer 920) is disposed with its release layer against an adhesive 950 (e.g. example, a pressure sensitive adhesive.) The adhesive is disposed on a substrate 960. The release liner can be removed, with the low release force of the release layer allowing separation between the release layer and the adhesive, exposing thus the adhesive, which can be used to adhere another article to the substrate.

[0239] But the person skilled in the art will appreciate that the release layers described herein can provide release properties (and other properties, such as antifouling properties) to a wide variety of articles. Therefore, the disclosed release layers can be formed on any desirable surface to provide desirable release properties thereto. The skilled artisan will appreciate that the compositions and release layers described herein can be used in a wide variety of applications. A wide variety of articles can be formed using the compositions and methods described herein, including those suitable for life science applications (e.g., medical devices or biopharma), retail and consumer applications (such as pressure-sensitive adhesive materials), and various industrial applications (e.g. electronic devices such as microelectronic devices, electro-optical devices and optical devices, and in construction, fluid system and automotive applications). In certain embodiments, the release layer of the disclosure is used for a pressure-sensitive adhesive tape, a pressure-sensitive adhesive film, a label, or a medical dressing.

[0240] The release layer can be applied to the back layer of the coating with a thickness sufficient to provide the desired release force properties. In one embodiment of the disclosure, the coating is in the form of a thin film. In certain embodiments, the thin film may have a thickness of about 0.01 μm to about 20 μm, or about 0.01 μm to about 10 μm, or about 0.01 μm to about 5 μm, or 0.01 µm to about 1 µm or about 0.01 µm to about 0.5 µm, or about 0.01 µm to 0.1 µm, or about 0.01 µm to 0.07 µm or about 0.04 μm to 0.07 μm.

[0241] The release layer, as described herein, can be further characterized by improved release force properties. Release force can be measured using the PSTC 4 test procedure ("Relative Performance of Release Coatings") as set forth in the Pressure Sensitive Tape Council Test Methods. For example, the release layer may have a release force of about 200 gf/inch (e.g., no more than 100 gf/inch or no more than 50 gf/inch), e.g., about 1 gf/in to about 100 gf/inch or about 1 gf/in to about 50 gf/inch, or about 1 gf/inch to about 10 gf/inch, or about 10 gf/inch to about 150 gf/inch inch, or about 10 gf/inch to about 100 gf/inch, or about 10 gf/inch to about 50 gf/inch, or about 50 gf/inch to about 150 gf/inch, or about 50 gf/inch to about 100 gf/inch, or about 100 gf/inch to about 150 gf/inch.

[0242] The release layer of the disclosure can be prepared by the method comprising: disposing a polymerizable composition of the disclosure on a first surface; and polymerizing the polymerizable composition to provide the release layer. A general method for doing this is described: One or more organosiloxanes are added to a glass container. The mixture is then dissolved in toluene until a homogeneous solution is obtained. A mechanical mixer is then used to stir the mixture. During mixing, the glass container is maintained at a temperature of 60 °C. The borane catalyst is then added dropwise to the mixture and mixing is continued for an additional 30 minutes. The mixture is then applied to the back coating layer and, after removing the solvent by evaporation, the release coating of the disclosure was obtained.

[0243] A disclosure release coating is prepared according to the general procedure provided above. The materials used are described in the table below. 1 ream = 3000 square feet

[0244] Certain aspects of the disclosure are now explained in more detail through the following non-limiting examples.

EXAMPLES

[0245] General Procedure: Formulation

[0246] One or more organosiloxanes and the reactive organic compound were added to a glass container. The mixture was then dissolved in toluene until a homogeneous solution was obtained. A mechanical mixer was then used to stir the mixture. During mixing, the glass container was maintained at a temperature of 60 °C. The borane catalyst was then added dropwise to the mixture and mixing was continued for an additional 30 minutes. After removing the solvent by evaporation under reduced pressure, the polymerizable composition was obtained.

[0247] In one embodiment, the polymerization of the polymerizable composition can be represented by Scheme III:

[0248] Scheme III

[0249] Example 1

[0250] A polymerizable composition of the disclosure was prepared in accordance with the general procedure provided above. The silicone and epoxy components in Table 1 below were mixed and then dissolved in toluene to provide a homogeneous solution. The solution was stirred and heated to ~60 °C; the catalyst (BCF, 750 ppm) was added dropwise slowly. After 30 minutes, the solution was removed from the heat and the solvent was removed by evaporation under reduced pressure.

[0251] Table 1.

[0252] Example 2

[0253] A polymerizable composition of the disclosure was prepared in accordance with the general procedure provided above. The materials used are described in Table 2 below.

[0254] Table 2.

[0255] Example 3

[0256] A polymerizable composition of the disclosure was prepared in accordance with the general procedure provided above. The materials used are described in Table 3 below.

[0257] Table 3.

[0258] The polymerized compositions of Examples 1, 2 and 3 are illustrated in Figure 10. The polymerized composition of Examples 1 was the least transparent, but had the greatest hardness; the polymerized composition of examples 3 was the most transparent, but had the lowest hardness.

[0259] The thermal stability of the polymerized composition of Example 1 (marked as silicone-bisphenol A copolymer) is provided in Figure 11, along with the thermal stability of two comparative materials. "Silicone elastomer" was prepared by combining 5 to 7% (EPOXYPROPOXIPROPYL) METHYLSILOXANE] - DIMETHYLSILOXANE COPOLYMER, 200-300 cSt (1.86 g), DMS-H25 (10 g) and B(C6F5)3 (100 ppm) and curing at 80 °C for 10 min and then post-curing at 120 °C for 2 h. The "Bisphenol A" material was prepared by mixing bisphenol A diglycidyl ether with BCF (200 ppm) and heating to cure (80 °C for 10 min). In thermogravimetric analysis was carried out with gradual heating from room temperature to 800 °C (temperature increase = 5 °C/min) in nitrogen.

[0260] Additional aspects of the disclosure are described in the embodiments enumerated below, which may be combined in any number and in any manner that is not logically or technically inconsistent. Modality 1. Polymerizable composition, characterized by the fact that it comprises: one or more organosiloxanes or organosilanes, one or more organosiloxanes or organosilanes comprising one or more of one or more first organosiloxanes or organosilanes , each comprising a plurality of silicon hydride functional groups, present in an amount within the range of about 0.05% by weight to about 99.95% by weight (e.g., about 0.05% by weight). weight to about 95% by weight, or about 0.05% by weight to about 90% by weight); one or more second organosiloxanes or organosilane, each comprising a plurality of reactive heterocycloalkyl functional groups, present in an amount within the range of about 0.05% by weight to about 99.95% by weight (e.g. example, about 0.05% by weight to about 95% by weight, or about 0.05% by weight to about 90% by weight); and one or more third organosiloxanes or organosilanes, each comprising at least about one silicon hydride functional group and at least about one reactive heterocycloalkyl functional group, present in an amount within the range of about 0.05 % by weight to about 99.95% by weight (e.g., about 0.05% by weight to about 95% by weight, or about 0.05% by weight to about 90% by weight); one or more reactive organic compounds, each comprising at least about one reactive heterocycloalkyl functional group, present in an amount in the range of about 0.05% by weight to about 99.95% by weight (e.g., about 0.05% by weight to about 95% by weight, or about 0.05% by weight to about 90% by weight); and an effective amount of a borane catalyst, present, for example, in an amount in the range of 0.0005% by weight to about 10% by weight (e.g., about 0.5% by weight to about 10 % by weight), wherein the ratio of reactive heterocycloalkyl functional groups to reactive silicon hydride functional groups in the composition is in the range of 1:5 to 5:1. Embodiment 2. A polymerizable composition according to embodiment 1, wherein the polymerizable composition includes one or more first organosiloxanes or organosilanes and one or more second organosiloxanes or organosilanes. Embodiment 3. A polymerizable composition according to embodiment 2, wherein the polymerizable composition includes less than 1% of third organosiloxanes or organosilanes. Embodiment 4. A polymerizable composition according to embodiment 1, wherein the polymerizable composition includes one or more third organosiloxanes. Embodiment 5. Polymerizable composition according to embodiment 4, wherein the polymerizable composition includes less than 1% of the first organosiloxanes or organosilanes and the second organosiloxanes or organosilanes. Embodiment 6. Polymerizable composition according to any one of embodiments 1 to 4, wherein, if present, the one or more first organosiloxanes or organosilanes are present in a total amount of about 1% by weight to about 70% by weight. Embodiment 7. A polymerizable composition according to any one of embodiments 1 to 4, wherein the one or more first organosiloxanes or organosilanes are present in a total amount of about 25% by weight to about 90% by weight. Weight. Embodiment 8. Polymerizable composition according to any one of embodiments 1 to 7, wherein one or more of (e.g., each of) the first organosiloxanes or organosilanes includes about two silicon hydride functional groups (e.g. For example, functional groups of 1.7 to 2.3 silicon hydrides) (i.e., per molecule averaged over the sample). Embodiment 9. Polymerizable composition according to any one of embodiments 1 to 8, wherein one or more of (e.g., each of) the first organosiloxanes or organosilanes comprises about three or more silicon hydride functional groups , for example, various silicon hydride functional groups within the range of about 4 to about 1000 or 5 to about 1000. (i.e., per molecule, averaged over the sample). Embodiment 10. A polymerizable composition according to any one of embodiments 1 to 9, wherein one or more of (e.g., each) first organosiloxanes or organosilanes comprises a number of silicon hydride functional groups within the range from about 10 to about 100. (i.e., per molecule averaged over the sample). Embodiment 11. Polymerizable composition according to any one of embodiments 1 to 10, wherein one or more of (e.g., each of) the first organosiloxanes or organosilanes is an organosiloxane comprising about two or more units siloxane repeat unit, wherein the number of siloxane repeat units comprising a silicon hydride functional group is in the range of about 0.01% to about 100% of the total number of siloxane repeat units; for example, it is within the range of about 0.1% to about 100% of the total number of siloxane repeating units (i.e., per molecule, averaged over the sample). Embodiment 12. Polymerizable composition according to any one of embodiments 1 to 10, wherein one or more of (e.g., each of) the first organosiloxanes or organosilanes is an organosiloxane comprising about two or more units siloxane repeat unit, wherein the number of siloxane repeat units comprising a silicon hydride functional group is within the range of about 0.5% to about 20% of the total number of siloxane repeat units (i.e. is, per molecule, on average over the sample). Embodiment 13. Polymerizable composition according to any one of embodiments 1 to 12, wherein one or more of (e.g., each) first organosiloxanes or organosilanes is an organosiloxane comprising two or more repeating units of siloxane, wherein the number of siloxane repeating units comprising a silicon hydride functional group is within the range of about 20% to about 60% of the total number of siloxane repeating units (i.e., per molecule , on average, over the sample). Embodiment 14. A polymerizable composition according to any one of embodiments 1 to 13, wherein at least one of (e.g., each of) the first organosiloxanes or organosilanes is a compound of Formula IA: wherein: each of R1, R2, and R3 is independently hydrogen, C1-C60 (e.g., C1-C6 or C1-C3) hydrocarbon; each of R4, R5, and R6 is independently C1-C60 hydrocarbon (e.g., C1-C6 or C1-C3); each of R7, R9, R10, and R12 independently hydrogen or hydrocarbon C1-C60 (e.g., C1-C6 or C1-C3); R8 is hydrogen, O, or hydrocarbon C1-C60 (e.g., C1-C6 or C1-C3); R11 is a covalent bond to R8, if R8 is O and is otherwise hydrogen or C1-C60 hydrocarbon (e.g. C1-C6 or C1-C3); and each of X, Y and Z is independently from 0 to 20,000, provided that at least one of Modality 15. Polymerizable composition according to modality 14, wherein R8 and R11 are hydrogen; and each of R7, R9, R10, and R12 is independently hydrocarbon. C1-C60 (e.g. C1-C6 or C1-C3). Embodiment 16. A polymerizable composition according to embodiment 15, wherein each of R1, R2, and R3 is independently C1-C60 hydrocarbon (e.g., C1-C6 or C1-C3. Embodiment 17. A polymerizable composition according to embodiment 15 or embodiment 16, wherein C6 or C1-C3); R1, R2 and R3 is hydrogen. Embodiment 20. Polymerizable composition according to embodiment 19, wherein each of R1 and R3 is independently hydrocarbon C1-C60; to 1000 (e.g., 0 to 500); Y is 1 to 2000 (e.g., 1 to 500. A polymerizable composition according to embodiment 20, wherein the ratio of Y to the total of Z is within the range of 1:199 to 1:4. Embodiment 22. A polymerizable composition according to embodiment 20, wherein the ratio of Y to the total of X and Z is within the range of 1:4 to 3:2. Embodiment 23. A polymerizable composition according to any one of embodiments 19 to 22, wherein R8 and R11 are not hydrogen. Embodiment 24. A polymerizable composition according to any one of embodiments 29 to 23, wherein R8 is O and R11 is a covalent bond of R8. Embodiment 25. Polymerizable composition according to any one of embodiments 1 to 24, wherein one or more of (e.g., each of) the first organosiloxanes or organosilanes is a compound of Formula IB: wherein: each of R13, R14, R15, and R16 is independently hydrogen, hydrocarbon C1-C60 (e.g., C1-C6 or C1-C3), or RL; and RL is in which each of R17 and R18 is independently C1-C4 hydrocarbon, provided that the compound has at least two reactive silicon hydride groups. Embodiment 26. Polymerizable composition according to any one of embodiments 1 to 25, wherein the one or more first organosiloxanes or organosilanes comprise a hydride-terminated polysiloxane, or a polysiloxane with silicon hydrides along its main chain of polysiloxane, or a silane or disiloxane containing two silicon hydrides. Embodiment 27. A polymerizable composition according to any one of embodiments 1 to 26, wherein the one or more first organosiloxanes or organosilanes comprise one or more hydride-terminated PDMS; methylhydrosiloxane-dimethylsiloxane copolymer; polymethylhydrosililoxanes; and methylhydrogen silicone fluid (side chain type); 2,4,6,8-tetramethylcyclotetrasiloxane; and methylhydrosiloxane-phenylmethylsiloxane copolymer. Embodiment 28. Polymerizable composition according to any one of embodiments 1 to 27, wherein the molecular weight of one or more of (e.g., each) first organosiloxanes or organosilanes is within the range of about 130 Da at about 10 kDa. Embodiment 29. The polymerizable composition of any one of embodiments 1 to 28, wherein one or more (e.g., each) first organosiloxane or organosilane has a Mw of about 88 Da to about 1 MDa; for example, about 500 Da to about 500 kDa, or about 1 kDa to about 100 kDa; or about 1 kDa to about 10 kDa. Embodiment 30. Polymerizable composition according to any one of embodiments 1 to 29, wherein the molecular weight of one or more of (e.g., each) first organosiloxanes or organosilanes is within the range of about 10 kDa to about 65 kDa. Embodiment 31. Polymerizable composition according to any one of embodiments 1 to 30, wherein the molecular weight of one or more of (e.g., each) the first organosiloxanes or organosilanes is within the range of about 25 kDa to about 1 MDa. Embodiment 32. Polymerizable composition according to any of embodiments 1 to 4 and 6 to 31, wherein, if present, the one or more second organosiloxanes or organosilanes are present in a total amount of about 1% in weight to about 70% by weight. Embodiment 33. Polymerizable composition according to any one of embodiments 1 to 4 and 6 to 31, wherein the one or more second organosiloxanes or organosilanes are present in a total amount of about 25% by weight to about 90% by weight. Embodiment 34. Polymerizable composition according to any one of embodiments 1 to 33, wherein one or more of (e.g., each of) the second organosiloxanes or organosilanes comprises about two (e.g., 1,7- 2.3) reactive heterocycloalkyl functional groups (e.g., per molecule, on average, above the sample). Embodiment 35. A polymerizable composition according to any one of embodiments 1 to 34, wherein one or more of the second organosiloxanes or organosilanes comprises at least about two reactive heterocycloalkyl functional groups; or about three or more reactive heterocycloalkyl functional groups, for example, a number of reactive heterocycloalkyl functional groups within the range of about 2 to about 1000 or about 5 to about 500. Embodiment 36. A polymerizable composition of according to any one of embodiments 1 to 35, wherein one or more of (e.g., each of) the second organosiloxanes or organosilanes comprises a number of reactive heterocycloalkyl groups within the range of about 10 to about 100 (i.e. per molecule averaged over the sample). Embodiment 37. Polymerizable composition according to any one of embodiments 1 to 36, wherein one or more of (e.g., each) of the second organosiloxane or organosilanes is an organosiloxane comprising about two or more units of siloxane and wherein the number of siloxane units comprising a reactive heterocycloalkyl functional group is within the range of about 0.5% to about 20% of the total number of siloxane units or is in the range of about 0.01 % to about 100% of the total number of siloxane repeating units (i.e., per molecule, averaged over the sample). Embodiment 38. Polymerizable composition according to any one of embodiments 1 to 36, wherein one or more of (e.g., each) of the second organosiloxane or organosilanes is an organosiloxane comprising about two or more units of siloxane and wherein the number of siloxane units comprising a reactive heterocycloalkyl functional group is within the range of about 2% to about 10% of the total number of siloxane units (i.e., per molecule, on average, over the sample). Embodiment 39. Polymerizable composition according to any one of embodiments 1 to 38, wherein at least one (e.g., each) of the second organosiloxanes or organosilanes is a compound of Formula II-A: wherein: each of R21, R22, R23, R27, and R30 is independently C1-C60 hydrocarbon (e.g., C1-C6 or C1-C3), RA, or RB; RA is in which each of Q 1 and T 1 is, independently, O, or S; RC is C1-C20 hydrocarbonylene; each of RD and RE is independently C1-C6 carbonylene or a covalent bond; r is 0 or 1; and RF is C1-C6 hydrocarbonylene; RB is in which each of Q 2 and T 2 is, independently, O, or S; RL is C1-C20 hydrocarbonylene; each of RH and RJ is independently C1-C5 hydrocarbonylene; r is 0 or 1; RK is C1-C6 hydrocarbonylene and r is 1; and RK is C1-C6 hydrocarbonylene; or a covalent bond when r is 0; each of R24, R25, and R26 is independently C1-C60 (e.g., C1-C6 or C1-C3) hydrocarbon; each of R29 and R32 is independently hydrogen or C1-C60 (e.g., C1-C6 or C1-C3) hydrocarbon; R28 is O, or C1-C60 hydrocarbon; R31 is a covalent bond to R28 if R28 is O or otherwise is C1-C60 (e.g. C1-C6 or C1-C3) hydrocarbon; each of A, B, and C is independently 0 to 20,000, provided that at least one of A, B, and C is nonzero and that the molecule has at least two reactive heterocycloalkyl groups. Embodiment 40. Polymerizable composition according to embodiment 39, wherein each of R21, R23, R27, and R30 is independently C 1 -C 60 hydrocarbon (e.g., C 1 -C 6 or C 1 -C 3 ); R22 is RA or RB; the sum of A and C is independently 0-1,000; B is 1-2000. Embodiment 41. A polymerizable composition according to embodiment 39 or embodiment 43, wherein the ratio of B to the total of A and C is within the range of 1:199 to 1:9. Embodiment 42. A polymerizable composition according to any one of embodiments 39 to 41, wherein R28 is O and R31 is a covalent bond to R28. Embodiment 43. Polymerizable composition according to any one of embodiments 39 to 42, wherein at least one (e.g., each) of the second organosiloxanes or organosilanes is a compound of Formula II-B: wherein: each of R33, R34, R35, and R36 is independently hydrocarbon C1-C60 (e.g., C1-C6 or C1-C3), RA, RB, or RM; RM is R38; wherein each of R37 and R38 is independently C1-C60 hydrocarbon (e.g., C1-C6 or C1-C3); and R39 is from RA or RB; RA is in which each of Q 1 and T 1 is, independently, O, or S; RC is C1-C20 hydrocarbonylene; each of RD and RE is independently C1-C6 carbonylene or a covalent bond; r is 0 or 1; and RF is C1-C6 hydrocarbonylene; RB is in which each of Q 2 and T 2 is, independently, O, or S; RL is C1-C20 hydrocarbonylene; each of RH and RJ is independently C1-C5 hydrocarbonylene; r is 0 or 1; RK is C1-C6 hydrocarbonylene and r is 1; and RK is C1-C6 hydrocarbonylene or a covalent bond, if r is 0, provided that the compounds have at least two reactive heterocycloalkyl functional groups; Embodiment 44. A polymerizable composition according to any one of embodiments 39 to 43, wherein RG is linear or branched C1-C6 alkylene. Embodiment 45. Polymerizable composition according to any one of embodiments 1 to 44, wherein the one or more second organosiloxanes or organosilanes comprise an epoxy-terminated polysiloxane or a polysiloxane with epoxides along its polysiloxane backbone . Embodiment 46. A polymerizable composition according to any one of embodiments 1 to 45, wherein the one or more second organosiloxanes or organosilanes comprise one or more of the epoxide-terminated polysiloxanes; epoxycyclohexylethylmethylsiloxane-dimethylsiloxane copolymer; 2,4,6,8-tetramethyl-2,4,6,8-tetrakis (propyl glycidyl ether) cyclotetrasiloxane; and epoxy-modified side-chain type silicone fluids (e.g., epoxypropoxypropyl)methylsiloxane-siloxane copolymer). Embodiment 47. Polymerizable composition according to any one of embodiments 1 to 46, wherein the molecular weight of one or more of (e.g., each) second organosiloxanes or organosilanes is within the range of about 350 Da at about 5 kDa. Embodiment 48. The polymerizable composition according to any one of embodiments 1 to 47, wherein one or more (e.g., each) second organosiloxane or organosilane has a Mw of about 200 Da to about 1 MDa; for example, about 1 kDa to about 50 kDa. Embodiment 49. Polymerizable composition according to any one of embodiments 1 to 48, wherein the molecular weight of one or more of (e.g., each) second organosiloxanes or organosilanes is within the range of about 5 kDa at about 25 kDa. Embodiment 50. Polymerizable composition according to any one of embodiments 1 to 49, wherein the molecular weight of one or more of (e.g., each) of the second organosiloxanes or organosilanes is within the range of about 25 kDa to about 1 MDa. Embodiment 51. Polymerizable composition according to any of embodiments 1, 2 and 4 to 50, wherein, if present, the one or more third organosiloxanes or organosilanes are present in a total amount of about 1% in weight to about 70% by weight. Embodiment 52. Polymerizable composition according to any one of embodiments 1, 2 and 4 to 50, wherein the one or more third organosiloxanes or organosilanes are present in a total amount of about 25% by weight to about 90% by weight. Embodiment 53. Polymerizable composition according to any one of embodiments 1 to 52, wherein one or more of (e.g., each of) the third organosiloxanes or organosilanes comprises about one (e.g., 0.7 to 1.3) silicon hydride functional group and about one (e.g., 0.7 to 1.3) reactive heterocycloalkyl functional group (i.e., per molecule, on average, over the sample). Embodiment 54. Polymerizable composition according to any one of embodiments 1 to 53, wherein one or more of the third organosiloxanes or organosilanes comprises about two or more silicon hydride functional groups and/or about two or more reactive heterocycloalkyl functional groups (i.e., per molecule, on average, above the sample). Embodiment 55. Polymerizable composition according to any one of embodiments 1 to 54, wherein one or more of the third organosiloxane or organosilanes is an organosiloxane comprising two or more siloxane units and wherein the number of siloxane units is siloxane comprising a heterocycloalkyl functional group or a silicon hydride functional group is within the range of about 0.01% to about 100% (e.g., about 0.5% to about 50%) of the total number of units of siloxane. Embodiment 56. Polymerizable composition according to any one of embodiments 1 to 55, wherein at least one of (e.g., each) third organosiloxanes or organosilanes is a compound of Formula III-A: wherein: each of R41, R42, R43, R47, and R50 is independently hydrocarbons C1-C60 (e.g., hydrogen C1-C6 or C1-C3), RA or RB; RA is in which each of Q 1 and T 1 is, independently, O, or S; RC is C1-C20 hydrocarbonylene; each of RD and RE is independently C1-C6 carbonylene or a covalent bond; r is 0 or 1; and RF is C1-C6 hydrocarbonylene; RB is in which each of Q 2 and T 2 is, independently, O, or S; RL is C1-C20 hydrocarbonylene; each of RH and RJ is independently C1-C5 hydrocarbonylene; r is 0 or 1; RK is C1-C6 hydrocarbonylene and r is 1; and RK is C1-C6 hydrocarbonylene; or a covalent bond when r is 0; each of R44, R45 and R46 is independently C1-C60 hydrocarbon (e.g., C1-C6 or C1-C3); each of R49 and R52 is independently C1-C60 hydrocarbon (e.g., C1-C6 or C1-C3); R48 is O, or C1-C60 hydrocarbon; R51 is a covalent bond to R48 if R48 is O or otherwise is C1-C60 hydrocarbon (e.g. C1-C6 or C1-C3); each of D, E and F is independently from 0 to 20,000, provided that at least one of D, E and F is non-zero, provided that the molecule has at least one reactive silicon hydride and at least one reactive heterocycloalkyl group. Embodiment 57. Polymerizable composition according to embodiment 56, wherein each of R43, R47, and R50 is independently C1-C60 hydrocarbon (e.g., C1-C6 or C1-C3); R41 is H; R42 is RA or RB; D is 1 to 2000; E is 1a 2000; and F is 0 to 1,000. Embodiment 58. A polymerizable composition according to embodiment 56 or embodiment 57, wherein the ratio of E to the total of D and F is within the range of 1:199 to 1:9; and the ratio of D to the total of E and F is within the range of 1:199 to 1:9. Embodiment 59. A polymerizable composition according to any one of embodiments 56 to 58, wherein R48 is O and R51 is a covalent bond to R48. Embodiment 60. Polymerizable composition according to any one of embodiments 1 to 59, wherein at least one of (e.g., each) third organosiloxanes or organosilanes is a compound of Formula III-B: wherein: each of R53, R54, R55, and R56 is independently C1-C60 hydrocarbon, H, RA, RB, or RM; RM is wherein each of R57 and R58 is independently C1-C60 hydrocarbon; and R59 is from RA or RB; RA is in which each of Q 1 and T 1 is, independently, O, or S; RC is C1-C20 hydrocarbonylene; each of RD and RE is independently C1-C6 carbonylene or a covalent bond; r is 0 or 1; and RF is C1-C6 hydrocarbonylene; RB is each of Q 2 and T 2 is, independently, O, or S; RL is C1-C20 hydrocarbonylene; each of RH and RJ is independently C1-C5 hydrocarbonylene; r is 0 or 1; RK is C1-C6 hydrocarbonylene and r is 1; and RK is C1-C6 hydrocarbonylene or a covalent bond, if r is 0, provided that the molecule has at least one silicon hydride and at least one reactive heterocycloalkyl group. Embodiment 61. A polymerizable composition according to any one of embodiments 56 to 60, wherein RG is linear or branched C1-C6 alkylene. Embodiment 62. Polymerizable composition according to any one of embodiments 1 to 61, wherein the one or more third organosiloxanes or organosilanes comprise one or more of a polysiloxane terminated with one or more epoxides and having one or more hydrides of silicon along its main chain, a polysiloxane terminated with one or more silicon hydrides and with one or more epoxides along its main chain; a polysiloxane terminated with a silicon hydride and an epoxide; or a polysiloxane with one or more silicon hydrides and one or more epoxides along its polysiloxane backbone. Embodiment 63. Polymerizable composition according to any one of embodiments 1 to 62, wherein the molecular weight of one or more of (e.g., each) the third organosiloxanes or organosilanes is within the range of about 350 Gives about 5 kDa. Embodiment 64. The polymerizable composition of any one of embodiments 1 to 63, wherein one or more (e.g., each) third organosiloxane or organosilane has a Mw of about 120 Da to about 1 MDa; or about 1 kDa to about 100 kDa. Embodiment 65. Polymerizable composition according to any one of embodiments 1 to 64, wherein the molecular weight of one or more of (e.g., each) third organosiloxanes or organosilanes is within the range of about 5 kDa at about 25 kDa. Embodiment 66. Polymerizable composition according to any one of embodiments 1 to 65, wherein the molecular weight of one or more of the third organosiloxanes or organosilanes is within the range of about 25 kDa to about 1 MDa. Embodiment 67. A polymerizable composition according to any one of embodiments 14 to 66, wherein each of RD and RE is a covalent bond. Embodiment 68. A polymerizable composition according to any one of embodiments 14 to 66, wherein each of RD and RE is independently C1-C2 alkylene. Embodiment 69. A polymerizable composition according to any one of embodiments 14 to 68, wherein RF is linear or branched C1-C4 alkylene. Embodiment 70. A polymerizable composition according to any one of embodiments 14 to 68, wherein RF is methylene. Embodiment 71. A polymerizable composition according to any one of 14 to 70, wherein each of Q 1 and T 1 is O. Embodiment 72. A polymerizable composition according to any one of embodiments 14 to 71, wherein r is 0. Embodiment 73. A polymerizable composition according to any one of embodiments 14 to 72, wherein Embodiment 74. A polymerizable composition according to any one of embodiments 14 to 73, wherein RC is C1-C6 linear or branched heteroalkylene. Embodiment 75. A polymerizable composition according to any one of embodiments 14 to 74, wherein Embodiment 76. A polymerizable composition according to any one of embodiments 17 to 75, wherein RH is C1-C2 alkylene. Embodiment 77. A polymerizable composition according to any one of embodiments 17 to 76, wherein RJ is a methylene group. Embodiment 78. A polymerizable composition according to any one of embodiments 17 to 77, wherein RK is methylene. Embodiment 79. A polymerizable composition according to any one of embodiments 17 to 78, wherein each of Q 2 and T 2 is O. Embodiment 80. A polymerizable composition according to any one of embodiments 17 to 78, wherein r is 0. Embodiment 81. A polymerizable composition according to embodiment 80, wherein RK is a covalent bond. Embodiment 82. A polymerizable composition according to any one of embodiments 14 to 81, wherein RB is Embodiment 83. Polymerizable composition according to any one of embodiments 1 to 82, wherein the one or more reactive organic compounds are present in an amount within the range of about 0.05% by weight to about 80% by weight, for example, about 1% by weight to about 80% by weight. Embodiment 84. Polymerizable composition according to any one of embodiments 1 to 82, wherein the one or more reactive organic compounds are present in an amount within the range of about 10% by weight to about 90% by weight, e.g. , about 15% by weight to about 85% by weight. Embodiment 85. A polymerizable composition according to any one of embodiments 1 to 82, wherein the one or more reactive compounds are present in an amount within the range of about 1% by weight to about 70% by weight, e.g. , about 1% by weight to about 50% by weight, or about 1% by weight to about 30% by weight. Embodiment 86. The polymerizable composition according to any one of embodiments 1 to 85, wherein one or more of the reactive organic compounds comprises about one reactive heterocycloalkyl functional group. Embodiment 87. The polymerizable composition according to any one of embodiments 1 to 86, wherein one or more of the reactive organic compounds comprises at least about two (e.g., about two, e.g., 1.7 to 2.3 ) reactive heterocycloalkyl functional groups. Embodiment 88. The polymerizable composition of any one of embodiments 1 to 86, wherein one or more of the reactive organic compounds comprises reactive heterocycloalkyl functional groups within the range of about 2 to about 10,000, e.g., in the range of about 2 to 500, or in the range of about 2 to about 50. Embodiment 89. The polymerizable composition of any of embodiments 1 to 88, wherein the one or more reactive organic compounds is an epoxy-terminated portion or has one or more epoxides along its main chair. Embodiment 90. The polymerizable composition of any one of embodiments 1 to 89, wherein the one or more reactive organic compounds comprises an aliphatic hydrocarbon, an aromatic hydrocarbon, or a polymer. Embodiment 91. The polymerizable composition of any one of embodiments 1 to 90, wherein the one or more reactive organic compounds is, , wherein R is an aliphatic hydrocarbon (e.g., optionally substituted C1-C24 alkyl, alkenyl, C1-C24, C1-C24 alkynyl), an aromatic hydrocarbon, or a polymer (such as, without limitation, polyethylene, polypropylene, polyethylene glycol, polyacrylate , polymethacrylate, polyolefin, etc.) or a halogenated moiety, such as a haloalkyl or haloaryl-containing group. Embodiment 92. Polymerizable composition according to any one of embodiments 1 to 90, wherein each heterocycloalkyl functional group is a cyclic ether, e.g., an epoxide functional group or an oxetane functional group, or a cyclic thioether, e.g., a episulfide functional. Embodiment 93. A polymerizable composition according to any one of embodiments 1 to 90, wherein each heterocycloalkyl functional group is an epoxide. Embodiment 94. A polymerizable composition according to any one of embodiments 1 to 90, wherein each heterocycloalkyl functional group is an oxetane or an episulfide. Embodiment 95. The polymerizable composition according to any one of embodiments 1 to 94, wherein the polymerizable composition comprises: one or more first organosiloxanes or organosilanes in an amount within the range of about 10% by weight to about 95% by weight; and one or more reactive organic compounds in an amount within the range of about 5 wt % to about 90 wt % Embodiment 96. The polymerizable composition of Embodiment 95, wherein substantially none (e.g., no more than 0. 5% by weight of each) second or third organosiloxane or organosilane is present. Embodiment 97. The polymerizable composition according to any one of embodiments 1 to 94, wherein the polymerizable composition comprises one or more third organosiloxanes or organosilanes in an amount within the range of about 30% by weight to about 99.95% by weight; and one or more reactive organic compounds in an amount ranging from about 0.05% by weight to about 60% by weight. Embodiment 98. The polymerizable composition of embodiment 97, wherein substantially no (e.g., no more than 0.5% by weight of each) first organosiloxane or organosilane or second organosiloxane or organosilane is present. Embodiment 99. The polymerizable composition of any one of embodiments 1 to 94, wherein the polymerizable composition comprises one or more first organosiloxanes or organosilanes in an amount within the range of about 5% by weight to about 75% by weight. by weight; one or more second organosiloxanes or organosilanes in an amount within the range of about 5% by weight to about 75% by weight; one or more third organosiloxanes or organosilanes in an amount within the range of about 5% by weight to about 75% by weight; and one or more reactive organic compounds in an amount within the range of about 5% by weight to about 75% by weight. Embodiment 100. The polymerizable composition according to any one of embodiments 1 to 94, wherein the polymerizable composition comprises: one or more first organosiloxanes or organosilanes in an amount within the range of about 0.05% by weight to about 30% by weight (or about 30% by weight to about 70% by weight, or about 70% by weight to about 99.95% by weight); and one or more reactive organic compounds in an amount within the range of about 70% by weight to about 99.95% by weight (or about 30% by weight to about 70% by weight; or about 0. 05% by weight to about 30% by weight). Embodiment 101. The polymerizable composition of any one of embodiments 1 to 100, wherein the ratio of silicon hydride functional groups to reactive heterocycloalkyl functional groups in the composition is within the range of 1:3 to 3:1 or 1:2 to 2:1, or 1:1.5 to 1.5:1; or within the range of 1:1.2 to 1.2:1 or 1:1.1 to 1.1:1. Embodiment 102. A polymerizable composition according to any one of embodiments 1 to 100, wherein the ratio of silicon hydride functional groups to reactive heterocycloalkyl functional groups in the composition is within the range of 1:5 to 1:1, e.g. example, 1:2 to 1:1 or 1:1.5 to 1:1. Embodiment 103. Polymerizable composition according to any one of embodiments 1 to 102, wherein the composition is substantially free of ethylenic unsaturations capable of hydrosilylation (e.g., less than 0.05 in %, e.g., less than 0.01 in % of atoms that make up ethylenic unsaturations subject to hydrosilylation). Embodiment 104. A polymerizable composition according to any one of embodiments 1 to 103, wherein the ratio of ethylenic unsaturations capable of hydrosilylation to silicon hydride functional groups is less than 0.05, e.g., less than 0.01, less than 0.005 or even less than 0.001. Embodiment 105. The polymerizable composition of any of embodiments 1 to 104, wherein the catalyst comprises a borane compound of formula B(RC)q(RD)r, wherein each RC is independently C6-C14 aryl, optionally substituted with one or more groups that are independently C1-C3 fluoroalkyl, halogen, nitro, or CN; each RD is independently halogen; q is 1 to 3; r is 0 to 2; and the sum of q and r is 3. Embodiment 106. A polymerizable composition according to embodiment 105, wherein the borane catalyst comprises B(C6F5)3, or a tetra(pentafluorophenyl) borate salt, such as [(C6F5) 3PF] [B(C6F5)4]. Embodiment 107. A polymerizable composition according to any one of embodiments 1 to 104, wherein the borane catalyst comprises a borate complex. Embodiment 108. A polymerizable composition according to embodiment 107, wherein the borate complex comprises a borate carbamate. Embodiment 109. A polymerizable composition according to any one of embodiments 1 to 108, wherein the borane catalyst is present in an amount in the range of about 0.01% by weight to about 2% by weight. Embodiment 110. A polymerizable composition according to any one of embodiments 1 to 108, wherein the borane catalyst is present in an amount ranging from about 0.1% by weight to about 5% by weight. Embodiment 111. A polymerizable composition of any one of embodiments 1 to 110, wherein the polymerizable composition is substantially free (e.g., less than 0.1% by weight, or less than 0.01% by weight, or less than 0.001 % by weight) of transition metal hydrosilylation catalysts. Embodiment 112. The polymerizable composition according to any one of embodiments 1 to 111, wherein the polymerizable composition further comprises one or more adhesion promoters, for example, one or more silanes, or any combination thereof, in a total amount of up to 10% by weight of the composition, for example, within the range of about 0.1% by weight to about 10% by weight of the composition. Embodiment 113. The polymerizable composition of any one of embodiments 1 to 112, wherein the polymerizable composition further comprises one or more fillers (e.g., silicone resin, other polymers, silica, glasses, mineral and metal oxides, nitrides, carbonates or carbides, in the form of, for example, powder, flakes or fibers) in a total amount of up to about 75% by weight of the composition, for example, up to about 40% by weight of the composition or within the range of about 15% by weight to about 75% by weight of the composition, or within the range of about 0.1% by weight to about 40% by weight of the composition. Embodiment 114. Polymerizable composition according to any one of embodiments 1 to 113, wherein the total amount of first, second and third organosiloxanes or organosilanes, reactive organic compounds, adhesion promoters, fillers and borane catalyst is at least about 20% by weight, for example, at least about 30% by weight, at least about 50% by weight of the composition. Embodiment 115. Polymerizable composition according to any one of embodiments 1 to 113, wherein the total amount of first, second and third organosiloxanes or organosilanes, reactive organic compounds, adhesion promoters, fillers and borane catalyst is at least about 70% by weight, for example, at least about 80% by weight of the composition. Embodiment 116. Polymerizable composition according to any one of embodiments 1 to 113, wherein the total amount of first, second and third organosiloxanes or organosilanes, reactive organic compounds, adhesion promoters, fillers and borane catalyst is at least about 90% by weight or at least about 95% by weight of the composition. Embodiment 117. Solvent-based coating composition, comprising a polymerizable composition according to any one of embodiments 1 to 116, dispersed in a solvent. Embodiment 118. Coating composition according to embodiment 117, wherein the total amount of the first, second and third organosiloxanes or organosilanes, reactive organic compound and borane catalyst in the composition is at least about 0. 5% by weight, for example, at least about 2% by weight, or at least about 10% by weight of the coating composition. Embodiment 119. Coating composition according to embodiment 118, wherein the total amount of the first, second and third organosiloxanes or organosilanes, reactive organic compound, the borane catalyst and the solvent in the composition is at least about 70% by weight, for example, at least about 80% by weight, at least about 90% by weight, at least about 95% by weight, or even at least about 99% by weight. % by weight, at least about 90% by weight, at least about 95% by weight, or even at least about 99% by weight. Embodiment 120. A coating composition according to any one of embodiments 117 to 119, wherein the solvent has a boiling point not exceeding 250 ° C, for example, not exceeding 200 ° C, at atmospheric pressure. Embodiment 121. A method for preparing a cross-linked silicone material, the method comprising providing a polymerizable composition according to any one of embodiments 1 to 120 and polymerizing the polymerizable composition. Embodiment 122. A method according to embodiment 121, wherein the polymerization comprises exposing the polymerizable composition to a temperature in the range of about -20°C to about 250°C, e.g., about 0°C to about 180°C, or about 40°C to about 140°C. Embodiment 123. A method according to embodiment 121, wherein the polymerization comprises irradiating the polymerizable composition with light having a wavelength of less than about 400 nm. Embodiment 124. A method according to embodiment 123, wherein the borane catalyst of the polymerizable composition is in the form of a borate complex and wherein irradiation causes the borate complex to react to form a triarylborane. Embodiment 125. The method according to embodiment 123 or embodiment 124, wherein irradiation is carried out using standardized radiation, thereby providing a polymerized material with a shape. Embodiment 126. The method according to embodiment 125, wherein patterned radiation is formed by illumination through a photomask. Embodiment 127. The method according to embodiment 125, wherein patterned radiation is formed using diffractive optics. Embodiment 128. The method according to embodiment 125, wherein the patterned radiation is formed by rasterization. Embodiment 129. The method according to any one of embodiments 121 to 128, wherein the polymerizable composition is in the form of a thin film. Embodiment 130. The method according to any one of embodiments 121 to 128, wherein patterned radiation is delivered to the surface of a body of the polymerizable composition and operates to polymerize only an upper portion of the polymerizable composition. Embodiment 131. The method according to embodiment 121 or embodiment 122, wherein the polymerizable composition is formed and polymerized by a process selected from injection molding, transfer molding, reactive extrusion, continuous printing, batch printing, photolithography and printing 3D. Embodiment 132. A polymerized composition made by a method of any of embodiments 121 to 131. Embodiment 133. A polymerized composition that is the polymerization product of a polymerizable composition of any of embodiments 1 to 120. Embodiment 134. The polymerized composition of modality 132 or modality 133, wherein the molar ratio of a total of heterocycloalkylhydrosilyl addition products to a total of heterocycloalkyl-heterocycloalkyl addition products is at least 1.5:1, for example, at least 2: 1, or at least 2.5:1. Embodiment 135. The article of any of embodiments 132 to 134, wherein the polymerized composition is not fully polymerized (e.g., contains up to 1 mol%, or up to 5 mol%, or up to 10 mol%, or up to 50 mol% unreacted silicon hydride functional groups and/or unreacted reactive heterocycloalkyl functional groups). Embodiment 136. The use of a polymerized composition according to any one of embodiments 132 to 135 in a product for a life science application, an electronic device such as a microelectronic device or an electro-optical device. Embodiment 137. Electro-optical device, comprising: an electro-optical matrix; a matrix attachment material that adheres the electro-optical matrix to a substrate; and an encapsulating material that encapsulates the electro-optical matrix, one or more of the matrix fixing material, and the encapsulating material being a polymerized composition according to any one of embodiments 132 to 135. Embodiment 138. The electro-optical device according to with embodiment 137, in which the encapsulating material is shaped like a lens or a mirror. Embodiment 139. Electro-optical device, comprising: an electro-optical matrix; a matrix attachment material that adheres the electro-optical matrix to a substrate; and an encapsulating material that encapsulates the electro-optical matrix; and an optical material disposed in the encapsulant and configured in an operational optical beam path of the electro-optical array, one or more of the array attachment material, the optical material, and the encapsulant material being a polymerized composition in accordance with any one of the embodiments. 132 to 135. Embodiment 140. The electro-optical device according to embodiment 139, wherein the optical material is shaped like a lens or a mirror. Embodiment 141. The electro-optical device according to any one of embodiments 137 to 140, in the form of a light-emitting diode. Embodiment 142. The electro-optical device according to any one of embodiments 137 to 140, in the form of a photodetector. Modality 143. Article comprising: a first surface; a second surface; and a polymerized composition for adhering or sealing the first surface to the second surface, wherein the polymerized composition is a polymerization product of a polymerizable composition according to any one of embodiments 1 to 120. Embodiment 144. Method for affixing or sealing a first surface to a second surface to prepare the article of embodiment 143, the method comprising arranging a polymerizable composition according to any one of embodiments 1 to 120 so that it is in contact with the first surface and the second surface; and then polymerizing the polymerizable composition to adhere or seal the first surface to the second surface. Embodiment 145. The method of embodiment 144, wherein the polymerizable composition is polymerized by exposing the polymerizable composition to a temperature in the range of -20°C to about 200°C, e.g., about 0°C to about 180° C or about 40°C to about 140°C. Embodiment 146. The method of embodiment 144, wherein the polymerizable composition is polymerized by irradiating the polymerizable composition with light having a wavelength of less than about 400 nm. Embodiment 147. The method of any of embodiments 144 to 146, wherein polymerization of the polymerizable composition is carried out over a period of time of up to 1 minute, or up to 10 minutes, or up to 60 minutes, or up to more than 10 days. Embodiment 148. A polymerizable composition, polymerized composition, article or method of any of embodiments 1 to 147, wherein the one or more first organosiloxanes or organosilanes are present in an amount not exceeding about 89.95% by weight; the one or more second organosiloxanes or organosilanes are present in an amount not exceeding about 89.95% by weight; the one or more third organosiloxanes or organosilanes are present in an amount not exceeding about 89.95% by weight; and the one or more reactive organic compounds are present in an amount not exceeding about 89.95% by weight; and wherein the composition further includes one or more tackifiers, present in an amount within the range of about 10% by weight to about 99.95% by weight (e.g., about 10% by weight to about 90% by weight or about 25% by weight to about 75% by weight). Embodiment 149. The polymerizable composition of embodiment 148, wherein the total amount of first organosiloxane or organosilane, second organosiloxane or organosilane, third organosiloxane or organosilane and adhesive in the composition is at least about 30% in weight. Embodiment 150. The polymerizable composition of embodiment 148 or embodiment 149, wherein the total amount of first, second and/or third organosiloxanes or organosilanes, tackifier and borane catalyst is at least about 20% in weight, for example, at least about 30% by weight, at least about 50% by weight, at least about 70% by weight, at least about 80% by weight, at least about 90% by weight or at least about 95% by weight of the composition. Embodiment 151. The polymerizable composition of any one of embodiments 148 to 150, wherein one or more of the tackifiers are selected from resin, hydrogenated resin, hydrocarbon resin, hydrogenated hydrocarbon resin, phenolic resin, terpene resin, phenol terpene resin, styrenated terpene resin, hydrogenated terpene resin, polyester resin, silicone resins (e.g., dendrimer resins), and aromatic acrylic tackifiers. Embodiment 152. The polymerizable composition of any one of embodiments 148 to 151, wherein one or more of the tackifiers are selected from terpene resins, petroleum hydrocarbon resins, piperylene and isoprene resins, hydrogenated resins, and silicone resins . Embodiment 153. The polymerizable composition of any one of embodiments 148 to 152, wherein the one or more tackifiers are present in a total amount in the range of about 10% by weight to about 80% by weight, and the amount total of any first organosiloxanes or organosilanes, any second organosiloxanes or organosilanes and any third organosiloxanes or organosilanes are in the range of about 15% by weight to about 85% by weight. Embodiment 154. The polymerizable composition of any one of embodiments 148 to 153, wherein the one or more tackifiers are present in a total amount in the range of about 20% by weight to about 70% by weight, and the amount total of any first organosiloxanes or organosilanes, second organosiloxanes or organosilanes and third organosiloxanes or organosilanes are in the range of about 25% by weight to about 75% by weight. Embodiment 155. The polymerizable composition of any one of embodiments 148 to 152, wherein the polymerizable composition comprises one or more first organosiloxanes or organosilanes in an amount within the range of about 5% by weight to about 75% by weight. by weight; one or more second organosiloxanes or organosilanes in an amount of up to about 75% by weight; one or more third organosiloxanes or organosilanes in an amount of up to about 5% by weight to about 75% by weight; and one or more tackifiers in an amount within the range of about 10% by weight to about 85% by weight. Embodiment 155. A pressure-sensitive adhesive that is the polymerization product of the polymerizable composition of any one of embodiments 148 to 155. Embodiment 156. An article comprising: a substrate; and a pressure-sensitive adhesive disposed on the substrate, wherein the pressure-sensitive adhesive is a polymerized product of a polymerizable composition according to any one of embodiments 148 to 155. Embodiment 157. The article of embodiment 156, wherein the substrate is selected from cellulosic material, film (e.g., thermoplastic or polymer material, polymer blends or filled polymer films), cardboard, stock board, woven and non-woven fabrics, foams and foams for composites, sheet metal, metal foil , glass, ceramic Embodiment 158. The article of embodiment 156 or embodiment 157, wherein the pressure-sensitive adhesive has a thickness of about 0.01 μm to about 500 μm. Embodiment 159. The article of any one of embodiments 155 to 158, wherein the pressure-sensitive adhesive has adhesion of about 0.01 N/dm to about 100 N/dm at a peel angle of 180°, as measured according to PSTC-1. Embodiment 160. A polymerizable composition according to any one of embodiments 1 to 120, wherein the polymerizable composition when polymerized has a release force of no more than 200 gf/inch (e.g., no more than 100 gf/inch or no more at 50 gf/inch) as measured by the PSTC test procedure 4. Embodiment 161. The polymerizable composition of embodiment 160, further comprising an adhesion-inhibiting component, such as a polymeric adhesion-inhibiting component (e.g., a fluoropolymer or a polymer silicone, for example, bearing fluorinated or phenyl-containing side groups). Embodiment 162. Polymerizable composition of embodiment 160 or embodiment 161, wherein the polymerizable composition when polymerized has a release force of no more than about 100 gf/inch, no more than about 75 gf/inch, no more than about 50 gf/inch, no more than about 25 gf/inch, no more than about 10 gf/inch, or no more than about 5 gf/inch), for example, in the range from about 1 gf/inch to about from 100 gf/inch, or about 1 gf/inch to about 75 gf/inch, or about 1 gf/inch to about 50 gf/inch, or about 1 gf/inch to about 25 gf/inch , or about 1 gf/inch to about 10 gf/inch, or about 5 gf/inch to about 150 gf/inch, or about 5 gf/inch to about 100 gf/inch, or about 5 gf/inch to about 75 gf/inch, or about 5 gf/inch to about 50 gf/inch, or about 5 gf/inch to about 25 gf/inch, or about 10 gf/inch to about from 150 gf/inch, or about 10 gf/inch to about 100 gf/inch or about 10 gf/inch to about 75 gf/inch, or about 10 gf/inch to about 50 gf/inch, or about 25 gf/inch to about 150 gf/inch, or about 25 gf/inch to about 100 gf/inch or about 25 gf/inch to about 75 gf/inch, or about 25 gf/inch inch to about 50 gf/inch as measured by the PSTC 4 test procedure. Embodiment 163. Polymerizable composition of embodiment 160 or 161, wherein the polymerizable composition when polymerized has a release force not greater than about 25 gf/inch , as measured by the PSTC test procedure 4. Embodiment 164. Polymerizable composition of embodiment 160 or 161, wherein the polymerizable composition when polymerized has a release force not exceeding about 5 gf/inch, as measured by the PSTC test procedure 4. Embodiment 165. Release material that is the polymerized product of a polymerizable composition of any one of embodiments 160 to 164. Embodiment 166. Release material of embodiment 165, in the form of a layer having a thickness of about 0.01 µm to about 20 µm, for example, about 0.01 µm to about 0.5 µm or about 0.01 µm to 0.1 µm or about 0.01 µm to 0.07 µm or about 0.04μm to 0.07μm. Embodiment 167. The release material of embodiment 165 or 166 with a release force of no more than about 200 gf/inch (e.g., no more than about 100 gf/inch, no more than about 75 gf/inch , no more than about 50 gf/inch, no more than about 25 gf/inch, no more than about 10 gf/inch, or no more than about 5 gf/inch). Embodiment 168. The release material of embodiment 165 or 166 with a release force not exceeding about 25 gf/inch. Embodiment 169. The release material of embodiment 165 or 166 with a release force not exceeding about 5 gf/inch. Modality 170. Article comprising: a substrate; an adhesive (e.g., a pressure-sensitive adhesive) disposed on the substrate; and a release liner with the release material according to any one of embodiments 162 to 166 disposed against the adhesive. Embodiment 171. Method for exposing a sticker, comprising providing an article in accordance with embodiment 170; and removing the adhesive release liner, thereby exposing the adhesive. Embodiment 172. A release material (e.g., in the form of a layer) disposed on a first surface, the release material being a polymerization product of a polymerizable composition according to any one of embodiments 160 to 164.

[0261] It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light will be suggested to those skilled in the art and will be incorporated within the spirit and scope of this application and scope of the attached claims. All publications, patents and patent applications cited herein are incorporated herein by reference for all purposes.

Claims (34)

1. Polymerizable composition CHARACTERIZED by the fact that it comprises: one or more organosiloxanes or organosilanes, the one or more organosiloxanes or organosilanes comprising one or more of one or more first organosiloxanes or organosilanes including at least one organosiloxane comprising two or more siloxane repeat units, each comprising a plurality of reactive silicon hydride functional groups, present in an amount within the range of 0.05% by weight to 99.95% by weight; one or more second organosiloxanes or organosilane, each comprising a plurality of reactive heterocycloalkyl functional groups, present in an amount within the range of 0.05% by weight to 99.95% by weight; and one or more third organosiloxanes or organosilanes, each comprising at least one silicon hydride functional group and at least one reactive heterocycloalkyl functional group, present in an amount within the range of 0.05% by weight to 99, 95% by weight; provided that the composition includes at least one of the one or more first organosiloxanes or organosilanes, and the one or more third organosiloxanes or organosilanes; one or more reactive organic compounds, each comprising at least one reactive heterocycloalkyl functional group, present in an amount within the range of 0.05% by weight to 99.95% by weight; and an effective amount of a borane catalyst, wherein the ratio of reactive heterocycloalkyl functional groups to reactive silicon hydride functional groups in the composition is in the range of 1:5 to 5:1. 2. Polymerizable composition according to claim 1, CHARACTERIZED by the fact that it comprises one or more of the first organosiloxanes or organosilanes, wherein the at least one first organosiloxane comprising two or more siloxane repeat units includes a number of siloxane repeat units comprising a silicon hydride functional group that is within the range of 0.5% to 60% of the total number of siloxane repeat units thereof. 3. Polymerizable composition according to claim 1, CHARACTERIZED by the fact that it comprises one or more first organosiloxanes or organosilanes, wherein the one or more first organosiloxanes or organosilanes comprise a hydride-terminated polysiloxane, or a polysiloxane having silicon hydrides along its polysiloxane backbone, or a silane or disiloxane containing two silicon hydrides. 4. Polymerizable composition according to any one of claims 1 to 3, CHARACTERIZED by the fact that it comprises one or more first organosiloxanes or organosilanes, wherein the one or more first organosiloxanes or organosilanes comprise one or more hydride-terminated PDMS ; methylhydrosiloxane-dimethylsiloxane copolymer; polymethylhydrosiloxanes; and methylhydrogen silicone fluid (side chain type); 2,4,6,8-tetramethylcyclotetrasiloxane; and methylhydrosiloxanephenylmethylsiloxane copolymer. 5. Polymerizable composition according to any one of claims 1 to 4, CHARACTERIZED by the fact that, if present, the one or more second organosiloxanes or organosilanes are present in a total amount of 1% by weight at 70 % by weight. 6. Polymerizable composition according to any one of claims 1 to 5, CHARACTERIZED by the fact that it comprises one or more second organosiloxanes or organosilanes, wherein one or more of the second organosiloxane or organosilanes is an organosiloxane comprising two or more siloxane units, and wherein the number of siloxane units comprising a reactive heterocycloalkyl functional group is within the range of 0.5% to 20% of the total number of siloxane units. 7. Polymerizable composition, according to any one of claims 1 to 6, CHARACTERIZED by the fact that it comprises one or more second organosiloxanes or organosilanes, wherein the one or more second organosiloxanes or organosilanes comprises an epoxy-terminated polysiloxane or a polysiloxane having epoxides along its polysiloxane backbone. 8. Polymerizable composition according to any one of claims 1 to 7, CHARACTERIZED by the fact that the one or more second organosiloxanes or organosilanes comprise one or more of the epoxide-terminated polysiloxanes; epoxycyclohexylethylmethylsiloxanedimethylsiloxane copolymer; 2,4,6,8-tetramethyl-2,4,6,8-tetrakis (propyl glycidyl ether) cyclotetrasiloxane; and epoxy-modified side-chain silicone fluids. 9. Polymerizable composition according to any one of claims 1 to 8, CHARACTERIZED by the fact that, if present, the one or more third organosiloxanes or organosilanes are present in a total amount of 1% by weight at 70 % by weight. 10. Polymerizable composition, according to any one of claims 1 to 9, CHARACTERIZED by the fact that it comprises one or more third organosiloxanes or organosilanes, wherein the one or more third organosiloxanes or organosilanes comprises one or more of one terminated polysiloxane with one or more epoxides and having one or more silicon hydrides along its main chain, a polysiloxane terminated with one or more silicon hydrides and having one or more epoxides along its main chain; a polysiloxane terminated with a silicon hydride and an epoxide; or a polysiloxane having one or more silicon hydrides and one or more epoxides along its polysiloxane backbone. 11. Polymerizable composition according to any one of claims 1 to 10, CHARACTERIZED by the fact that the one or more reactive organic compounds are present in an amount within the range of 0.05% by weight to 80% by weight. 12. Polymerizable composition according to any one of claims 1 to 11, CHARACTERIZED by the fact that one or more of the reactive organic compounds comprises a reactive heterocycloalkyl functional group. 13. Polymerizable composition according to any one of claims 1 to 11, CHARACTERIZED by the fact that one or more of the reactive organic compounds comprises at least two reactive heterocycloalkyl functional groups. 14. Polymerizable composition according to any one of claims 1 to 13, CHARACTERIZED by the fact that each heterocycloalkyl functional group is an epoxide. 15. Polymerizable composition according to any one of claims 1 to 13, CHARACTERIZED by the fact that each heterocycloalkyl functional group is an oxetane or an episulfide. 16. Polymerizable composition, according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 13, 14 and 15, CHARACTERIZED by the fact that the polymerizable composition comprises: one or more first organosiloxanes or organosilanes in an amount within the range of 10% by weight to 95% by weight; and one or more reactive organic compounds in an amount within the range of 5% by weight to 90% by weight. 17. Polymerizable composition according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 12, 13, 14 and 15, CHARACTERIZED by the fact that the polymerizable composition comprises a or more third organosiloxanes or organosilanes in an amount within the range of 30% by weight to 99.95% by weight; and one or more reactive organic compounds in an amount within the range of 0.05% by weight to 60% by weight. 18. Polymerizable composition according to any one of claims 1 to 17, CHARACTERIZED by the fact that the ratio of reactive silicon hydride functional groups to reactive heterocycloalkyl functional groups in the composition is within the range of 1:2 to 2:1 . 19. Polymerizable composition according to any one of claims 1 to 17, CHARACTERIZED by the fact that the ratio of reactive silicon hydride functional groups to reactive heterocycloalkyl functional groups in the composition is within the range of 1:5 to 1:1 . 20. Polymerizable composition according to any one of claims 1 to 19, CHARACTERIZED by the fact that the polymerizable composition comprises less than 0.05 at. % (atomic percentage) of atoms that make up ethylenic unsaturations capable of hydrosilylation. 21. Polymerizable composition according to any one of claims 1 to 20, CHARACTERIZED by the fact that the proportion of ethylenic unsaturations subject to hydrosilylation to reactive silicon hydride functional groups is less than 0.05. 22. Polymerizable composition according to any one of claims 1 to 21, CHARACTERIZED by the fact that the borane catalyst comprises B(C6F5)3 or a tetra(pentafluorophenyl)borate salt. 23. Polymerizable composition according to any one of claims 1 to 22, CHARACTERIZED by the fact that the borane catalyst is present in an amount in the range of 0.01% by weight to 5% by weight. 24. Polymerizable composition according to any one of claims 1 to 23, CHARACTERIZED by the fact that the polymerizable composition is substantially free of transition metal hydrosilylation catalysts. 25. Polymerizable composition according to any one of claims 1 to 24, CHARACTERIZED by the fact that the polymerizable composition further comprises one or more adhesion promoters in a total amount of up to 10% by weight of the composition; and/or one or more fillers in a total amount of up to 75% by weight of the composition. 26. Polymerizable composition, according to any one of claims 1 to 25, CHARACTERIZED by the fact that the total amount of first, second and third organosiloxanes or organosilanes, reactive organic compounds, adhesion promoters, fillers and catalyst borane is at least 70% by weight. 27. Polymerizable composition according to claim 26, CHARACTERIZED by the fact that the polymerizable composition when polymerized has a release force not exceeding 0.0772 N/mm as measured by the PSTC 4 test procedure. 28. Polymerizable composition according to claim 27, CHARACTERIZED by the fact that the polymerizable composition further comprises one or more tackifying agents, present in an amount within the range of 10% by weight to 80% by weight. 29. Solvent-based covering composition CHARACTERIZED by the fact that it comprises a polymerizable composition, as defined in any one of claims 1 to 28, dispersed in a solvent. 30. Method for preparing a cross-linked silicone material CHARACTERIZED by the fact that it comprises providing a polymerizable composition, as defined in any one of claims 1 to 28, and polymerizing the polymerizable composition. 31. Method according to claim 30, CHARACTERIZED by the fact that the polymerizable composition is formed and polymerized by a process selected from injection molding, transfer molding, reactive extrusion, continuous printing, batch printing, photolithography and 3D printing . 32. Polymerized composition CHARACTERIZED by the fact that it is the polymerization product of a polymerizable composition, as defined in any one of claims 1 to 28. 33. Polymerized composition according to claim 32, CHARACTERIZED by the fact that the molar ratio of a total of heterocycloalkylhydrosilyl addition products to a total of heterocycloalkylheterocycloalkyl addition products is at least 2:1. 34. Polymerizable composition, as defined in claim 32, or a polymerized composition, according to claim 33, CHARACTERIZED by the fact that it further comprises one or more tackifying agents, present in an amount within the range of 10% by weight to 80% by weight.