Epoxy-functional resin-linear polyorganosiloxane copolymer, composition containing the copolymer, and methods for their preparation and use

Abstract

An epoxycyclohexylalkyl – functional resin – linear polyorganosiloxane block copolymer and methods for its preparation and use are provided. The epoxycyclohexylalkyl – functional resin – linear polyorganosiloxane block copolymer is useful in both thermally curable compositions and UV curable compositions.

Description

EPOXY-FUNCTIONAL RESIN-LINEAR POLYORGANOSILOXANE COPOLYMER, COMPOSITION CONTAINING THE COPOLYMER, AND METHODS FOR THEIR PREPARATION AND USECROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 550648 filed on 7 February 2024 under 35 U.S.C. §119 (e). U.S. Provisional Patent Application Serial No. 63 / 550648 is hereby incorporated by reference.FIELD

[0002] An epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer and methods for its preparation and use are provided. A curable composition containing the epoxy-functional resin-linear polyorganosiloxane copolymer is useful for forming an encapsulant film.INTRODUCTION

[0003] Light emitting diode (LED) enabled opportunities like mini and micro LED arrays for displays and automotive applications require encapsulant films that can be efficiently cured by heat and / or UV without compromising the long-term stability and optical quality of the light extraction. Specifically, materials are required with high performance such as high optical transmission, high thermal and photothermal stability, strong adhesion, and good mechanical properties. Epoxy based resins have been considered as candidates because of their advantages including good optical clarity, high mechanical strength, strong adhesion and fast cure, but epoxy based resins are limited by their poor thermal and photo / photothermal stability and discoloration. Silicone materials have been broadly applied in LED packaging because of their excellent thermal and photothermal stability, however some of their limitations may restrict the applications, such as weak adhesion and high gas permeability because of their highly flexible siloxane backbone.

[0004] Hydrosilylation or condensation curable silicones have been proposed for LED encapsulation applications as disclosed, for example, in US Patent 9045668 to Horstman, et al. and US Patent 9705056 to Amako, et al., because they may show high transparency, excellent thermal and / or photothermal stability and / or high toughness. However, these silicones may be limited as to which cure systems can be used. Condensation cure systems can generate water and / or alcohol as by products, which may be detrimental to (opto)electronic devices, such as LEDs.SUMMARY

[0005] An epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer and methods for preparation and use of the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer are provided.DETAILED DESCRIPTION

[0006] The epoxycycloalkyl-functional resin - linear polyorganosiloxane block copolymer, introduced above, comprises linear blocks and non - linear blocks, wherein each linear block comprises 10 to 400 disiloxy units of formula (R^SiOz / r), wherein each R2is an independently selected monovalent hydrocarbyl group of 1 to 30 carbon atoms; each non - linear block has a molecular weight of at least 500 g / mol; the non - linear blocks comprise trisiloxy units and hydrolyzable groups; and the non - linear blocks further comprise epoxycycloalkyl - functional groups bonded to silicon atoms. At least 30 mol % of the non - linear blocks may be crosslinked with each other, and each linear block is linked to at least one non - linear block. The copolymer may have a Mw of at least 20,000 g / mol measured by GPC.

[0007] Linear polyorganosiloxanes typically comprise mostly D units, which results in polydiorganosiloxanes that are fluids of varying viscosity, depending on the DP, indicated by the number of D units in the polydiorganosiloxanes. Linear polydiorganosiloxanes typically have Tg lower than 25 °C, alternatively lower than 0 °C, and alternatively lower than -20 °C.

[0008] “Resin” polysiloxane results when a majority of the siloxy units are T, Q, or both units. When T siloxy units are predominant, the resulting polysiloxane can be referred to as a “silsesquioxane resin”. When Q units are predominant, the resulting polysiloxane can be referred to as a silicate. Increasing the amount of T and / or Q siloxy units (relative to amount of M and / or D units) typically results in polysiloxanes having increasing hardness and / or glass like properties. “Resin” polysiloxanes thus have higher Tg values than linear polydiorganosiloxanes, for example resin polysiloxanes often have Tg values greater than 30 °C, alternatively greater than 40 °C, and alternatively greater than 50 °C. Alternatively up to 100 °C, alternatively up to 80 °C, alternatively up to 70 °C, and alternatively 50 °C to 100 °C.

[0009] As used herein, “resin - linear polyorganosiloxane block copolymer” refers to polyorganosiloxanes containing polydiorganosiloxane blocks comprising, alternatively consisting essentially of, alternatively consisting of, D units in combination with resin blocks comprising T units. The resin - linear polyorganosiloxane block copolymer is a block copolymer (not a random copolymer). The D units are primarily bonded together to form polymeric polydiorganosiloxane chains having 10 to 400 D units, referred to herein as linear blocks. The T units are primarily bonded to each other to form branched polymeric chains, and these are included in the non - linear blocks. A significant number of these non - linear blocks may aggregate to form nano-domains when solid forms of the epoxycycloalkyl - functional resin- linear polyorganosiloxane block copolymer are provided. The disiloxy units of formula (R22SiO2 / 2) that are arranged in linear blocks have an average of 10 to 400 units of formula (R22SiO2 / 2) per linear block. Alternatively, each linear block may have an average of at least 10, alternatively at least 50, alternatively at least 100, alternatively at least 150, and alternatively at least 200 disiloxy units; while at the same time each linear block may have up to 400, alternatively up to 300, and alternatively up to 200, disiloxy units per linear block. Alternatively, each linear block may have 100 to 150 disiloxy units, alternatively 115 to 125 disiloxy units, alternatively 90 to 170 disiloxy units. The linear blocks are covalently bonded to the non - linear blocks.

[0010] The trisiloxy units are arranged in the non - linear blocks. The non - linear blocks each have a molecular weight of at least 500 g / mol, alternatively 500 g / mol to 4,000 g / mol per block. Alternatively, each non - linear block may have a Mn of at least 500 g / mol, alternatively at least 1,000 g / mol, alternatively at least 1,500 g / mol; while at the same time each non - linear block may have a Mn of up to 4,000 g / mol, alternatively up to 3,000 g / mol; alternatively up to 2,500 g / mol; alternatively up to 2,000 g / mol; and alternatively up to 1,500 g / mol.

[0011] The epoxycycloalkyl-functional resin - linear polyorganosiloxane block copolymer may further comprise hydrolyzable groups in the non - linear blocks. The hydrolyzable groups may have formula (ZO1 / 2), wherein each Z is independently selected from H or a monovalent hydrocarbyl group of 1 to 30 carbon atoms. Alternatively, the monovalent hydrocarbyl group for Z may be an alkyl group, such as an alkyl group of 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms, and alternatively methyl. Alternatively, each Z may be H. The epoxycycloalkyl-functional resin - linear polyorganosiloxane block copolymer may comprise up to 50 mol % of the hydrolyzable groups, alternatively at least 0.5 mol%, alternatively at least 1 mol%, alternatively at least 5 mol %, alternatively at least 10 mol%, and alternatively at least 15 mol%; while at the same time the epoxycycloalkyl-functional resin - linear polyorganosiloxane block copolymer may comprise up to 50 mol %, alternatively up to 35 mol %, alternatively up to 30 mol%, alternatively up to 25 mol%, and alternatively up to 20 mol % of the hydrolyzable groups.

[0012] The hydrolyzable groups may allow the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer to further react or cure or to crosslink. Crosslinking of the non - linear blocks may be accomplished via a variety of chemical mechanisms and / or moieties. For example, crosslinking of the non - linear blocks within the copolymer may result from condensation of residual silanol and / or alkoxy groups present in the non - linear blocks. At least 30% of the non - linear blocks in the epoxycycloalkyl-functional resin - linear polyorganosiloxane block copolymer may be crosslinked with each other, alternatively at least40%, alternatively at least 50%, alternatively at least 60%, alternatively at least 70%, and alternatively at least 80%. Alternatively, 30% to 80% of the non - linear blocks may be crosslinked with each other, alternatively 30% to 70%, alternatively 30% to 60%, alternatively 30% to 40%, and alternatively 30% to 40% of the non - linear blocks are crosslinked with each other.

[0013] The epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer may have a Mw of 20,000 g / mol to 500,000 g / mol. Alternatively, the epoxycycloalkyl- functional resin - linear polyorganosiloxane block copolymer may have a Mw of at least 20,000 g / mol, alternatively at least 40,000 g / mol, alternatively at least 50,000 g / mol, alternatively at least 60,000 g / mol, alternatively at least 70,000 g / mol, and alternatively at least 80,000 g / mol; while at the same time Mw may be up to 500,000 g / mol, alternatively up to 450,000 g / mol, alternatively up to 400,000 g / mol, alternatively up to 350,000 g / mol, alternatively up to 300,000 g / mol; alternatively up to 250,000 g / mol; alternatively up to 200,000 g / mol; alternatively up to 150,000 g / mol and alternatively up to 100,000 g / mol. Alternatively, the epoxycycloalkyl- functional resin - linear polyorganosiloxane block copolymer may have a Mn of 15,000 to 50,000 g / mol. Alternatively, the copolymer may have Mn of at least 15,000 g / mol, alternatively at least 20,000 g / mol; while at the same time Mn may be up to 50,000 g / mol, alternatively up to 30,000 g / mol, alternatively up to 25,000 g / mol. Mw and Mn may be measured by GPC, using the test method provided in the EXAMPLES, below.

[0014] The epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer may be isolated in a solid form, for example, by casting a film of a solution of the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer in an organic solvent (e.g., benzene, toluene, xylene, or a combination thereof) and allowing the solvent to evaporate. The epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer may be provided in a solution in an organic solvent in an amount of 50% to 80%, alternatively 60% to 80%, copolymer solids with the balance being organic solvent in the solution. The solution may be cast as a film and then dried to remove the solvent and form a solid, and the non - linear blocks may further aggregate together to form nano - domains. As used herein, “predominately aggregated” means the majority of the non - linear blocks are found in certain regions of the solid composition, referred to herein as “nano - domains”. The nano - domains refer to phase regions within the solid epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer that are phase separated and possess at least one dimension sized from 1 nm to 100 nm. The nano - domains may vary in shape, providing at least one dimension of the nano - domains is sized from 1 to 100 nm. The nano - domains may be regularly or irregularly shaped, alternatively spherical, tubular, or lamellar shaped.Alternatively, the solid epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer may contain a first phase and an incompatible second phase, the first phase containing predominantly the linear block and the second phase containing predominantly the non - linear block, the non - linear blocks being sufficiently aggregated into nano - domains that are incompatible with the first phase.

[0015] More specifically, the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer may comprise unit Formula (A), as follows:In unit formula (A), each R1is an independently selected monovalent hydrocarbyl group of 1 to 30 carbon atoms; each R2is the independently selected monovalent hydrocarbyl group of 1 to 30 carbon atoms as introduced above: each D1is an independently selected divalent hydrocarbyl group of 2 to 30 carbon atoms; each R3is independently selected from an alkenyl group of 2 to 30 carbon atoms or an aryl group of 6 to 30 carbon atoms; each R4is an epoxycycloalkyl - functional group; each Z is independently selected from H or a monovalent hydrocarbyl group of 1 to 30 carbon atoms as described above; subscripts a, b, c, d, and e represent mole fractions of each siloxy unit in the unit formula, and have values such that 0 < a < 0.1; 0.3 < b < 0.8; 0 < c < 0.2; 0.3 < (b + c) < 0.8; 0.1 < d < 0.7; 0.035 < e < 0.285; subscript f represents a molar amount of hydrolyzable groups in the copolymer, and subscript f has a value such that 0 < f < 0.5.

[0016] The monovalent hydrocarbyl group for R1and / or R2may be an alkyl group or an aryl group. Suitable alkyl groups have 1 to 30 carbon atoms and may be linear, branched, cyclic or combinations of two or more thereof. Examples of suitable alkyl groups include methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, tert-butyl, sec-butyl, and / or isobuty l); pentyl, hexyl, hepty l, octy l, nonyl, decyl, undecyl, dodecyl, and octadecyl (and branched isomers having 5 to 18 carbon atoms), and the alkyl groups are further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Alternatively, the alkyl group may be methyl, ethyl, propyl, buty l, or hexyl; alternatively methyl or ethyl; and alternatively methyl. Suitable aryl groups for R1and / or R2may have 6 to 30 carbon atoms and may be monocyclic or polycyclic, optionally with pendant hydrocarbyl groups. The aryl groups are exemplified by phenyl, tolyl, xylyl, benzyl, naphthyl, anthracenyl, 1 -phenyl ethyl, and 2- phenyl ethyl. Alternatively, the aryl group may be monocyclic, such as phenyl, tolyl, or benzyl. Alternatively, the aryl group may be phenyl or naphthyl; alternatively phenyl. Alternatively, each R1may be selected from the group consisting of methyl and phenyl, alternatively methyl.Alternatively, each R2may be selected from the group consisting of methyl and phenyl.

[0017] In unit formula (A), each D1is an independently selected divalent hydrocarbyl group of 2 to 30 carbon atoms. Examples of divalent hydrocarbyl groups for D1include an alkylene group such as ethylene, propylene, butylene, or hexylene; and an arylene group such as phenylene,Alternatively, D1may be an alkylene group such as ethylene.

[0018] In unit formula (A), each R3is independently selected from an alkenyl group of 2 to 30 carbon atoms or an aryl group of 6 to 30 carbon atoms. The aryl group for R3may be as described and exemplified above for R1and R2. The alkenyl group may have terminal alkenyl functionality, e.g. , the alkenyl group for R3may have formulasubscript y is 0 to 6. Alternatively, each alkenyl group may be independently selected from the group consisting of vinyl, allyl, and hexenyl; alternatively, vinyl and allyl; alternatively, vinyl; and alternatively, allyl.

[0019] In unit formula (A), each R4is an independently selected epoxycycloalkyl - functional group. The epoxycycloalkyl - functional group may have formulawherein D2is a divalent hydrocarbyl group of 2 to 30 carbon atoms, and subscript x is 0 or 1. Alternatively, subscript x may be 1. Suitable divalent hydrocarbyl groups for D2are as described and exemplified above for D1. Alternatively, D2may be selected from the group consisting of ethylene, propylene, and hexylene; alternatively ethylene and propylene. Alternatively, R4may be selected from an (epoxycyclopentyl)alkyl- group or an (epoxycyclohexyl)alkyl- group. Alternatively, R4may be the (epoxycyclohexyl)alkyl- group, and R4may be selected from |2-(3,4-epoxycyclohexyl)ethyl]; [3-(3,4-epoxycyclohexyl)propyl]; or {6-(7-oxabicyclo[4.1.0]heptan-3-yl)hexyl}.

[0020] In unit formula (A), each Z is independently selected from H or a monovalenthydrocarbyl group of 1 to 30 carbon atoms. Alternatively, the monovalent hydrocarbyl group for Z may be an alkyl group as described above for R1and / or R2, such as an alkyl group of 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms; alternatively methyl. Alternatively, each Z may be H.

[0021] In unit formula (A), each of subscripts a, b, c, d, and e represent mole fractions of each siloxy unit in the unit formula. Subscripts a, b, c, d, and e have values such that 0 < a < 0.1 ; 0.3 < b < 0.8; 0 < c < 0.2; 0.3 < (b + c) < 0.8; 0. 1 < d < 0.7; and 0.035 < e < 0.285. Alternatively, subscript a may have a value such that 0 < a < 0.1 , alternatively 0.05 < a < 0. 1 , and alternatively 0.07 < a < 0.09. Alternatively, subscript b may have a value such that 0.35 < b < 0.75, alternatively 0.4 < b < 0.7; and alternatively 0.45 < b < 0.65. Alternatively , subscript c may have a value such that 0 < c < 0. 15; alternatively 0.01 < c < 0.2. Alternatively subscript d may have a value such that 0.15 < d < 0.65; alternatively 0.2 < d < 0.6. Alternatively, subscript e may have a value such that 0.035 < e < 0.1; alternatively 0.05 < e < 0.1; alternatively 0.06 < e < 0.08; and alternatively e = 0.7. Subscript f represents a molar amount of hydrolyzable groups in the copolymer, and subscript f has a value such that 0 < f < 0.5; alternatively 0.05 < f < 0.35; and alternatively 0.05 < f < 0.20.

[0022] The epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer described above may be prepared by a method comprising:(Al) combining, under conditions to effect hydrolysis reaction, starting materials comprising:(al - 1) an aryltrialkoxysilane of formula R6Si(OR5)3, where R6is an aryl group of 6 to 30 carbon atoms, and each Rsis an independently selected alkyl group of 1 to 6 carbon atoms;(al -2) an epoxycycloalkyl - functional trialkoxysilane of formula R4Si(OR5)3, wherein R4is the epoxycycloalkyl - functional group described and exemplified above, and each Rsis the independently selected alkyl group of 1 to 6 carbon atoms;(a 1-3) a bis-alkenyl-terminated dialkylsiloxane oligomer of unit formula (R7R12SiOi / 2)2(R22SiO2 / 2)g, where R1and R2are the monovalent hydrocarbyl groups of 1 to 30 carbon atoms as described above; subscript g represents an average number of disiloxy units per molecule, and subscript g is an integer with value such that g > 0; and each R7is an independently selected alkenyl group of 2 to 30 carbon atoms; and (a 1-4) water; in the presence of (cl) an acid catalyst, thereby forming a hydrolysis product comprising an aryl-, epoxycycloalkyl-, alkenyl- functional silsesquioxane (MT) resin; andoptionally adding a solvent to the hydrolysis product formed in step (Al); optionally neutralizing (cl) the acid catalyst after step (Al);(A2) combining, under conditions to effect hydrosilylation reaction, starting materials comprising(a) the aryl-, epoxycycloalkyl-, alkenyl- functional silsesquioxane resin prepared in step (Al),(a2-l) a linear polyorganohydrogensiloxane of unit formula (R12HSiOi / 2)2(R22SiO2 / 2)h, where each R1and each R2are the independently selected monovalent hydrocarbyl groups of 1 to 30 carbon atoms, subscript h represents an average number of disiloxy units per molecule, and subscript h is an integer with a value of 8 to 398;(a2-2) an aryl-functional siloxane oligomer of unit formula (R1HSiOi / 2)2(R82SiO2 / 2)j, where each R1is the independently selected monovalent hydrocarbyl group of 1 to 30 carbon atoms, each R8is an independently selected aryl group of 6 to 30 carbon atoms, and subscript) represents average number of disiloxy units per molecule, and subscript) is an integer with a value of 1 to 3; and in the presence of (c2) a hydrosilylation reaction catalyst, thereby forming a hydrosilylation reaction product comprising the copolymer; and optionally (A3) recovering the copolymer from the hydrosilylation reaction product.

[0023] Starting material (al-1) used in the method above is an aryltrialkoxy silane of formula R6Si(OR5)3, where R6is an aryl group of 6 to 30 carbon atoms, and each R5is an independently selected alkyl group of 1 to 6 carbon atoms. Suitable aryl groups for R6are as described and exemplified above. Alternatively, R6may be selected from phenyl or naphthyl, alternatively phenyl. R5is an alkyl group of 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms, and alternatively 1 to 2 carbon atoms. Alternatively, each R5may be methyl. Examples of suitable aryltrialkoxysilanes include phenyltrimethoxysilane (CAS No. 2996-92-1), phenyltrimethoxysilane (CAS No. 780-69-8), and naphthyltriethoxysilane (CAS No. 17938-06- 6), all of which are commercially available from sources such as Gelest, Inc. of Morrisville, Pennsylvania, USA and Sigma - Aldrich Inc. of St. Louis, Missouri, USA.

[0024] Starting material (al -2) is an epoxycycloalkyl - functional trialkoxysilane of formula R4Si(OR5)3, wherein R4is the epoxycycloalkyl - functional group described and exemplified above, and each R5is the independently selected alkyl group of 1 to 6 carbon atoms as described and exemplified above. Examples of epoxycycloalkyl - functional trialkoxysilanes include [2- (3,4-Epoxycyclohexyl)ethyl]trimethoxysilane (also called 2-(7-Oxabicyclo[4.1.0]hept-3- yl)ethyl-trimethoxysilane, with Cas No. 3388-0403); [2-(3,4-Epoxycyclohexyl)ethyl]triethoxysilane (also called 2-(7-Oxabicyclo[4.1.0]hept-3-yl)ethyl- triethoxysilane, with Cas No. 10217-34-2); both of which are commercially available from sources such as Gelest, Inc. The amount of (al -2) the epoxycycloalkyl - functional trialkoxy silane used may be 3 mol % to 20 mol % based on amounts of starting materials (al- 1), (al-2), and (al-3), combined.

[0025] Starting material (al-3) is a bis-alkenyl-terminated diorganosiloxane oligomer of unit formula (R7R12SiOi / 2)2(R22SiO2 / 2)g, where R1and R2are the monovalent hydrocarbyl groups of 1 to 30 carbon atoms as described above; subscript g represents an average number of disiloxy units per molecule, and subscript g is an integer with value such that 9 > g > 0; and each R7is an independently selected alkenyl group of 2 to 30 carbon atoms. The alkenyl group for R7may be as described and exemplified above for R3. Alternatively, R7may be selected from the group consisting of vinyl, allyl, or hexenyl; alternatively vinyl and hexenyl; alternatively vinyl. Subscript g may be 0, alternatively at least 1, alternatively at least 2, alternatively at least 3, alternatively at least 4; while at the same time, g may be up to 9, alternatively up to 8, alternatively up to 7, alternatively up to 6, and alternatively up to 5. Alternatively, R1and R2may be alkyl groups, alternatively methyl. Examples of oligomers suitable for use as starting material (al-3) include l,3-divinyl-l,l,3,3-tetramethyldisiloxane (CAS No. 2627-95-4) and 1,5- divinyl-l,l,3,3,5,5-hexamethyltrisiloxane (CAS No. 136777-27-0) both of which are commercially available from sources such as Gelest, Inc. The amount of (al-3) the bis-alkenyl- terminated diorganosiloxane oligomer used may be 5 mol % to 10 mol % based on amounts of starting materials (al- 1), (al-2), and (al-3), combined.

[0026] Starting material (a 1-4) is water. The water is not generally limited, and may be utilized neat (i.e., absent any carrier vehicles and / or solvents), and / or pure (i.e., free from, or substantially free from, minerals and / or other impurities). For example, the water may be processed or unprocessed prior to the hydrolysis reaction. Examples of processes that may be used for purifying the water include reverse osmosis, distilling, filtering, deionizing, and combinations of two or more thereof, such that the water may be deionized, distilled, and / or filtered. Alternatively, the water may be unprocessed (e.g. may be tap water, i.e., provided by a municipal water system or well water, used without further purification). Alternatively, the water may be purified before use in the method. Alternatively, the water may be utilized as a mixture (e.g. solution or suspension) comprising a carrier vehicle and / or solvent, such as any of those listed herein for solubilizing the epoxy - functional resin - linear polyorganosiloxane block copolymer. Water may be added in an excess amount sufficient to hydrolyze starting materials (al- 1) and (al-2) and to facilitate removal with alcohol (e.g., methanol) generated as a side product. The amount of water may be sufficient to provide a molar ratio of water to siliconatoms from starting materials (al - 1), (al-2), and (al-3) of 2:1 to 3:1.

[0027] Starting material (cl) is a catalyst capable of forming a hydrolysis product of starting materials (al-1), (al-2), (al-3), and (al-4). Starting material (cl) may be an acid catalyst, such as a carboxylic acid exemplified by acetic acid, ethanoic acid, propionic acid, octanoic acid, decanoic acid, lauric acid, lactic acid, fluoroacetic acid, and 4,4,4-trifluorobutanoic acid;Bronstedt acids Lewis acids such as HC1, acidic phosphoric esters, or a sulphonic acid such as trifluoromethane sulfonic acid. Suitable acids are known in the art and are commercially available. The amount of acid catalyst depends on various factors including the species selected and the species and amounts of starting materials (al-1), (al-2), (al-3) and the hydrolysis reaction conditions, such as temperature. However, the amount of acid catalyst may be, for example 100 to 1,000 ppm based on weights of starting materials (al-1) and (al-3) combined. Alternatively, the amount of acid catalyst may be 200 ppm to 900 ppm, alternatively 250 ppm to 750 ppm, alternatively 500 ppm, on the same basis.

[0028] Step (Al) may be performed by any convenient means such as mixing optionally with heating. For example, starting materials (al-1), (al-2), (al-3) and (cl) may be combined in a reactor with mixing and heating to a temperature of 50 °C to < 100 °C. Starting material (al-4) the water may be added slowly over time, either continuously or intermittently in two or more aliquots. The resulting mixture may then be heated, optionally with stirring for an additional time period such as 1 hour to 12 hours, alternatively 2 hours to 4 hours, and alternatively 3 hours.

[0029] The method above optionally comprises neutralizing (cl) the acid catalyst after step (Al). Neutralizing may be performed by combining (e.g., by simple mixing) a neutralizing agent with the hydrolysis product formed in step (Al). The neutralizing agent is not critical and may be, for example, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, or potassium hydroxide. The amount of neutralizing agent depends on various factors including the type and amount of catalyst used in step (Al), however, the amount of neutralizing agent may be, for example 500 ppm to 2,000 ppm based on weight of the silsesquioxane resin to be produced in step (Al). The neutralizing agent may be removed by filtration after neutralizing is complete, e.g., before or after step (A2).

[0030] A solvent may optionally be included during and / or after step (Al) and / or step (A2) of the method described above to facilitate mixing of the starting materials and the aryl-, epoxycycloalkyl-, alkenyl- functional silsesquioxane resin produced in step (Al). The solvent is not critical and may be, for example, an aromatic hydrocarbon exemplified by benzene, toluene, xylene, or a combination thereof.

[0031] Alternatively, in step (Al), starting materials (al-1) the aryltrialkoxysilane, (al-3) thebis-alkenyl-terminated dialkylsiloxane oligomer, (cl) the catalyst, and (a 1-4) the water may be combined and heated, optionally with solvent. Thereafter, the neutralizing agent described above may be added, for example, when a strong acid catalyst such as trifluoromethane sulfonic acid is used for starting material (c2). The neutralizing agent may be a strong base, such as KOH. In this method, (a 1-2) the epoxycycloalkyl - functional trialkoxysilane may then be added, and additional water may be added, with heating. Without wishing to be bound by theory, it is thought that the strong acid catalyst may be neutralized and thereby prevented from catalyzing a ring opening reaction of the epoxy- moiety of starting material (al -2). And, when a molar excess of the strong base is used, this may function as a catalyst to react starting material (al -2) with the reaction product described above. Thereafter, step (A2) of the method may be performed.

[0032] In step (A2) of the method, the aryl-, epoxy cycloalkyl-, alkenyl- functional silsesquioxane resin prepared in step (Al) (which silsesquioxane resin will form the non - linear block of the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer described above), is combined with additional starting materials under conditions to effect hydrosilylation reaction to bond the linear block to the non - linear block. The block with subscript c, shown above in unit Formula (A) forms via the hydrosilylation reaction in step (A2) (i.e., of the alkenyl group from the aryl-, epoxycycloalkyl-, alkenyl- functional silsesquioxane (e.g., MV1T) resin formed in step (Al) with a silicon bonded hydrogen atom of starting material (a2-l) and / or (a2-2) in step (A2) of the method described above). Hydrosilylation may be performed by any convenient means, such as heating under inert atmosphere. The hydrosilylation may be performed in the same reactor as step (Al) or a different reactor.

[0033] Starting material (a2-l) used in step (A2) of the method described above is a linear polyorganohydrogensiloxane that may be used to form the linear blocks of the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer of unit formula (R12HSiOi / 2)2(R22SiO2 / 2)h, where each R1and each R2are the independently selected monovalent hydrocarbyl groups of 1 to 30 carbon atoms, subscript h represents an average number of disiloxy units per molecule, and subscript h is an integer with a value of 8 to 398. Alternatively, each R1may be alkyl, alternatively methyl. Alternatively, each R2may be alkyl or aryl; alternatively methyl or phenyl. Alternatively, subscript h may have a value of at least 8, alternatively at least 10, alternatively at least 20, alternatively at least 48, alternatively at least 98, alternatively at least 148, alternatively at least 198; while at the same time, subscript h may be up to 398, alternatively up to 298, alternatively up to 198. Alternatively, subscript h may be 8 to 298, alternatively 23 to 224, alternatively 48 to 198, alternatively 73 to 148, alternatively 73 to 123, and alternatively h = 97. Starting material (a2-l) may be used to form the linear blocksof the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer. Examples of suitable linear polyorganohydrogensiloxanes suitable as starting material (a2-l) are exemplified by bis-dimethylhydridosiloxy-terminated polydimethylsiloxanes with varying degrees of polymerization, as described above. Linear polyorganohydrogensiloxanes suitable as starting material (a2-l) are commercially available, such as those available from Gelest, Inc., for example, hydride terminated polydimethylsiloxanes with product codes DMS-H03, DMS-H05, DMS-H11, DMS-H21, DMS-H25, DMS-H31, or DMS-H41. Methods of preparing linear polyorganohydrogensiloxanes suitable for use herein, such as hydrolysis and condensation of organohalosilanes, are well known in the art, as exemplified in: US Patent 3957713 to Jeram et al. and US Patent 4329273 to Hardman, et al.

[0034] Starting material (a2-2) is an organohydrogensiloxane crosslinker that crosslinks non - linear blocks of the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer, as described above. This crosslinker may comprise an organohydrogensiloxane comprising two or more siloxane units selected from, HR^SiOic, R SiO , HR2SiC>2 / 2, R22SiO / 2, R2SiO3 / 2, HSiO3 / 2 and SiC>4 / 2 units, with the proviso that at least 2 units per molecule contain a silicon bonded hydrogen atom. In the preceding formulae, each R1and each R2are a monovalent hydrocarbyl groups as described above. Alternatively in this crosslinker, each R1may be alkyl such as methyl. Alternatively, in this crosslinker, each R2may be alkyl such as methyl or aryl such as phenyl. This organohydrogensiloxane crosslinker may be linear, branched, cyclic, resinous, or a combination thereof. Alternatively, the organohydrogensiloxane crosslinker may be linear or branched. Alternatively, the organohydrogensiloxane may be linear.

[0035] For example, the linear organohydrogensiloxane crosslinker may comprise an aryl- functional siloxane oligomer of unit formula (R1HSiOi / 2)2(R82SiO2 / 2)j, where each R1is the independently selected monovalent hydrocarbyl group of 1 to 30 carbon atoms, as described above; each R8is an independently selected aryl group of 6 to 30 carbon atoms as described above; and subscript j represents average number of disiloxy units per molecule, and subscript j is an integer with a value of 1 to 3. Alternatively, in this unit formula each R1may be alkyl such as methyl. Alternatively, in this unit formula each R8may be aryl such as phenyl. Subscript j may be 1, 2, or 3; alternatively 1 or 2, and alternatively ] may be 1. The crosslinker, may be, for example l,l,5,5-tetramethyl-3,3-diphenyltrisiloxane (CAS No. 17875-55-7) which is commercially available from Sigma Aldrich, Inc.

[0036] Starting material (c2) is a hydrosilylation reaction catalyst. The hydrosilylation reaction catalyst will promote a reaction between the alkenyl groups of the silsesquioxane resin and the silicon bonded hydrogen atoms of starting materials (a2-l) and (a2-2), described above. The hydrosilylation reaction catalyst comprises a platinum group metal. The platinum groupmetal may be selected from the group consisting of platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the platinum group metal may be platinum. The hydrosilylation reaction catalyst may be the platinum group metal or a compound or complex of the platinum group metal. For example, the hydrosilylation reaction catalyst may be a compound such as chloridotris(triphenylphosphane)rhodium(I) (Wilkinson’s Catalyst), a rhodium diphosphine chelate such as [l,2-bis(diphenylphosphino)ethane]dichlorodirhodium or [l,2-bis(diethylphospino)ethane]dichlorodirhodium, chloroplatinic acid (Speier’s Catalyst), chloroplatinic acid hexahydrate, platinum dichloride, or a complex of such a compound with an organopolysiloxane such as l,3-diethenyl-l,l,3,3-tetramethyldisiloxane complexes with platinum (Karstedt’s Catalyst) or Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane (Ashby’s Catalyst). Alternatively, the compound or complex may be microencapsulated in a matrix or coreshell type structure. Hydrosilylation reaction catalysts are known in the art, for example, as described in PCT Patent Application Publication WO2021 / 081822 to Guo, et al. and the references cited therein. Hydrosilylation reaction catalysts are commercially available, for example, SYL-OFF™ 4000 Catalyst and SYL-OFF™ 2700 are available from Dow Silicones Corporation of Midland, Michigan, USA. The amount of hydrosilylation reaction catalyst depends on various factors including the selections and SiH contents of starting materials (a2-l) and (a2-2), the alkenyl content of the silsesquioxane resin, and the hydrosilylation reaction conditions, such as temperature, however the amount may be sufficient to provide 0.1 to 5,000 ppm of platinum group metal, alternatively 1 to 1,000 ppm, alternatively 1 to 100 ppm, and alternatively 1 to 10 ppm, based on combined weights of the silsesquioxane resin and starting materials (a2-l) and (a2-2).

[0037] In step (A2) of the method described above, the silsesquioxane resin and starting materials (a2-l), (a2-2), and (c2) and optionally a solvent to aid mixing may be combined in a reactor with heating to a temperature of 50 °C to 150 °C, alternatively 90 °C to 110 °C. Typically, the silsesquioxane resin is used in a molar excess such that the resulting epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer may have residual silicon bonded alkenyl groups, and does not contain unreacted SiH. Alternatively, starting material (a2-l) may be reacted with the silsesquioxane resin until all of its SiH is reacted, thereby preparing a resin - linear intermediate and thereafter starting material (a2-2) may be reacted with the resin - linear intermediate. Typically, the hydrosilylation reaction is performed under inert conditions (i.e., < 2% oxygen atmosphere) for safe handling of SiH functional starting material.

[0038] In step (A3) of the method described above, recovering the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer may be performed by anyconvenient means, such as stripping and / or distillation, optionally with reduced pressure.

[0039] Alternatively, the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer may comprise unit Formula (B) as follows(ZOi / 2)s (B), whereinR1, R2, D1, R3, R4, and Z are as described and exemplified above for Formula (A); subscripts m, n, o, p, q, and r represent mole fractions of each siloxy unit in the unitFormula (B), and have values such that0 < m < 0.1;0.3 < n < 0.8;0.035 < o < 0.285;0.3 < (n + o) < 0.8;0.035 < p < 0.285;0.1 < q < 0.7;0.035 < r < 0.285; a quantity (m + n + o + p + q + r) = l; and subscript s represents a molar amount of hydrolyzable groups in the copolymer, and subscript s has a value such that 0 < s < 0.5.

[0040] In Formula (B), each of subscripts m, n, o, p, q, and r represent mole fractions of each siloxy unit in the unit formula. Subscripts m, n. o, p, q, and r have values such that 0 < m < 0. 1; 0.3 < n < 0.8; 0.035 < o < 0.8; 0.3 < (n + o) < 0.8; 0.035 < p < 0.8; 0.1 < q < 0.7; and 0.035 < r < 0.285. Alternatively, subscript o may have a value such that 0.035 < o < 0.1. Alternatively, subscript p may have a value such that 0.035 < p < 0.1. Alternatively, subscript r may have a value such that 0.035 < r < 0.1. In Formula (B), subscript s represents a molar amount of hydrolyzable groups in the copolymer. Subscript s has a value such that 0 < s < 0.5, alternatively 0.05 < s < 0.35; and alternatively 0.05 < s < 0.2. Alternatively, subscript m may have a value such that 0 < m < 0.1, alternatively 0 < m < 0.05, and alternatively 0.01 < m < 0.05. Alternatively, subscript n may have a value such that 0.3 < n < 0.6, alternatively 0.3 < n < 0.5; and alternatively 0.35 < n < 0.65. Alternatively , subscript o may have a value such that 0 < o < 0. 15; alternatively 0.01 < o < 0.2. Alternatively , subscript p may have a value such that 0 < p < 0. 15; alternatively 0.01 < p < 0.2. Alternatively subscript q may have a value such that 0.15 < q< 0.65; alternatively 0.2 < q < 0.6, and alternatively 0.3 < q < 0.5. Alternatively, subscript r mayhave a value such that 0.035 < r < 0.1; alternatively 0.05 < r < 0.1; alternatively 0.06 < r < 0.08; and alternatively r = 0.7. Subscript s represents a molar amount of hydrolyzable groups in the copolymer, and subscript s has a value such that 0 < s < 0.5; alternatively 0.05 < s < 0.35; and alternatively 0.05 < s < 0.20.

[0041] The epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer comprising unit Formula (B) may be prepared by a method comprising:(Bl) combining, under conditions to effect hydrosilylation reaction, starting materials comprising(b 1-1) an alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer comprising difunctional siloxy units and trifunctional siloxy units, wherein (bl -1 ) the alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer comprises unit formula (R142SiO2 / 2)t(R15SiO3 / 2)u(ZOi / 2)v, wherein each R14and each R15are independently selected monovalent hydrocarbyl groups of 1 to 30 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and a monovalent hydrocarbyl group of 1 to 30 carbon atoms; subscripts t and u represent mole fractions of siloxy units in (bl - 1 ) the alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer, and subscripts t and u have values such that0.4 < t < 0.9 and0.1 < u < 0.6, and a quantity (t + u) = 1 , subscript v represents a mole fraction of hydrolyzable groups and has a value such that0 < v < 0.5, wherein the disiloxy units are arranged in linear blocks having an average of 10 to 400 units of formula (R142SiO2 / 2) per linear block; and wherein the trisiloxy units of formula (R15SiO3 / 2) are arranged in non - linear blocks, wherein each non - linear block has a molecular weight of at least 500 g / mol; and (bl -2) an epoxy cycloalkyl-functional silyl hydride compound of formula;wherein each R16is an independently selected monovalent hydrocarbyl group of 1 to 30 carbonatoms,R4is the epoxycycloalkyl-functional group as described and exemplified above, and subscript w is an integer with a value of 0, 1 , or 2; and (c2) a hydrosilylation reaction catalyst, as described and exemplified above; and optionally (B2) recovering the copolymer from the hydrosilylation reaction product.

[0042] Starting material (bl -1) is an alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer that may be prepared by known methods, such as those described in US Patent 9765192 to Horstman, et al., which is hereby incorporated by reference. Starting material (b 1 - 1 ) may comprise unit formula (R142SiO2 / 2)t(R15SiO3 / 2)u(ZOi / 2)v, wherein each R14and each R15are independently selected monovalent hydrocarbyl groups of 1 to 30 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and a monovalent hydrocarbyl group of 1 to 30 carbon atoms; subscripts t and u represent mole fractions of siloxy units in (b 1 - 1 ) the alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer, and subscripts t and u have values such that 0.4 < t < 0.9 and 0.1 < u < 0.6, and a quantity (t + u) = 1 , subscript v represents a mole fraction of hydrolyzable groups and has a value such that 0 < v < 0.5. In starting material (bl -1 ), each R14is an independently selected monovalent hydrocarbyl group of 1 to 30 carbon atoms. Each R14may be free of aliphatically unsaturated bonds, e.g., R14may be selected from alkyl or aryl, as described and exemplified above for R1and R2. Alternatively, each R14may be alkyl. Alternatively, each R14may be methyl.

[0043] In starting material (bl - 1 ), each R15may be independently selected from alkyl, alkenyl, and aryl; alternatively each R1Smay be independently selected from alkenyl and aryl. The alkyl group and the aryl group for R15may be as described above for R1and R2. The alkenyl for R15may be as described above for R3. Alternatively, the alkyl group for R15may be methyl. Alternatively, the aryl group for R15may be phenyl or naphthyl, alternatively phenyl. Alternatively, the alkenyl group for R15may be vinyl, allyl, or hexenyl; alternatively vinyl or hexenyl; alternatively vinyl or allyl; and alternatively vinyl. The alkenyl-, aryl- functional resin - linear copolymer may comprise 0.5 mol% to 5 mol% of alkenyl groups. The balance of instances of R15that are not alkenyl groups may be aryl groups.

[0044] Subscripts t and u represent mole fractions of siloxy units in (bl-1) the alkenyl-, aryl- functional resin - linear copolymer, and subscripts t and u have values such that 0.4 < t < 0.9 and 0.1 < u < 0.6, and a quantity (t + u) = 1. Subscript v represents a mole fraction of hydrolyzable groups and has a value such that 0 < v < 0.5. Alternatively, subscript v may have a value such that 0.05 < v < 0.35, alternatively 0.05 < v < 0.2.

[0045] The alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer is ablock copolymer (not a random copolymer). The difunctional units of formula (R142SiO2 / 2) are primarily bonded together to form polymeric polydiorganosiloxane chains having 10 to 400 (R142SiO2 / 2) units, which are linear blocks. The (R15SiO3 / 2) units are primarily bonded to each other to form branched polymeric chains, which are non - linear blocks. A significant number of these non - linear blocks may aggregate to form nano-domains when solid forms of the alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer are provided. The disiloxy units of formula (R142SiO2 / 2) that are arranged in linear blocks have an average of 10 to 400 units of formula (R142SiO2 / 2) per linear block. Alternatively, each linear block may have an average of at least 10, alternatively at least 50, alternatively at least 100, alternatively at least 150, and alternatively at least 200 units of formula (R142SiO2 / 2): while at the same time each linear block may have up to 400, alternatively up to 300, and alternatively up to 200, units of formula (R142SiO2 / 2) per linear block. Alternatively, each linear block may have 100 to 150 (R142SiO2 / 2) units, alternatively 115 to 125 (R142SiO2 / 2) units, alternatively 90 to 170 (R142SiO2 / 2) units. The linear blocks are covalently bonded to the non - linear blocks.

[0046] The (R15SiO3 / 2) units are arranged in the non - linear blocks. The non - linear blocks each have a molecular weight of at least 500 g / mol, alternatively 500 g / mol to 4,000 g / mol per block. Alternatively, each non - linear block may have a Mn of at least 500 g / mol, alternatively at least 1,000 g / mol, alternatively at least 1,500 g / mol; while at the same time each non - linear block may have a Mn of up to 4,000 g / mol, alternatively up to 3,000 g / mol; alternatively up to 2,500 g / mol; alternatively up to 2,000 g / mol; and alternatively up to 1,500 g / mol, measured by GPC according to the test method described in the EXAMPLES, below.

[0047] The hydrolyzable groups may allow the alkenyl-, aryl- functional resin - linear copolymer to further react or cure or to crosslink. Crosslinking of the non - linear blocks may be accomplished via a variety of chemical mechanisms and / or moieties. For example, crosslinking of the non - linear blocks within the copolymer may result from condensation of residual silanol and / or alkoxy groups present in the non - linear blocks. At least 30% of the non - linear blocks in the copolymer may be crosslinked with each other, alternatively at least 40%, alternatively at least 50%, alternatively at least 60%, alternatively at least 70%, and alternatively at least 80%. Alternatively, 30% to 80% of the non - linear blocks may be crosslinked with each other, alternatively 30% to 70%, alternatively 30% to 60%, alternatively 30% to 40%, and alternatively 30% to 40% of the non - linear blocks are crosslinked with each other.

[0048] The alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer may have a Mw of 20,000 g / mol to 500,000 g / mol. Alternatively, the copolymer may have a Mw of at least 20,000 g / mol, alternatively at least 40,000 g / mol, alternatively at least 50,000 g / mol, alternatively at least 55,000 g / mol, alternatively at least 60,000 g / mol, and alternatively at least65,000 g / mol; while at the same time Mw may be up to 500,000 g / mol, alternatively up to 450,000 g / mol, alternatively up to 400,000 g / mol, alternatively up to 350,000 g / mol, alternatively up to 300,000 g / mol; alternatively up to 250,000 g / mol; alternatively up to 200,000 g / mol; alternatively up to 150,000 g / mol and alternatively up to 125,000 g / mol. Alternatively, the alkenyl-, aryl- functional resin - linear copolymer may have a Mn of 15,000 to 50,000 g / mol. Alternatively, the alkenyl-, aryl- functional resin - linear copolymer may have Mn of at least 15,000 g / mol, alternatively at least 20,000 g / mol; while at the same time Mn may be up to 50,000 g / mol, alternatively up to 30,00 g / mol, alternatively up to 25,000 g / mol. Mw and Mn may be measured by GPC using the test method described in the EXAMPLES, below.

[0049] The alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer may be isolated in a solid form, for example, by casting a film of a solution of the alkenyl-, aryl- functional resin - linear copolymer in an organic solvent (e.g., benzene, toluene, xylene, or combinations thereof) and allowing the solvent to evaporate. The alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer may be provided in a solution in an organic solvent in an amount of 50% to 80%, alternatively 60% to 80%, copolymer solids with the balance being organic solvent in the solution. The solution may be cast as a film and then dried to remove the solvent and form a solid, and the non - linear blocks may further aggregate together to form nano - domains, as described above. Alternatively, the solid alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer may contain a first phase and an incompatible second phase, the first phase containing predominantly the linear block and the second phase containing predominantly the non - linear block, the non - linear blocks being sufficiently aggregated into nano - domains that are incompatible with the first phase.

[0050] Starting material (bl -2) is an epoxycycloalkyl-functional silyl hydride compound of formula, wherein each R16is an independently selected monovalent hydrocarbyl group of 1 to 30 carbon atoms, R4is the epoxycycloalkyl-functional group as described and exemplified above, and subscript w is an integer with a value of 0, 1 , or 2. The monovalent hydrocarbyl group for R16is as described and exemplified above for R1and R2. Alternatively, each R16may be independently selected from the group consisting of an alkyl group and an aryl group. Alternatively, each R16may be an alkyl group. Alternatively, each R16may be methyl. Epoxycycloalkyl-functional silyl hydride compounds of the formula shown above are known in the art see for example, US Patent Publications 20220112223 and 20220098222, both to Eldred, et al., which are hereby incorporated by reference for the purposeof disclosing epoxycycloalkyl-functional silyl hydride compounds. The amount of starting material (bl-2) may be sufficient to provide 3.5 mol% to 15 mol%, based on mole number of starting material (bl-1).

[0051] Starting material (c2) is the hydrosilylation reaction catalyst, which is as described and exemplified above. Alternatively, in step (Bl), the hydrosilylation reaction catalyst may be a compound such as chloridotris(triphenylphosphane)rhodium(I) (Wilkinson’s Catalyst), a rhodium diphosphine chelate such as [l,2-bis(diphenylphosphino)ethane]dichlorodirhodium or [l,2-bis(diethylphospino)ethane]dichlorodirhodium, chloroplatinic acid (Speier’s Catalyst), chloroplatinic acid hexahydrate, platinum dichloride, or a complex of such a compound with an organopolysiloxane such as l,3-diethenyl-l,l,3,3-tetramethyldisiloxane complexes with platinum (Karstedt’s Catalyst) or Pt(O) complex in tetramethyltetravinylcyclotetrasiloxane (Ashby’s Catalyst). Alternatively, the compound or complex may be microencapsulated in a matrix or coreshell type structure. The amount of hydrosilylation reaction catalyst used in this method depends on various factors including the selection and SiH content of starting materials (bl-2), the alkenyl content of (bl-1) the alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer, and the hydrosilylation reaction conditions, such as temperature, however the amount may be sufficient to provide 0.1 to 5,000 ppm of platinum group metal, alternatively 1 to 1,000 ppm, alternatively 1 to 100 ppm, and alternatively 1 to 10 ppm, based on combined weights of starting materials (bl-1) and (bl-2).

[0052] A solvent may optionally be included during and / or after step (Bl) of the method described above to facilitate mixing of the starting materials. The solvent is not critical and may be, for example, an aromatic hydrocarbon exemplified by benzene, toluene, xylene, or a combination thereof.

[0053] In step (Bl) of the method described above, the starting materials (bl-1), (bl-2), and (c2), and optionally a solvent to aid mixing, may be combined in a reactor with heating at a temperature of 50 °C to 150 °C, alternatively 90 °C to 110 °C. Typically, (bl-1) the alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer used in a molar excess such that the resulting epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer may have residual silicon bonded alkenyl groups, and does not contain unreacted SiH. Typically, the hydrosilylation reaction is performed under inert conditions (i.e., < 2% oxygen atmosphere) for safe handling of SiH functional starting material.

[0054] In step (B2) of the method described above, recovering the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer may be performed by any convenient means, such as stripping and / or distillation, optionally with reduced pressure.

[0055] The epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymerdescribed above is useful in curable compositions. For example, a curable composition may comprise: (I) the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer, and a catalytically effective amount of (II) a catalyst. The curable composition may optionally further comprise an additional starting material, which may be selected from the group consisting of: a solvent, an organosiloxane resin, a stabilizer, a phosphor, a moisture scavenger, a metal-ligand complex, a filler, and a combination of two or more thereof.

[0056] Suitable solvents are exemplified by the aromatic hydrocarbons described above (e.g., benzene, toluene, xylene, and combinations thereof). Alternatively, a polar solvent, such as that described in US Patent Publication US20160118555 paragraph

[0104] may be used. The optional additional organosiloxane resin may be, for example, a polyorganosilicate resin, or may be a resin used in preparation of the copolymer herein (such as the silsesquioxane resin made in step (Al) of the first method for making the copolymer, described above). Alternatively, the optional additional resin may comprise the resin - linear intermediate made in step (A2) and / or an unreacted alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer as described above for starting material (bl-l) in the methods described above. Suitable stabilizers include boron compounds exemplified by boronic acid comprising an aromatic group, which is optionally fluorinated, such as those disclosed in US Patent 9006356. Suitable phosphors are known in the art and are disclosed, for example, in US Patent 9175140 at col. 22, lines 1 to 57; in US Patent 9927703 at col. 6, lines 19-63; or in US Patent Publication US20160009866 at paragraphs

[0222] to

[0223] . The moisture scavenger may be an alkoxy silane, such as isobutyltriethoxysilane. Suitable moisture scavengers are disclosed in US Patent 9051436 at col. 28 line 59. Suitable metal - ligand complexes are as disclosed in US Patent 9175140 at col. 16, line 53-col. 20, line 57. Fillers are disclosed, for example, in US Patent 9175140 at col. 20 line 58-col. 21, line 67, and US Patent Publication US20160009866 at paragraphs

[0217] -

[0221] . Alternatively, the filler may comprise nanoparticles, such as those disclosed in US Patent publication US20160118555 at paragraphs

[0132] to

[0139] .

[0057] The curable composition may be prepared by any convenient means. For example the curable composition may be prepared by a method comprising: mixing starting materials comprising (I) the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer and (II) the catalyst under ambient conditions, and if present, any of the optional additional starting materials described above. The method may further comprise preparing the epoxycyclohexyl - functional resin - linear polyorganosiloxane block copolymer by the method described above, before mixing said epoxycyclohexyl - functional resin - linear polyorganosiloxane block copolymer with the other starting materials of the curable composition.

[0058] The curable composition described above may be a thermally curable composition, wherein the catalytically effective amount of (II) the catalyst comprises > 100 ppm of an inhibited arylborane Lewis acid. Suitable inhibited arylborane Lewis acids are known in the art and are disclosed, for example, in US Patent Publication 20220169855 at paragraphs

[0044] to

[0057] , which is hereby incorporated by reference. For example, the Lewis acid may comprise a triaryl borane, such as those having the formula:, wherein R9is independently in each occurrence selected from H, F, Cl and CF3. Alternatively, at least one R9, per molecule, is F or CF3. The arylboraneLewis acid may be inhibited with an amine. The selection of amine is important because it must complex with the Lewis acid at 23 °C to inhibit catalytic activity of the Lewis acid in a reaction composition at that temperature, yet must release the Lewis acid at an elevated temperature so as to rapidly (within 10 minutes or less, alternatively 5 minutes or less, alternatively one minute less) gel the reaction composition at 90 °C. Reaction compositions can be monitored at 23 °C and 90 °C to determine gel times. Alternatively, or additionally, one can characterize by differential scanning calorimetry the temperature at which the curing reaction exotherm occurs (Tpeak). The Tpeak value for a composition should increase relative to the Tpeak for an identical amine-free composition if the proper amine is present, but desirably remains below 130 °C, alternatively below 120 °C, alternatively below 110 °C so as to reflect dissociation sufficient to rapidly cure at 90 °C.

[0059] Amines have been reported as irreversibly complexing with Lewis acid catalysts, except for triaryl amines which are reported to not compromise Lewis acid catalysts. Without wishing to be bound by theory, having one or more conjugated moiety attached the nitrogen of an amine through a conjugated carbon, the conjugated moiety helps delocalize the free electrons of the amine and weaken it as a Lewis base. As a result, amines having at least one conjugated moiety attached to the nitrogen of the amine through a conjugated carbon complex with and block Lewis acid catalyst at 23 °C so as preclude gelling of a reaction composition at 23 °C in 4 hours or less, alternatively 8 hours or less, alternatively 10 hours or less, alternatively 12 hours less, while at the same time complexes weakly enough so as to release the Lewis acid catalyst upon heating to 90 °C so as to gel the composition in 10 minutes or less, alternatively 5 minutesor less, alternatively one minute or less.

[0060] To be a sufficiently weak Lewis base, the amines have at least one, alternatively at least two, and can have three conjugated moieties attached to the nitrogen of the amine through a conjugated carbon so that the free electron pair on the nitrogen can dissociate with the conjugated moiety and weaken the amine as a Lewis base. Alternatively, the conjugated moieties are aromatic moieties.

[0061] Triaryl amines have three aromatic conjugated moieties attached to the amine nitrogen each through a conjugated carbon. As a result, triaryl amines are examples of amines that optimally delocalize the nitrogen free electrons to create a weak Lewis base. Nonetheless, triaryl amines have been surprisingly discovered to have a blocking effect on Lewis acid catalysts at 23 °C and inhibit Lewis acid catalyzed reaction at 23 °C and are in scope of the broadest scope of the amines suitable for use in the catalyst used in the thermally curable composition described herein. Desirably, the amines used herein are stronger Lewis bases than triaryl amines in order to achieve greater blocking effect (hence, longer shelf stability) at 23 °C. In that regard, while the amine can have one, two or three conjugated moieties attached to the nitrogen of the amine through a conjugated carbon, it is desirable that the amine is other than a triaryl amine. Compositions described herein can be free of triarylamines.

[0062] The ability of a conjugated moiety to weaken the strength of the amine as a Lewis base is further tunable with substituent groups that can be attached to the conjugated moiety.Including electron withdrawing groups (such as halogens) on the conjugated moiety will further draw the nitrogen electrons into the delocalized conjugated system and weaken the strength of the amine as a Lewis base. Including electron donating groups on the conjugated moiety has the opposite effect and increases the resulting amine strength as a Lewis base relative to the same amine with the conjugated moiety without the electron donating group(s).

[0063] The amine needs to be strong enough to bind to and block the Lewis acid catalyst at 23 °C in order to achieve shelf stability. The amine will release the acid at lower temperatures if it is a weaker Lewis base than if it were a stronger Lewis base. Hence, selection of the moieties attached to the nitrogen of the amine can be selected to achieve shelf stability and reactivity at a desired temperature.

[0064] Suitable amines have the amine nitrogen that is not a member of an N=C-N linkage such as in amidines, guanidines, and N-methylimidazole. Desirably, the composition is free of amines having an N=C-N linkage. For example, the composition can be free of amidines and guanidines.

[0065] In general, the amine has the following formula: RnR12R13N; wherein each of R11,R 1 , and R 17 is independently selected from a group consisting of hydrogen, alkyl, substitutedalkyl, and conjugated moieties; and wherein at least one of R11, R12and R13is a conjugated moiety connected to the nitrogen by a conjugated carbon. One, two or three of R11, R12and R13can be a conjugated moiety connected to the nitrogen by a conjugated carbon. Alternatively, the conjugated moiety may be an aromatic moiety.

[0066] Examples of suitable amines for use herein include any one or any combination of more than one amine selected from a group consisting of: aniline, 4-methylaniline, 4- fluoroaniline, 2-chloro-4-fluoroaniline, diphenylamine, diphenylmethylamine, triphenylamine , 1 -naphthylamine, 2-naphthylamine, 1 -aminoanthracene, 2-aminoanthracene, 9-aminoanthracene, P-aminostyrene, 1,3,5-hexatrien-l-amine, N,N-dimethyl-l,3,5-hexatrien-l-amine, 3-amino-2- propenal and 4-amino-3-buten-2-one.

[0067] The concentration of amine is at least at a molar equivalent to the concentration of Lewis acid so as to be able to complex with and block all of the Lewis acid catalyst at 23 °C. The concentration of amine can exceed the molar concentration of Lewis acid catalyst, but may be present at a concentration of 110 mol% or less, alternatively 105 mol% or less, alternatively 103 mol% or less and alternatively 101 mol% or less while also being present at 100 mol% or more relative to total moles of Lewis acid catalyst.

[0068] The amine and Lewis acid form a complex in the thermally curable composition that blocks the Lewis acid from catalyzing a reaction between the other composition components sufficiently to be shelf stable at 23 °C. Upon heating, the amine releases the Lewis acid to allow the Lewis acid to catalyze a reaction.

[0069] The amount of inhibited arylborane Lewis acid catalyst in the thermally curable composition may be > 100 ppm, alternatively at least 200 ppm, alternatively at least 300 ppm; while at the same time the amount may be up to 1,000 ppm, alternatively up to 500 ppm, alternatively up to 400 ppm, based on weight of the epoxycyclohexyl - functional resin - linear polyorganosiloxane block copolymer.

[0070] Alternatively, the curable composition described above may be a UV curable composition, wherein (II) the catalyst comprises a photoacid generator. Without wishing to be bound by theory, it is thought that a ring opening reaction of the epoxycycloalkyl - functional group may be initiated under UV irradiation by photoacid generators (PAGs), which are known in the art, for example, as described in US Patent 8367,212 at col. 10, lines 1-14. Suitable PAGs for use in the UV curable composition herein are exemplified by, but not limited to, diaryliodonium or triarylsulfonium based photoacid generators. Suitable PAGs include (4- dodecyl-3’-methyldiphenyliodonium antimonate salt; triarylsulfonium hexafluoroantimonate salt (TAS-SbFe from Aldrich), 4,4’-didodecyldiphenyliodonium antimonate salt (CizAr l-SbFe from GE), and 4-isopropyl-4’-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (Ar2l-BCF4from Gelest). The amount of photoacid generator depends on various factors including the epoxy - content of the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer, however the amount in the UV curable composition may be at least 0.1 %, alternatively at least 0.3%, while at the same time the amount may be up to 20%, alternatively up to 10%, alternatively up to 1% alternatively up to 0.5%, based on weight of epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer.

[0071] The curable composition described above is useful for preparing an encapsulant, such as an optical encapsulant film. The curable composition, and cured product thereof, may be used, for example, in addition to, or instead of, the encapsulant and / or the resin - linear polyorganosiloxane block copolymer described in US Patents 8921493, 8921494, 9045668, 9051436, 9076934, 9175140, 9181402, 9212262, 9705056, 9765192, 9927703, 10155885, and 11015025; US Patent Publications 20160009866, 20160032148, 20160118555, and 20170194539; and PCT Patent Publications WO2013134018 and WO2014002919. The curable composition may be used in a method comprising: 1) applying the curable composition described above to a substrate (such as that disclosed in any of the references cited above), optionally 2) removing solvent, when present, and 3) curing the composition. Curing the composition may be performed by any convenient means, such as heating when the catalyst comprises > 100 ppm of an inhibited fluorinated arylborane Lewis acid or exposure to UV radiation when the catalyst comprises a photoacid generator.EXAMPLES

[0072] The following examples are provided to illustrate the invention to one skilled in the art and are not to be interpreted as limiting the scope of the invention set forth in the claims. The starting materials used in these examples are summarized below in Table 1.Table 1 - Starting Materials

[0073] In this synthesis example 1 , epoxy-functional resin intermediates were prepared by combining phenyltrimethoxysilane (420.22 g), l,3-divinyl-l,l,3,3-tetramethyldisiloxane (22.83 g), FC-24 (0.223 g, which is an amount sufficient to provide 500 ppm by weight based onweights of the phenyltrimethoxysilane and l,3-divinyl-l,l,3,3-tetramethyldisiloxane). The resulting mixture was heated to 50 °C, and deionized water (8.82 g) was added slowly. The resulting mixture was heated at 65 °C for 3 hours.

[0074] Toluene (255.12 g) was added to the above mixture, and KOH solution (0.888 g, an amount sufficient to provide 1 ,000 ppm KOH based on theoretical yield of the resin) to neutralize the FC-24.

[0075] Next, [2-(3,4-epoxycyclohexyl)ethyl] trimethoxy silane (21.11 g) was added to the mixture prepared as described above. The resulting mixture was heated to 50 °C, and deionized water (92.48 g) was added slowly. The total amount of water added up to this step was 0.85 mol water : 1 mol methoxy moieties. The reaction mixture was heated at 65 °C for 1 hour.

[0076] Next, the reaction mixture was distilled, and 200.74 g of volatiles were removed. Toluene (155.78 g) was added. Distillation was repeated, and 155.54 g volatiles were removed. Toluene (156.61 g) was added. Distillation was repeated, and 154.44 g of volatiles were removed. Toluene (68.3 g) was added. The resulting mixture was heated at reflux for 10 hours, and the aqueous phase was removed within the first hour.

[0077] The resulting solution was cooled to 60 °C, and glacial acetic acid (0.37 g) was added. The resulting mixture was stirred at room temperature overnight. After this, the resulting mixture was filtered through a 47 mm diameter Magna, Nylon, Supported, Plain, 0.45 Micron filter. Some of the solvent was removed by rotary evaporation under vacuum at 30 °C. The resulting solution was re- filtered solution after setting at room temperature over the weekend. The solution had just a faint haze before filtration and was clear afterwards.

[0078] The resulting solventless resin intermediate (NVC sample) was a brittle solid at room temperature. The sample was analyzed by GPC and was found to have Mn= 1,508 g / mol and Mw= 2,155 g / mol (relative to polystyrene standards in THF). Isolated Yield: 405.4g of solution (at an NVC of 72.27% this amounts to 293.0g of solids). The resin had unit formula: MVi T-CEP ’-rPh 0.11 0.035 1 0.865-

[0079] In this synthesis example 2, synthesis example 1 was repeated two times, except that the amount of [2-(3,4-epoxycyclohexyl)ethyl] trimethoxysilane was changed. The resulting resins had unit formulas MV1o.o9TCEPo.o7TPho.83i and MV1o.72TCEPo.o7TPho.s5. These are summarized below in Table 4.

[0080] In this synthesis example 3, synthesis example 2 was repeated except 3- glycidoxypropyltrimethoxy silane was used instead of 2-(3,4-epoxycyclohexyl)ethyl] trimethoxysilane. The resulting resin intermediate had unit formula MV1o.iTPEPo.o7TPho.83.

[0081] In this synthesis example 4, the three resin intermediates prepared in synthesis examples 1-3 were used to synthesize epoxy - functional resin - linear polyorganosiloxaneblock copolymers by hydrosilylation between the vinyl groups on each resin intermediate and the silicon bonded hydrogen atoms of and MHDPh2MH(shown above in Table 1), as follows. A three neck flask equipped with a Teflon stir paddle attached to a glass stir shaft, thermocouple, and a Dean Stark apparatus and water cooled condenser was used for this example. Into the flask were added a solution of resin intermediate dissolved in toluene prepared as described above (124.53 g of which 90 g is resin solids with 0.0648 mol Vi), 110 g of MHD9gMH, and 265.47 g toluene plus an amount of toluene equal to the volume of the Dean Stark apparatus. The resulting mixture was heated to reflux, and the Dean Stark apparatus filled with toluene. The first milliliters of toluene collected in the Dean Stark apparatus were hazy, and the remainder was clear. The reaction mixture was opaque at reflux. The reaction mixture was cooled to 105 °C, and Pt catalyst solution in an amount sufficient to provide 5 ppm Pt based on resin and linear siloxanes. The reaction mixture turned translucent after 2 minutes. By the time the reaction mixture reached reflux, the reaction mixture was clear. The reaction mixture was heated at reflux for 1 hour, and then a sample analyzed by FTIR showed no SiH remained.

[0082] Next, MHDPh2MH(2.90g) was added at RT with mixing. The resulting mixture was heated at 100 °C for 1 hour. The sample was then analyzed by FTIR, which showed no SiH left. The sample was used to prepare a solventless film on a glass slide, and the film was clear.

[0083] The sample was then cooled to RT and pressure filtered through a 142mm diameter Magna, Nylon, Supported, Plain, 5.0 Micron filter. The solids content of the sample was increased using a rotary evaporator at an oil bath temperature of 50 °C under vacuum. The resulting product NVC films were clear, smooth, and flexible. The calculated epoxy content was: 8,230 g / mol epoxy (solids basis). This procedure produced Sample 4- 1 in Table 2, below. The above procedure was repeated with the resin intermediates of Synthesis examples 2 and 3. The copolymers produced are described below in Table 2.Table 2 - Resin - Linear Polyorganosiloxane Block Copolymer Samples Prepared by Synthesis Example 4

[0084] In this synthesis example 5, EP-MHintermediate (described above in Table 1) was prepared as follows: To a 500 mL flask were added 24.8 g (0.2 mol) 4-Vinyl-cyclohexane 1.2- epoxide, 80.4 g (0.6 mol) MHMH, 60 mL toluene and Karstedt’s catalyst (in an amount sufficient to provide 3 ppm Pt), followed by stirring at 80 °C for 3 hours. Sampling to NMR after 3 hours and NMR results showed all vinyl groups converted. The solvent and excess MHMHwere removed by rotary evaporator to obtain 103 g product EP-MH, with formula:1 -(2-(7-oxabicyclo[4.1 ,0]heptan-3-yl)ethyl)-l , 1 ,3,3-tetramethyldisiloxane

[0085] In this synthesis example 6, a vinyl-functional resin - linear polyorganosiloxane block copolymer intermediate (TV1-RL) was prepared as follows: A 3L 4 neck round bottom flask was equipped with a thermocouple, Teflon stir paddle attached to a glass stir shaft, and a Dean Stark apparatus attached to a water-cooled condenser. The flask was loaded with: 217 Flake (270.00g, 1.977mols Si), toluene (722.31g) + an amount of toluene equal to the volume of the Dean Stark apparatus. A nitrogen blanket was applied. The flask was heated at reflux for 30 minutes to remove trace water from the 217 Flake. The flask was cooled to a couple of degrees below reflux and contained a resin solution.

[0086] Next, RL Coupling was performed as follows: A solution of toluene (177.69g) and Silanol Terminated PDMS (330.0g, 4.430mols Si) was capped with acetoxysilanes. The sample was prepared in a glove box (same day) under nitrogen by adding VTA (25.50g, 0.1098mols Si) and OFS-1579 (10.36g, 0.0456mols Si) to the Silanol Terminated PDMS and mixing at roomtemperature for 1 hour. Acetoxysilane capped PDMS solution was formed. The acetoxysilane capped PDMS solution was added to the above resin solution quickly. The resulting mixture was heated at reflux for 2 hours, and then left overnight at room temperature.

[0087] Next, Water Treatments 1 & 2 (each-20: 1 molar ratio, water: MTA / ETA + VTA) were performed. The following process was repeated two times: At ~90 °C added DI water (56.0g) and then removed water by azeotropic distillation, in which were distilled off 300 g of volatiles to increase the solids content up to -50%.

[0088] Next, Water Treatments 3, 4 & 5 were performed. The following process was repeated three times: At ~90°C added DI water (56.0g), and thereafter removed water by azeotropic distillation. The resulting mixture was cooled to room temperature and then pressure filtered through a 142mm diameter Magna, Nylon, Supported, Plain, 5.0 Micron filter to obtain TV1-R product.

[0089] The product was analyzed. The results showed product NVC films were clear, smooth, and flexible. Yield after filtration: 1153.7g of solution =581.5g solids. Estimated vinyl equivalent weight: 5537g / mol vinyl (based on the assumption of all acetoxy groups hydrolyzing and condensing with silanols on resin and PDMS).

[0090] In this Synthesis Example 7, an epoxycyclohexyl - functional resin - linear polyorganosiloxane block copolymer (sample 7-1) was prepared from the vinyl-functional resin - linear polyorganosiloxane block copolymer intermediate (TV1-RL) prepared as described above in synthesis example 6, as follows: To a 500 mL 3 necked flask were added 100 g of the TV1-RL prepared by the above procedure, 4.86 g Epoxy convertor (EP-MH) prepared as described above in synthesis example 5, Karstedt’s catalyst in an amount sufficient to provide 5 ppm Pt and 100 mL toluene under Nitrogen. The reaction mixture was heated to reflux for 5 hours while stirring under nitrogen. After cooling down, the reaction solution was concentrated by using a rotary evaporator under 100°C / 6mmHg. Finally 170 g concentrated liquid EP-RL product was obtained with NVC of 65%.

[0091] NMR spectra showed 96% of vinyl groups converted to epoxycyclohexyl - functional groups of formula. The epoxycyclohexyl - functional resin linear polyorganosiloxane produced in this example had Mw of 56,300 g / mol and Mn of 21,800 g / mol.

[0092] In this synthesis example 8, BCF-TEA catalysts were prepared as follows:(1) Dissolve BCF in toluene as BCF stock solution (typically 5 weight % BCF in toluene);(2) Dissolve TEA (triethylamine) or DMA (dimethylaniline) in toluene as TEA / DMA stock solution (typically 5%);(3) Add a desired amount of TEA / DMA solution into the BCF stock solution to make 1 : 1 mol ratio of [BCF] / [TEA] or [BCF] / [DMA], and then sonicate the mixture for a couple of minutes;(4) Leave the resulting prepared catalyst solution still on bench or shelf overnight before use; (because without wishing to be bound by theory, it is thought that the binding of all TEA or DMA molecules to BCF requires at least a couple of hours).

[0093] The [BCF] / [TEA] produced as described above is shown below.

[0094] Above, the structures of BCF-TEA thermal latent catalyst and the released BCF, the formation of BCF-TEA complex at RT and the dissociation of the complex to release of BCF catalyst upon heating are shown.

[0095] The samples prepared as described above were tested for ability to cure via thermal and UV mechanisms, according to the thermal cure and UV cure test methods, respectively, described below. Additional test methods used in the examples herein are also described below. Test Methods

[0096] In this Thermal cure test method, formulations comprising an epoxy - functional resin - linear polyorganosiloxane copolymer prepared according to a synthesis example described above and BCF-TEA prepared as described in synthesis example 8 were cured by thermal heating. Samples were dried at RT for 3 days and then cured for 30 min in 150 °C oven. The cure% of each cured film sample produced by this method was measured by the gel swelling test described below.

[0097] In this UV cure test method, formulations comprising an epoxy - functional resin - linear polyorganosiloxane copolymer prepared according to a synthesis example described above and a photoacid generator were cured by UV cure (365 nm UV LED lamp, 10 second, 30% intensity). Samples were dried under darkness and at RT for three days or 70 °C for 30 minand then cured for 10 seconds under 365 nm UV light. The cure% of each cured film sample produced by this method was measured by the gel swelling test, described below.

[0098] The gel swelling tested (cure%) referenced above was performed by (1) immersing each cured film sample in toluene for 45 minutes, (2) drying the sample in 150 °C oven for 2 hours, and (3) measuring the weight loss to decide the cure% (the cure% = Wd / Wo, Wd: the weight of the dried sample after immersing in toluene and drying at 150 °C, Wo: the weight of the original cured sample). The cure degree was not acceptable if the cure% < 80%.

[0099] Analysis of samples described above by29Si NMR was performed as follows: 5 g of an epoxy - functional resin - linear polyorganosiloxane block copolymer as described above was mixed with 1 mL De-benzene for NMR characterization. The29Si NMR spectra of each product were collected by a Bruker 600 MHz NMR instrument (NS = 256, dl = 60).

[0100] Analysis of samples described above by GPC was performed as follows: Samples were prepared in certified ACS grade toluene at 1 % concentration, filtered through a 0.45 um PTFE syringe filter, and analyzed against polystyrene standards. The relative calibration (3rd order fit) used for molecular weight determination was based on 12 polystyrene standards ranging in molecular weights from 580 to 906,600 Daltons. The chromatographic apparatus was a Viscotek GPC Max equipped with a vacuum degasser, a Viscotek VE358O RI detector and two (300 mm x 7.5 mm) Polymer Laboratories mixed C columns (molecular weight separation range of 200 to 3,000,000) preceded by a guard column. Separations were performed using certified grade THF programmed to flow at 1.0 mL / min, injection volume was set at 100 uL and columns and detector were heated at 35 °C. Data collection was 45 minutes and processing was performed using OmniSEC 4.7.0 software.

[0101] Tensile analysis according to CTM 0137A, ASTM D412 was performed as follows: 1 mm thick films for each epoxy - functional resin - linear polyorganosiloxane block copolymer composition were prepared in a Teflon coated Al pan, followed by either thermal cure or UV cure according to the test methods described above. Dog-bone shaped specimens were die cut from the cured films typically. Specimens were tested at ambient temperature and humidity with an Instron universal test machine utilizing Bluehill 2 software. Test speed used was 2 inch / min, and specimens were pulled to failure. Median elongation and tensile strength, at both peak and breaking point, were reported along with Young’s modulus. Raw stress-strain strain curves were also exported for further analysis and comparison with other materials.

[0102] Adhesion testing was performed as follows: The adhesion data for each sample were measured according to ASTM method D3359 by using a Gardco PA-2000 adhesion test kit after cure (according to the thermal cure or UV cure test method described above) and aging. After scratching the film surface by using a Crosshatch tool, the amount of the coating materialsremained on the Al panel surface indicated the adhesion capability of the film. The higher the remained%, the stronger the adhesion of the materials to the substrate. The adhesion was not acceptable if the amount that remained was < 80%.

[0103] Color testing for CIE B* value was performed on the cured films prepared according to the thermal cure or UV cure test method described above. CIE b* values of samples were measured by using BYK color meter. 1x3 cm2samples were cut from ~1 mm thick cured film, followed by aging at 150 °C for 5 days and then measuring b* values by using BYK color meter.The discoloration was not acceptable ifb* value was > 5.

[0104] The results are as follows: Table 3 shows data for thermally cured epoxy - functional resin - linear polyorganosiloxane block copolymers. SAMPLE 7-1, SAMPLE 4-2 and SAMPLE 4-3, each contained 7 mol% cyclohexyl epoxy and SAMPLE 4-1 contained 3.5 mol% cyclohexyl epoxy; and SAMPLE 4-4 contained 7 mol% propyl epoxy. Cl and C2 are two comparative examples which contained Vinyl functional groups and were curable by Pt catalyzed hydrosilylation. C3 is a comparative example which contained physically blended epoxy-functional phenyl-T resin (the resin intermediate prepared in synthesis example 3, above, with unit formula MV1o.iTPEPo.o7TPho.83) and epoxy terminated PDMS (MCEPDIOOMCEP). Note: all samples were cured at 150 °C for 30 minutes.Table 3

[0105] Table 3 displays the key data measured for thermally cured epoxy - functional resin - linear polyorganosiloxane block copolymers prepared as described above. The copolymer SAMPLE 7-1, SAMPLE 4-2 and SAMPLE 4-3 each contained 7 mol% Si atoms attached with cyclohexyl epoxide (CEP) functional groups, but SAMPLE 4-1 contained only 3.5 mol% Si atoms attached with cyclohexyl epoxide (CEP). SAMPLE 4-4 (Cl) contained 7 mol% propylene epoxide (PEP) - functional groups, which was less reactive than CEP. C2 is a comparative example which contained Vinyl functional resin-linear polyorganosiloxane block copolymer that did not have epoxy - functional groups and was curable by Pt catalyzed hydrosilylation. C3 was a comparative example which contained physically blended epoxy-functional phenyl-T resin (the resin intermediate prepared in synthesis example 3 with unit formula M^o.iT^o.ovT^o.ss) that was not a resin - linear polyorganosiloxane block copolymer, and epoxy terminated PDMS (MCEP2DIOO). The example compositions comprised the copolymer or comparative siloxanes described above, BCF-TEA catalyst prepared according to synthesis example 8, and 30 % toluene. Each composition was poured into a Teflon coated Al pan or PET films to make thin film (125-800 pm), and left at RT in a hood over three days to dry / remove the remained solvent toluene, and then put in 150 °C oven for 30 min to cure. Gel swelling test was done to measure the cure degree by (1) immersing each film sample in toluene for 45 minutes, (2) drying thesample in 150 °C oven for 2-3 hours, and (3) measuring the weight loss to decide the cure% (the cure% = Wd / Wo, W : the weight of the dried sample after immersing in toluene and drying at 150°C, Wo: the weight of the original sample).

[0106] Gel swelling test indicated that (i) all examples 1 to 7 showed more than 7 days shelf life at room temperature because the uncured samples completely dissolved in toluene in 30 min; (ii) the loading of BCF had to be more than 100 ppm to obtain enough thermal cure with 30 min heating at 150 °C; (iii) SAMPLE 4-1 (example 5) cured a little less than SAMPLE 7-1 (used in example 2), SAMPLE 4-2 (example 6) and SAMPLE 4-3 (example 7) since SAMPLE 4-1 contained less epoxy groups; (iv) SAMPLE 4-4 (Cl) with propyl epoxy - functional groups did not cure enough at same cure conditions because of the much lower reactivity of propyl epoxy - functional group than cyclohexyl epoxy - functional group (CEP).

[0107] The formulation of comparative example C3 was very hazy before and after cure because the phenyl-T resin (intermediate prepared in synthesis example 3 with unit formula MVio iTPEPoo7TPho 83) was not compatible with epoxy terminated PDMS polymer. The cure% of C3 was about 58%. The haze and low cure% of C3 were caused by the incompatibility between phenyl-T resin and epoxy terminated PDMS polymer, which proved the advantages of the present epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer over the a physically blended mixture of conventional epoxy functional resins and PDMS polymers.

[0108] The adhesion data in Table 3 were measured by Crosshatch Adhesion Test on F4 board or Al plate. The higher the remained%, the stronger the adhesion of the materials to substrates. Compared with the comparative hydrosilylation curable example C2, the compositions of this invention (e.g., examples 3-7) showed much stronger adhesion.

[0109] All thermally cured examples showed good thermal stability as indicated by the color (or the b* value) of all samples did not change much, and the samples were still very tough and flexible after 5 days aging at 150 °C. The good thermal stability of the cured epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymers of this invention was also confirmed by the limited change in Young’s modulus and the remaining high elongation% measured for examples 8 and 9 in Table 4 after aging at 150 °C for 5 days.Table 4: Thermal stability of BCF catalyzed thermally cured copolymers with thermally aging at 150 °C for 5 days. Triethylamine (TEA) was used as inhibitor.

[0110] The ring opening polymerization (ROP) of epoxy moieties can be also initiated under UV irradiation by photoacid generators (PAGs) such as diaryliodonium or triarylsulfonium based photoacid generators. Four commonly used and commercially available photoacid generators are shown below. PAG- Dow photoacid generator (was 4-dodecyl-3’-methyldiphenyliodonium antimonate salt). TAS-SbR, is triarylsulfonium hexafluoroantimonate salt (from Aldrich), Ci2Ar2l-SbF6 is 4,4’-didodecyldiphenyliodonium antimonate salt (from GE), and Ar2l-BCF4 is 4-isopropyl-4’-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (bought from Gelest). Most UV cured samples herein used PAG-Dow as the photoacid generator.

[0111] The structures of some commonly used diaryliodonium and triarylsulfonium based photoacid generators are shown above for reference.

[0112] Table 5 shows data for UV cured epoxy - functional resin - linear polyorganosiloxane copolymers. All examples cured by 10 second irradiation of 365 nm LED UV light with UV power of 2 J / cm2. SAMPLE 7-1, SAMPLE 4-2 and SAMPLE 4-3 containing about 7 mol% cyclohexyl epoxy and SAMPLE 4-1 containing 3.5 mol% cyclohexyl epoxy; C4 is a comparative example SAMPLE 4-4 with 7 mol% propyl epoxy. C5 was a comparative example, which comprised Vi-RL (the vinyl -functional resin - linear polyorganosiloxane block copolymer intermediate prepared in Synthesis Example 6) and was curable via hydrosilylation in the presence of UV activated Pt catalyst Pt(acac)2. C6 was a comparative example which contained physically blended epoxy-functional phenyl-T resin (intermediate prepared in synthesis example 3 with unit formula MV1o.iTPEPo.o7TPho.83) and epoxy terminated PDMS (MCEP2DIOO). C7 is a comparative example of only epoxy terminated PDMS (MCEP2D o). C8 is another comparative example containing APZ-55 (MV12sDPEP4oTPh75).

[0113] Compositions to test the UV cure efficiency and the thermal stability of the UV curable EP-RL copolymers were developed. Table 5 above shows the data measured for U V cured compositions. All examples comprised a cyclohexyl epoxide functional resin-linear (CEP-RL) (either SAMPLE 7-1, SAMPLE 4-2, SAMPLE 4-1, or SAMPLE 4-3) and photoacid generator (PAG-Dow). C4 was a comparative example of propylene epoxide functional resin-linearpolyorganosiloxane copolymer (PEP-RL, SAMPLE 4-4 above). C5 was a comparative examples which contained Vinyl functional groups curable via hydrosilylation in the presence of UV activated Pt catalyst, Pt(acac)2. Each composition was coated as a film on Teflon coated Al or PET substrates with thickness from 125 to 800 pm, dried at 70 °C for 30 min or at RT for 3 days to remove the solvent toluene. The UV cure was done by irradiating the resulting samples with 365 nm UV LED light with UV power of 2 J / cm2for 10 seconds.

[0114] The gel swelling test indicated that (1) all CEP functional resin - linear polyorganosiloxane copolymer composition examples cured well with 2J / cnr UV power (cure% > 90%); (2) all CEP functional resin - linear polyorganosiloxane copolymer composition examples cured much faster and better than hydrosilylation cured Vi-RL (in comparative example C5); (3) PEP functional resin - linear polyorganosiloxane block copolymer composition examples cured slightly less than CEP functional resin - linear polyorganosiloxane block copolymer composition (see comparative example C4)); (4) SAMPLE 7-1, SAMPLE 4-2 and SAMPLE 4-3 with higher epoxy contents cured better than SAMPLE 4-1 with less epoxy content; (5) the shelf life of the prepared films from each example was over 30 days at RT and under dark storage conditions.

[0115] Comparative example C6 was a physically blended mixture of epoxy-functional phenyl-T resin (intermediate prepared in synthesis example 3 with unit formula MVi0.iTPEP0.07TPh0.83) and CEP terminated PDMS with dp=100 (MCEPD]OoMCEP) with PAG-Dow. C6 was very hazy before and after UV irradiation. The gel swelling test showed the cure% of C6 after UV cure was 50%. The haze and low cure% of C6 were thought to be caused by the incompatibility between phenyl-T resin and the CEP terminated PDMS polymer, which proved the advantages of the present invention (i.e., the epoxycycloalkyl - functional resin linear copolymers) over the physically blended mixture of conventional resins and PDMS polymers. Comparative example C7 comprised only CEP terminated PDMS (MCEP2DIOO) and PAG-Dow. The incompatibility between the photoacid generator, PAG-Dow, and MCEPDIOOMCEPwas thought to indicate the benefit of the epoxycycloalkyl - functional resin - linear polyorganosiloxane block copolymer of the present invention. Without wishing to be bound by theory, it is thought that the incorporation of TPhresin with linear PDMS polymer provided better solubility of photoacid generators in the composition with the epoxycyclohexyl - functional resin - linear polyorganosiloxane block copolymer of this invention.

[0116] Table 6 The cure and adhesion data (Extractable% and ROR%) for release coating compositions prepared from UV cured epoxy - functional resin - linear polyorganosiloxane block copolymers or Vi-RL (the vinyl-functional resin - linear polyorganosiloxane block copolymer intermediate prepared at the beginning of Synthesis Example 6) were measured onthermal paper substrates (Lintec / Mactac thermal paper).Table 6.

[0117] CEP functional resin - linear polyorganosiloxane block copolymers were applied as UV curable release coatings on thermal paper substrates (e.g., Lintec / Mactac thermal paper used here) to compare their performance vs that of hydrosilylation curable Vi-RL composition. Extractable% and ROR% are two data measured to show their performance as release coatings for thermal paper. Extractable% is the weight percentage extracted from the cured film and was measured and calculated as the weight loss percentage of the film after 30 min immersing in a MIBK (methyl isobutyl ketone) solution. ROR% is the percentage of rub off resistance which was measured and calculated as the weight percentage of the film remained on the substrate after a rubbing off test. The lower the extractable%, the better the UV cure, and the higher the ROR%, the stronger the adhesion of the release coating to the substrate. Cured films made from epoxycyclohexyl alkyl - functional resin - linear polyorganosiloxane block copolymers of examples 15 and 16, in Table 6 showed much lower Extractable% and higher ROR% than Vi-RL (comparative example C9), indicating much better cure and stronger adhesion on thermal paper substrates with the copolymer of the present invention. The surface of thermal paper is coated with a layer of thermochromic coatings which contains a variety of organic functional groups such as amine, thiol, carboxylic acid. Some of the functional groups (e.g., amine, thiol) may inhibit Pt catalysts resulting in slow cure and poor adhesion of hydrosilylation cured Vi-RL composition on thermal paper but have no inhibition effects on UV initiated epoxy cure.

[0118] Table 7 below has results of thermal aging and adhesion tests, which showed that (i) PAG- Dow cured composition examples 10-14 had good thermal stability indicated by the little change of the color (or b* value) and the high toughness and flexibility of the aged samples; (ii) Epoxycycloakyl - functional resin - linear polyorganosiloxane block copolymers showed better cure and much higher adhesions on substrates (thermal paper, F4 boards or Al) than hydrosilylation curable Vi-RL (comparative examples C5 and C7). The good thermal stability of the UV cured epoxycycloakyl - functional resin - linear polyorganosiloxane block copolymers was also confirmed by the only slightly changed Young’s modulus and the remained highelongation% measured for examples 17, 18 and 19 in Table 7 after aging at 150 °C for 5 days. In addition, the mechanical properties of the UV cured epoxycycloakyl - functional resin - linear polyorganosiloxane block copolymer compositions can be easily tuned by adding epoxyfunctional crosslinkers such as MCEPMCEPused in examples 18 and 19. The Young’s modulus of the UV cured compositions according to this invention were from 45.2 to 68.7 to 84 MPa with the increase of the MCEPMCEPcontent from 0 to 2 % to 5 %.

[0119] Table 7 Thermal stability of photoacid generator catalyzed UV cured epoxy - functional resin - linear polyorganosiloxane copolymers with thermally aging at 150 °C for 5 days. 0.5 wt% of PAG-Dow was used as UV initiated catalysts. The higher amount of MCEPMCEPmakes the compatibility of the formulations worse.Table 7

[0120] Epoxy containing materials (e.g., Dow commercial epoxy functional adhesion promoter APZ-55) may suffer from yellowing issues during high temperature applications (e.g., temperature over 100 °C). The comparative example C8 in Table 5 (containing APZ-55) showed much higher b* value after aging. The epoxycycloalkyl - functional resin - linear polyorganosiloxane copolymers described herein did not show much yellowing issues, which was proved by the low b* values measured for thermally aged composition samples cured by either thermal or UV cure, e.g., as shown above in Table 5. The mole% of epoxy-functionality was 3.5 to 7 mole% which was much lower than the epoxy mole% (28.5%) in APZ-55. In addition, epoxycycloalkyl - functional resin - linear polyorganosiloxane copolymers described herein with 3.5 mole% epoxy showed relatively lower cure% under either thermal or UV cure. Therefore, it may be desirable for the epoxycycloalkyl - functional resin - linear polyorganosiloxane copolymers described herein to include an epoxy content > 3.5 mol % to < 28.5 mol %, alternatively > 3.5 mole % to 10 mole %, to improve curability in the compositions described herein with minimized discoloration issues.PROBLEMS TO BE ADDRESSED

[0121] Development of LED lighting continuously requires encapsulants which have high transparency, high thermal and / or photothermal stability, strong adhesion, excellent mechanical properties, fast cure, and low cost. Especially fast cure at RT or under UV is highly desirable considering the sustainability and energy savings. The current hydrosilylation and condensationcure systems were found to have limitations as far as inhibition and poisons that can inhibit or prevent cure. For example, hydrosilylation curable silicone release coating products may show slow cure speed and poor adhesion on thermal paper substrates because the additives (e.g., thiol and amine) in the top coating layer of thermal paper act as poisons for the Pt based hydrosilylation catalyst.SOLUTION

[0122] The present inventors found that grafting epoxycycloalkyl-functional groups onto resin- linear polyorganosiloxane block copolymers provided unique epoxycycloalkyl-functional resin- linear polyorganosiloxane block copolymers with benefits from both epoxycycloalkyl groups and polyorganosiloxanes without compromising either one. Benefits may include one or more of improved adhesion, high hardness and fast cure (especially fast UV cure) from the epoxycycloalkyl functionality and high thermal and / or photothermal stability and flexibility from the polyorganosiloxane functionality. In addition, epoxycycloalkyl as a cure moiety does not suffer from the same inhibition as hydrosilylation and does not generate moisture as a side product as condensation reaction.DEFINITIONS AND USAGE OF TERMS

[0123] All amounts, ratios, and percentages are by weight unless otherwise indicated by the context of the specification. The articles ‘a’, ‘an’, and ‘the’ each refer to one or more, unless otherwise indicated by the context of specification. The singular includes the plural unless otherwise indicated by the context of the specification. The SUMMARY and ABSTRACT are hereby incorporated by reference. The amounts of all starting materials in a composition total 100%. The transitional phrases “comprising”, “consisting essentially of’, and “consisting of” are used as described in the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018 at section §2111.03 I., IL, and III. The use of “for example,” “e.g. " “such as,” and “including” to list illustrative examples does not limit to only the listed examples. Thus, “for example” or “such as” means “for example, but not limited to” or “such as, but not limited to” and encompasses other similar or equivalent examples. The disclosure of ranges includes the range itself and also anything subsumed therein, as well as endpoints. Similarly, the disclosure of Markush groups includes the entire group and also any individual members and subgroups subsumed therein. For example, disclosure of the Markush group a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, includes the member alkyl individually; the subgroup alkyl and aryl; and any other individual member and subgroup subsumed therein. Any feature or aspect of the invention may be used in combination with any other feature or aspect recited herein. Abbreviations are as defined below in Table A.Table A - Abbreviations

Claims

CLAIMS:

1. An epoxycycloalkyl-functional resin - linear polyorganosiloxane block copolymer, wherein the copolymer comprises linear blocks and non - linear blocks, wherein each linear block independently comprises 10 to 400 disiloxy units of formula (R22SiO2 / 2), wherein each R2is an independently selected monovalent hydrocarbyl group of 1 to 30 carbon atoms; each non - linear block has a molecular weight of at least 500 g / mol, the non - linear blocks comprise trisiloxy units and hydrolyzable groups, and wherein the non - linear blocks further comprise epoxycycloalkyl - functional groups bonded to silicon atoms: at least 30 mol % of the non - linear blocks are crosslinked with each other, each linear block is linked to at least one non - linear block, and the copolymer has a weight average molecular weight of at least 20,000 g / mol measured by gel permeation chromatography.

2. The copolymer of claim 1 , wherein the copolymer comprises unit formula:wherein each R1is an independently selected monovalent hydrocarbyl group of 1 to 30 carbon atoms; each R2is the independently selected monovalent hydrocarbyl group of 1 to 30 carbon atoms as described above; each D1is an independently selected divalent hydrocarbyl group of 2 to 30 carbon atoms; each R3is independently selected from an alkenyl group of 2 to 30 carbon atoms and an aryl group of 6 to 30 carbon atoms; each R4is an epoxycycloalkyl - functional group; each Z is independently selected from H or a monovalent hydrocarbyl group of 1 to 30 carbon atoms; subscripts a, b, c, d, and e represent mole fractions of each siloxy unit in the unit formula, and have values such that0 < a < 0.1;0.3 < b < 0.8;0 < c < 0.2;0.3 < (b + c) < 0.8;0.1 < d < 0.7;0.035 < e < 0.285;a quantity (a + b + c + d + e) = l; and subscript f represents a molar amount of hydrolyzable groups in the copolymer, and subscript f has a value such that 0 < f < 0.5.

3. A method for making the copolymer of 1 or claim 2, wherein the method comprises:(Al) combining, under conditions to effect hydrolysis, starting materials comprising:(al-1) an aryltrialkoxysilane of formula R6Si(OR5)s, where R6is an aryl group of 6 to 30 carbon atoms, and each R5is an independently selected alkyl group of 1 to 6 carbon atoms;(al-2) an epoxycycloalkyl - functional trialkoxysilane of formula R4Si(OR5)3, wherein R4is the epoxycycloalkyl - functional group, and each Rsis an independently selected alkyl group of 1 to 6 carbon atoms;(al-3) a bis-alkenyl-terminated dialkylsiloxane oligomer of unit formula (R7R12SiOi / 2)2(R22SiO2 / 2)g, where R1and R2are the monovalent hydrocarbyl groups of 1 to 30 carbon atoms as described above; subscript g represents an average number of disiloxy units per molecule, and subscript g is an integer with value such that g > 0; and each R7is an independently selected alkenyl group of 2 to 30 carbon atoms; and(a 1-4) water; in the presence of (cl) an acid catalyst, thereby forming a hydrolysis product comprising an aryl-, epoxycycloalkyl-, alkenyl- functional silsesquioxane resin; and optionally adding a solvent to the hydrolysis product formed in step (Al); optionally neutralizing (cl) the acid catalyst after step (Al);(A2) combining, under conditions to effect hydrosilylation reaction, starting materials comprising the aryl-, epoxycycloalkyl-, alkenyl- functional silsesquioxane resin prepared in step (Al),(a2-l) a linear polyorganohydrogensiloxane of unit formula (R12HSiOi / 2)2(R22SiO2 / 2)h, where each R1and each R2are the independently selected monovalent hydrocarbyl groups of 1 to 30 carbon atoms, subscript h represents an average number of disiloxy units per molecule, and subscript h is an integer with a value of 20 to 1 ,000;(a2-2) an aryl-functional siloxane oligomer of unit formula (R1HSiOi / 2)2(R82SiO2 / 2)j, where each R1is the independently selected monovalent hydrocarbyl group of 1 to 30 carbon atoms, each R8is an independently selected aryl group of 6 to 30 carbon atoms, and subscript) represents average number of disiloxy units per molecule, and subscript j is an integer with a value of 1 to 3; and in the presence of (c2) a hydrosilylation reaction catalyst, thereby forming a hydrosilylation reaction product comprising the copolymer; andoptionally (A3) recovering the copolymer from the hydrosilylation reaction product.

4. The copolymer of claim 1 , wherein the copolymer comprises unit formula:(ZOi / 2)s, wherein each R1is an independently selected monovalent hydrocarbyl group of 1 to 30 carbon atoms; each R2is an independently selected monovalent hydrocarbyl group of 1 to 30 carbon atoms; each D1is an independently selected divalent hydrocarbyl group of 2 to 30 carbon atoms; each R3is independently selected from an alkenyl group of 2 to 30 carbon atoms and an aryl group of 6 to 30 carbon atoms; each R4is an epoxycycloalkyl - functional group; each Z is independently selected from H or a monovalent hydrocarbyl group of 1 to 30 carbon atoms; subscripts m, n, o, p, and q represent mole fractions of each siloxy unit in the unit formula, and have values such that0 < m < 0.1;0.3 < n < 0.8;0.035 < o < 0.285;0.3 < (n + o) < 0.8;0.035 < p < 0.285;0.1 < q < 0.7;0.035 < r < 0.285, (alternatively 0.035 < r < 0.1); a quantity (m + n + o + p + q + r) = l; subscript s represents a molar amount of hydrolyzable groups in the copolymer, and subscript s has a value such that 0 < s < 0.5.

5. A method for making the copolymer of claim 4, wherein the method comprises:(Bl) combining, under conditions to effect hydrosilylation reaction, starting materials comprising(b 1-1) an alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer comprising difunctional siloxy units and trifunctional siloxy units, wherein starting material (bill comprises unit formula (R142SiO2 / 2)t(R15SiO3 / 2)u(ZOi / 2)v, wherein each R14and each R15are independently selected monovalent hydrocarbyl groups of1 to 30 carbon atoms; each Z is independently selected from the group consisting of a hydrogen atom and a monovalent hydrocarbyl group of 1 to 30 carbon atoms; subscripts t and u represent mole fractions of siloxy units in (b 1-1) the alkenyl-, aryl- functional resin - linear polyorganosiloxane block copolymer, and subscripts t and u have values such that0.4 < t < 0.9 and0.1 < u < 0.6, and a quantity (t + u) = 1 , subscript v represents a mole fraction of hydrolyzable groups, and subscript v has a value such that 0 < v < 0.5, wherein the disiloxy units are arranged in linear blocks having an average of 10 to 400 units of formula (R142SiO2 / 2) per linear block; and wherein the trisiloxy units of formula (R15SiO3 / 2) are arranged in non - linear blocks, wherein each non - linear block has a molecular weight of at least 500 g / mol; and(bl -2) an epoxy cycloalkyl-functional silyl hydride compound of formulaeach R16is an independently selected monovalent hydrocarbyl group of 1 to 30 carbon atoms,R4is the epoxycycloalkyl-functional group, and subscript w is an integer with a value of 0. 1, or 2; and (c2) a hydrosilylation reaction catalyst; and optionally (B2) recovering the copolymer from the hydrosilylation reaction product.

6. The copolymer of any one of claims 1, 2, and 4, wherein the epoxycycloalkyl - functional groups each have formula, whereinD2is a divalent hydrocarbyl group of 2 to 30 carbon atoms, and subscript x is 0 or 1.

7. The copolymer of claim 6, wherein the epoxycycloalkyl - functional group is selected from an (epoxycyclopentyl)alkyl- group or an (epoxycyclohexyl)alkyl- group.

8. The copolymer of claim 7, where the (epoxycyclohexyl)alkyl- group is selected from [2- (3,4-epoxycyclohexyl)ethyl]; [3-(3,4-epoxycyclohexyl)propyl]; or { 6-(7- oxabicyclo[4.1 .0]heptan-3-yl)hexyl } .

9. A curable composition comprising:(I) a copolymer according to any one of claims 1, 2, 4, 6, 7, or 8, and a catalytically effective amount of (II) a catalyst.

10. The curable composition of claim 9, wherein the composition is thermally curable, and wherein the catalytically effective amount of (II) the catalyst comprises > 100 ppm of an inhibited fluorinated arylborane Lewis acid.

11. The curable composition of claim 9, wherein the composition is UV curable, and wherein the catalyst comprises a photoacid generator.

12. The curable composition of any one of claims 9 to 11, further comprising an additional starting material selected from the group consisting of: a solvent, an organosiloxane resin, a stabilizer, a phosphor, a moisture scavenger, a metal-ligand complex, a filler, and a combination of two or more thereof.

13. A method for preparing the composition of any one of claims 9 to 12, wherein the method comprises: mixing starting materials comprising the copolymer and the catalyst under ambient conditions.

14. A method comprising:1) applying the composition of any one of claims 9 to 12 to a substrate, and optionally 2) removing solvent, when present, and3) curing the composition.

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