WO2025178761A1 - Epoxy-functionalized polyorganosiloxane and alkylsilyl functionalized photo-acid generator - Google Patents

Abstract

The present invention is a composition comprising and epoxy-functionalized polyorganosiloxane and a compound of Formula (1) where R, R¹, R², and M^- are as defined herein. The composition of the present invention is useful in UV-induced reactions of an epoxy-functionalized polyorganosiloxane in the presence of a photo-acid generator.

Description

Epoxy-functionalized Polyorganosiloxane and Alkylsilyl Functionalized Photo-Acid Generator Background of the Invention The present invention relates to a composition comprising an epoxy-functionalized polyorganosiloxane and an alkylsilyl functionalized photo-acid generator. Polyorganosiloxanes functionalized with epoxy groups can be cured by UV irradiation; such systems are attractive because, unlike free-radical polymerization, UV-induced polymerization of epoxides proceeds rapidly and with high oxygen tolerance; moreover, once UV curing has been initiated, it can be continued in the dark, long after initial UV irradiation has ceased. Mechanistically, UV curable epoxide systems proceed through a Cationic Ring Opening Epoxide Polymerization (CREOP) mechanism. The polymerization of epoxy groups is advantageously initiated by way of a photo-acid generator (PAG), most commonly an onium salt initiator that contains a diazonium, iodonium, sulfonium, or phosphonium cation, and a non-nucleophilic counter anion such as BF₄-, PF₆- , AsF₆-, and SbF₆-. (See, for example, US 5,703,137.) Timely curing is elusive, however, for formulations containing PAGs and epoxy-terminated polyorganosiloxanes with a degree of polymerization of > 100, due to incompatibility of the relatively polar PAG and the relatively non-polar high molecular weight polymer. Attempts to address incompatibility with solvents or reactive diluents have failed. It would therefore be advantageous in the field of UV-induced polymerization of epoxides to discover a PAG that is compatible with an epoxy-terminated polyorganosiloxane with a high degree of polymerization. Summary of the Invention The present invention addresses a need in the art by providing a composition comprising an epoxy-functionalized polyorganosiloxane and a compound of Formula 1: where R is either C1-C6-alkyl or -Y-CH2CH2-Si(R³)3; R¹ and R² are each independently H, C1-C6-alkyl, or -X-Z-CH2CH2Si(R³)3; where each R³ is independently C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy, -OSi(C₁-C₆-alkyl), or phenyl; X is Si(CH3)2 or CH2; Y is a divalent C1-C12-hydrocarbyl group; Z is a bond or a divalent C₁-C₁₂-hydrocarbyl group; and each M⁻ is a borate, phosphate, arsenate, or antimonate anion; with the proviso that when R is -Y-CH₂CH₂-Si(R³)₃, R¹ and R² are each independently H or C1-C6-alkyl; and with the further proviso that when R is C1-C6-alkyl, at least one of R¹ and R² is -X-Z-CH₂CH₂-Si(R³)₃. The composition of the present invention is useful in UV-induced reactions of an epoxy- functionalized polyorganosiloxane in the presence of a photo-acid generator. Detailed Description of the Invention The present invention addresses a need in the art by providing a composition comprising an epoxy-functionalized polyorganosiloxane and a compound of Formula 1: where R is either C₁-C₆-alkyl or -Y-CH₂CH₂-Si(R³)₃; R¹ and R² are each independently H, C1-C6-alkyl, or -X-Z-CH2CH2Si(R³)3; where each R³ is independently C1-C12-alkyl, C1-C12-alkoxy, -OSi(C1-C6-alkyl), or phenyl; X is Si(CH₃)₂ or CH₂; Y is a divalent C₁-C₁₂-hydrocarbyl group; Z is a bond or a divalent C1-C12-hydrocarbyl group; and each M⁻ is a borate, phosphate, arsenate, or antimonate anion; with the proviso that when R is -Y-CH2CH2-Si(R³)3, R¹ and R² are each independently H or C1-C6-alkyl ; and with the further proviso that when R is C1-C6-alkyl, at least one of R¹ and R² is -X-Z-CH₂CH₂-Si(R³)₃. The epoxy-functionalized polyorganosiloxane is preferably an epoxy-functionalized polydimethylsiloxane (PDMS) of Formula 2: where x is 2 to 1000; y is from 0 to 10; p =1 and r = 1, or p = 0 and r = 0; each R′ is independently H, methyl, OH, vinyl, or an epoxy-functionalized fragment; and R′′ is an epoxy- functionalized fragment; with the proviso that when y is 0, at least one R′ is an epoxy- functionalized fragment; when each R′ is H, methyl, OH, or vinyl, y is from 1 to 10; and when one R′ is an epoxy-functionalized fragment, and the other R′ is H, methyl, OH, or vinyl, p =1 and r = 1. Preferably, x is in the range of from 40, or from 100 to 1000. Preferably, y is 0 or 1, and more preferably y is 0. It is understood that the compound of Formula 2 is a homopolymer, or a random or block copolymer. As used herein, “epoxy-functionalized fragment” refers to a C2-C12 hydrocarbyl or hydrocarbyl ether group connecting an oxirane group and a silicon atom. The hydrocarbyl group may be linear, branched, cyclic, or fused cyclic. Examples of suitable epoxy functionalized fragments include 2-(3,4-epoxycyclohexyl) ethyl, 3-glycidoxy propyl, and 3-epoxy propyl fragments, as illustrated: where the dotted lines represent the point of attachment to the silicon atom. A preferred compound of Formula 2, where y is 0 and R′ is 2-(3,4-epoxycyclohexyl) ethyl may be prepared by contacting the polyorganosiloxane with 4-vinyl-cyclohexene 1,2-epoxide in the presence of a suitable catalyst such as rhodium, as illustrated in Scheme 1: Scheme 1 epoxycyclohexyl) ethyl and the other of the R′ is groups is H, methyl, OH, or vinyl can be prepared as illustrated in Scheme 2: isopropyl, and n-butyl groups, with methyl being preferred. When R is C1-C6-alkyl, at least one of R¹ and R² is a -Si(CH₃)₂-Z-CH₂CH₂Si(R³)₃ or a CH₂-Z-CH₂CH₂Si(R³)₃ group. When R is -Y-CH2CH2-Si(R³)3, R¹ and R² are preferably each independently H, methyl, ethyl, n-propyl, or n-butyl. More preferably, when R is -Y-CH₂CH₂-Si(R³)₃, R¹ and R² are H. Examples of suitable R³ groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, methoxy, ethoxy, n-butoxy, OSi(CH3)3, and phenyl groups, as well as combinations thereof. The term “divalent hydrocarbyl group” is used herein to describe an unsubstituted linear or branched divalent hydrocarbyl group or a linear or branched divalent hydrocarbyl group incorporated with an oxygen atom or a dimethylsilyl group. Examples of suitable M^⁻ groups include SbF6^⁻, PF6^⁻, B[C6H3(CF3)2]4^⁻, and B(C6F5)4^⁻ groups. The compound of Formula 1 where R is -Y-CH2CH2-Si(R³)3, and R¹ and R² are H, and M⁻ is B[C₆H₃(CF₃)₂]₄⁻ can be prepared in accordance with Scheme 3: Scheme 3 R² is H, and M⁻ is B[C₆H₃(CF₃)₂]₄ can be prepared in accordance with Scheme 4: Scheme 4 The compound of Formula 1 where both R¹ and R² are Me₂Si-Z-CH₂CH₂SiR³ can be prepared analogously using a 2,3-dibromo-C1-C6-alkoxybenzene, a 2,5-dibromo-C1-C6-alkoxybenzene, or a 2,6-dibromo-C₁-C₆-alkoxybenzene as the starting material. Examples of compounds of Formula 1 are illustrated: where Me The composition of the present invention is useful in UV-induced reactions of an epoxy- functionalized polyorganosiloxane, especially high molecular weight epoxy functionalized polyorganosiloxanes with a degree of polymerization (dp) > 100. In contrast, PAGs that are not functionalized with alkylsilyl groups have been shown to be incompatible with epoxy functionalized polyorganosiloxanes with degree of polymerization of > 100. Examples Intermediate Example 1 – Preparation of (2-Methoxyphenyl)dimethyl(vinyl)silane A three-neck 2-L round bottom flask equipped with a stir bar was charged with 2-bromoanisole (2.5 mmol) under N2, followed by addition of sufficient diethyl ether to make a 0.5 M solution. The mixture was cooled to -20 °C, whereupon n-butyl lithium (2.75 mmol, 1.6 M in hexane) was added to the solution. The reaction mixture was then stirred at -20 °C for 3 h, after which time dimethylvinylchlorosilane (2.75 mmol) was slowly added to the reaction mixture. Once the addition was complete, the mixture was slowly warmed to room temperature and stirring was continued overnight. The reaction was quenched with saturated NH₄Cl (30 mL) and the mixture was transferred to a separatory funnel. The organic layer was separated, and the aqueous layer was further washed with diethyl ether. The organic layers were combined and dried over anhydrous MgSO4. The solvent was removed under in vacuo to yield the crude product, which was purified via silica gel column chromatography (5% ethyl acetate in hexane) to isolate the pure material in 66% yield. ¹H NMR (400 MHz, C6D6) δ 7.47 (dd, J = 7.2, 1.8 Hz, 1H), 7.20 (ddd, J = 8.2, 7.4, 1.8 Hz, 1H), 6.91 (td, J = 7.3, 0.9 Hz, 1H), 6.58 – 6.42 (m, 2H), 6.03 (dd, J = 14.6, 3.8 Hz, 1H), 5.91 – 5.71 (m, 1H), 3.29 (s, 3H), 0.45 (s, 6H). ¹³C NMR (101 MHz, C6D6) δ 164.80, 139.16, 135.95, 131.90, 131.28, 120.97, 109.95, 54.66, -2.40. Intermediate Example 2 – Preparation of (2-Methoxy-1,3-phenylene)bis(dimethyl(vinyl)silane) A three-neck 2-L round bottom flask equipped with a stir bar was charged with 2,6-dibromoanisole (2.5 mmol), followed by addition sufficient of diethyl ether to make 0.5 M solution. The mixture was cooled to -20 °C, whereupon n-butyl lithium (5.5 mmol, 1.6 M in hexane) was added to the solution. The reaction mixture was then stirred at -20 °C for 3 h, after which time dimethylvinylchlorosilane (5.5 mmol) was slowly added to the reaction mixture. Once the addition was complete, the reaction was slowly warmed up to room temperature and stirring was continued overnight. The reaction was quenched with saturated NH4Cl (30 mL) and the mixture was then transferred to a separatory funnel. The organic layer was separated, and the aqueous layer was further washed with diethyl ether. The organic layers were combined and dried over anhydrous MgSO4. The solvent was removed in vacuo to yield the crude product, which was purified via silica gel column chromatography (100% hexane) to isolate the pure material in 45% yield. ¹H NMR (400 MHz, CDCl₃) δ 7.55 – 7.46 (m, 1H), 7.16 – 7.06 (m, 1H), 6.50 – 6.30 (m, 1H), 6.14 – 5.98 (m, 1H), 5.85 – 5.67 (m, 1H), 3.71 – 3.67 (m, 1H), 0.43 – 0.38 (m, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 171.62, 139.46, 138.17, 132.04, 130.26, 123.47, 63.84, -1.65. Intermediate Example 3 – Preparation of Triethyl(2-((2-methoxyphenyl)dimethylsilyl)ethyl)silane A 40-mL glass vial was charged with (2-methoxyphenyl)dimethyl(vinyl)silane (1 mmol) and Karstedt’s catalyst (10 ppm, 2 wt% in xylene) in a N2-purged glove box. The mixture was warmed to 50 °C, followed by the slow addition of triethylsilane (1.1 mmol). After the addition was complete, the mixture was allowed to stir at room temperature for 1 h, after which time an aliquot of the reaction mixture was removed and analyzed by ¹H NMR spectroscopy. Once the reaction showed full conversion, the mixture was removed from the glovebox and was purified by silica gel column chromatography (100% hexane) to isolate the pure product (>90% yield). ¹H NMR (500 MHz, CDCl3) δ 7.40 – 7.32 (m, 2H), 6.96 (t, J = 7.1 Hz, 1H), 6.83 (d, J = 8.2 Hz, 1H), 3.80 (s, 3H), 0.92 (t, J = 8.0 Hz, 9H), 0.74 – 0.67 (m, 2H), 0.52 (q, J = 8.0 Hz, 6H), 0.46 – 0.38 (m, 2H), 0.26 (s, 6H). ¹³C NMR (126 MHz, CDCl3) δ 164.52, 135.53, 130.76, 127.28, 120.49, 109.55, 55.02, 7.60, 7.56, 3.28, 3.07, -3.20. Intermediate Example 4 – Preparation of (2-Methoxyphenyl)dimethyl(2-(tri-n- octylsilyl)ethyl)silane A 40-mL glass vial was charged with (2-methoxyphenyl)dimethyl(vinyl)silane (1 mmol) and Karstedt’s catalyst (10 ppm, 2 wt% in xylene) in a N2-purged glove box. The mixture was warmed to 50 °C, followed by the slow addition of tri-n-octylsilane (1.1 mmol). After the addition was complete, the mixture was allowed to stir at room temperature for 1 h, after which time an aliquot of the reaction mixture was removed and analyzed by ¹H NMR spectroscopy. Once the reaction showed full conversion, the mixture was removed from the glovebox and was purified by silica gel column chromatography (100% hexane) to isolate the pure product (>90% yield). ¹H NMR (400 MHz, CDCl3) δ 7.39 – 7.31 (m, 2H), 6.95 (td, J = 7.3, 0.9 Hz, 1H), 6.82 (d, J = 8.1 Hz, 1H), 3.79 (s, 3H), 1.26 (m, 36H), 0.88 (t, J = 6.7 Hz, 9H), 0.75 – 0.62 (m, 2H), 0.54 – 0.44 (m, 6H), 0.44 – 0.33 (m, 2H), 0.23 (m, 6H). ¹³C NMR (101 MHz, CDCl3) δ 164.53, 135.51, 130.73, 127.36, 120.49, 109.58, 55.04, 34.12, 32.13, 29.47, 24.07, 22.85, 14.27, 12.23, 7.68, 4.54, -3.19. Intermediate Example 5 – Preparation of (2-Methoxy-1,3-phenylene)bis(dimethyl(2-(tri-n- octylsilyl)ethyl)silane) A 40-mL glass vial equipped with a stir bar was placed in a N2-purged glove box and charged with (2-methoxy-1,3-phenylene)bis(dimethyl(vinyl)silane) (1 mmol) and Karstedt’s catalyst (10 ppm, 2 wt% in xylene). The mixture was heated to 50 °C, followed by the slow addition of tri-n-octylsilane (2.2 mmol). After the addition was complete, the mixture was allowed to stir at room temperature for 1 h, after which time an aliquot of the reaction mixture was removed and analyzed by ¹H NMR. Once the reaction showed full conversion, the mixture was removed from the glove box and was further purified by silica gel column chromatography (100% hexane) to isolate the pure product (> 80% yield). ¹H NMR (400 MHz, CDCl₃) δ 7.46 (d, J = 7.3 Hz, 2H), 7.10 (t, J = 7.2 Hz, 1H), 3.69 (s, 3H), 1.27 (s, 72H), 0.89 (t, J = 6.8 Hz, 18H), 0.75 – 0.64 (m, 4H), 0.51 – 0.47 (m, 12H), 0.46 – 0.37 (m, 4H), 0.30 (s, 12H). ¹³C NMR (101 MHz, CDCl₃) δ 171.60, 165.14, 140.83, 137.57, 136.39, 130.87, 129.70, 126.40, 123.18, 108.86, 63.42, 54.70, 34.00, 33.97, 31.99, 29.33, 23.93, 22.72, 14.14, 12.05, 8.61, 4.51, -2.25, -3.33. Intermediate Example 6 – Preparation of (3-(Dimethyl(2-(triethylsilyl)ethyl)silyl)-4- methoxyphenyl)(phenyl)iodonium Tosylate PhI(OH) of Intermediate Example 3 (1.0 mmol) in 2,2,2-trifluoroethanol (5 mL). The mixture was stirred for 3 h, after which time solvents were removed in vacuo. The resulting crude product was directly used for the next step. ¹H NMR (400 MHz, CDCl3) δ 8.01 (dd, J = 8.9, 2.4 Hz, 1H), 7.90 (dd, J = 8.4, 1.1 Hz, 2H), 7.70 (d, J = 2.4 Hz, 1H), 7.65 – 7.59 (m, 2H), 7.55 – 7.49 (m, 1H), 7.38 (dd, J = 8.4, 7.3 Hz, 2H), 7.08 (d, J = 7.9 Hz, 2H), 6.81 (d, J = 8.9 Hz, 1H), 3.80 (s, 3H), 2.32 (s, 3H), 1.03 – 0.81 (m, 6H), 0.69 – 0.57 (m, 2H), 0.55 – 0.43 (m, 9H), 0.32 – 0.25 (m, 2H), 0.20 (s, 6H). ¹³C NMR (101 MHz, CDCl3) δ 166.82, 141.77, 141.30, 140.26, 138.82, 134.27, 134.01, 131.84, 131.72, 128.72, 126.15, 114.99, 113.22, 103.71, 55.46, 21.34, 7.47, 7.44, 2.89, 2.84, -3.74. Intermediate Example 7 – Preparation of (3-(Dimethyl(2-(tri-n-octanoylsilyl)ethyl)silyl)-4- methoxyphenyl)(phenyl)iodonium Tosylate The reaction was carried out substantially as described for Intermediate Example 6, except that PhI(OH)OTs was added to a stirred solution of Intermediate Example 4 under the same reaction conditions. ¹H NMR (400 MHz, CDCl₃) δ 8.01 (dd, J = 8.9, 2.4 Hz, 1H), 7.93 – 7.84 (m, 2H), 7.67 (d, J = 2.4 Hz, 1H), 7.62 (d, J = 8.0 Hz, 2H), 7.55 – 7.46 (m, 1H), 7.36 (t, J = 7.9 Hz, 2H), 7.07 (d, J = 7.9 Hz, 2H), 6.80 (d, J = 8.9 Hz, 1H), 3.79 (s, 3H), 2.32 (s, 3H), 1.35 – 1.15 (m, 36H), 0.87 (t, J = 6.8 Hz, 9H), 0.64 – 0.55 (m, 2H), 0.53 – 0.41 (m, 6H), 0.31 – 0.23 (m, 2H), 0.19 (s, 6H). ¹³C NMR (126 MHz, CDCl3) δ 166.62, 142.32, 141.68, 139.58, 138.87, 134.42, 133.70, 131.62, 131.47, 128.55, 126.05, 115.44, 113.07, 104.32, 55.39, 33.92, 31.97, 31.95, 29.29, 23.88, 22.69, 21.29, 14.11, 11.98, 7.10, 4.29, -3.81. Intermediate Example 8 – Preparation of Tri-n-octyl(11-phenoxyundecyl)silane A 40-mL glass vial equipped with a stir bar was placed in a nitrogen-purged glove box and charged with (undec-10-en-1-yloxy)benzene (1 mmol) and Karstedt’s catalyst (10 ppm, 2 wt% in xylene). The reaction mixture was heated to 50 °C followed by the slow addition of tri-n-octylsilane (1.1 mmol) The mixture was allowed to stir at room temperature for 1 h, after which time an aliquot of the reaction mixture was removed and analyzed by ¹H NMR spectroscopy. Once the reaction showed full conversion, the mixture was removed from the glove box and was further purified by silica gel column chromatography (100% hexane) to isolate the pure product (> 90% yield). ¹H NMR (500 MHz, CDCl₃) δ 7.31 – 7.27 (m, 2H), 6.98 – 6.85 (m, 3H), 3.96 (t, J = 6.6 Hz, 2H), 1.78 (dt, J = 14.8, 6.8 Hz, 2H), 1.51 – 1.41 (m, 2H), 1.41 – 1.22 (m, 50H), 0.89 (t, J = 6.9 Hz, 9H), 0.52 – 0.45 (m, 8H). Intermediate Example 9 – Preparation of Phenyl(4-((11-(tri-n-octanoylsilyl)undecyl)oxy)phenyl) Iodonium Tosylate The was as that PhI(OH)OTs was added to a stirred solution of Intermediate Example 8 (1.0 mmol) under the same reaction conditions.¹H NMR (400 MHz, CDCl3) δ 7.91 (d, J = 8.0 Hz, 2H), 7.85 (d, J = 8.7 Hz, 2H), 7.55 (d, J = 7.9 Hz, 2H), 7.48 (t, J = 7.4 Hz, 1H), 7.33 (t, J = 7.7 Hz, 2H), 7.05 (d, J = 7.8 Hz, 2H), 6.83 (d, J = 8.7 Hz, 2H), 3.92 (t, J = 6.6 Hz, 2H), 2.31 (s, 3H), 1.82 – 1.69 (m, 2H), 1.49 – 1.37 (m, 2H), 1.36 – 1.19 (m, 50H), 0.88 (t, J = 6.6 Hz, 9H), 0.52 – 0.41 (m, 8H). Intermediate Example 10 – Preparation of (3,5-bis(Dimethyl(2-(tri-n-octanoylsilyl)ethyl)silyl)-4- methoxyphenyl)(phenyl)iodonium Tosylate PhI(OH)OTs was added to a stirred solution of Intermediate Example 5 under the same reaction conditions. ¹H NMR (400 MHz, CDCl₃) δ 7.95 – 7.88 (m, 2H), 7.84 (s, 2H), 7.66 – 7.60 (m, 2H), 7.59 – 7.49 (m, 1H), 7.42 – 7.33 (m, 2H), 7.09 (d, J = 7.9 Hz, 2H), 3.68 (s, 3H), 2.32 (s, 3H), 1.26 (d, J = 6.1 Hz, 72H), 0.89 – 0.85 (m, 18H), 0.63 (dq, J = 12.0, 3.9 Hz, 4H), 0.55 – 0.42 (m, 12H), 0.42 – 0.26 (m, 4H), 0.24 (s, 12H). Intermediate Example 11 – General Procedure for the Preparation of M^CEPDnM^CEP M^HD_nM^H (0.32 mol, 0.064 equiv.), Winkonson’s catalyst (50 ppm Rh), and toluene (80 mL) were added to a 500-mL 3-neck dry flask equipped with a stir bar. The contents were heated to 80 °C, whereupon 4-vinyl-cyclohexene 1,2-epoxide (VCE, 0.70 mol) in toluene (20 mL) was added dropwise over 25 min. The mixture was then heated to reflux (110 °C) for 6 h. Solvent and excess 4-vinyl-cyclohexene epoxide were removed in vacuo to obtain M^CEPD_nM^CEP at 95% yield.

Intermediate Example 12 – Preparation of M^CEPD495M^Vi of toluene (50 mL) and Karstedt’s catalyst (5 ppm Pt). The solution was stirred and heated to 90 °C, whereupon 1,1,3,3-tetramethyl-3-ethylcyclohexyl-1,2-epoxide-disloxane (2.2 g, 0.0085 mol SiH was added over 20 min. The mixture was heated for 3 h, then allowed to cool to room temperature. Solvent was removed in vacuo and the product was confirmed by ¹H NMR spectroscopy (195 g, yield: 96%). Example 1 – Preparation of (3-(dimethyl(2-(triethylsilyl)ethyl)silyl)-4- methoxyphenyl)(phenyl)iodonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate Sodium was a to a vessel containing a solution of Intermediate Example 6 (1 mmol) dissolved in 5 mL of anhydrous diethyl ether. The mixture was stirred for 12 h at room temperature, after which time solvent was removed in vacuo. The mixture was dissolved in toluene (30 mL) and vacuum filtered. The filtrate was then concentrated in vacuo to isolate the pure product (> 50% yield). ¹H NMR (400 MHz, CDCl3) δ 7.73 (p, J = 2.2 Hz, 10H), 7.66 – 7.58 (m, 3H), 7.49 (s, 4H), 7.42 (dd, J = 8.5, 7.4 Hz, 1H), 6.82 (d, J = 8.9 Hz, 1H), 3.82 (s, 3H), 0.87 (t, J = 7.9 Hz, 9H), 0.73 – 0.59 (m, 2H), 0.48 (q, J = 7.9 Hz, 6H), 0.35 – 0.26 (m, 2H), 0.24 (s, 6H). ¹⁹F NMR (376 MHz, CDCl3) δ -62.30. Example 2 – Preparation of (3-(Dimethyl(2-(tri-n-octylsilyl)ethyl)silyl)-4- methoxyphenyl)(phenyl)iodonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate The tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (1.0 mmol) was added to a solution of Intermediate Example 7 (1 mmol) dissolved in anhydrous diethyl ether. (Yield > 50%). ¹H NMR (400 MHz, CDCl3) δ 7.77 (s, 8H), 7.71 – 7.58 (m, 5H), 7.51 (s, 4H), 7.46 – 7.36 (m, 2H), 6.84 (d, J = 8.8 Hz, 1H), 3.83 (s, 3H), 1.37 – 1.19 (m, 36H), 0.93 – 0.84 (m, 9H), 0.73 – 0.64 (m, 2H), 0.55 – 0.46 (m, 6H), 0.37 – 0.30 (m, 2H), 0.26 (s, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 168.48, 161.79 (dd, J = 99.6, 49.8 Hz), 141.72, 138.32, 137.97, 137.90, 136.11, 134.79, 134.06, 133.71, 133.64, 133.58, 129.67 – 128.56 (m), 128.52, 125.83, 123.12, 120.41, 117.57 (p, J = 4.0 Hz), 114.78, 111.84, 99.92, 55.82, 33.91, 31.94, 29.29, 29.28, 23.88, 22.67, 14.04, 11.93, 6.94, 4.35, -4.10. ¹⁹F NMR (376 MHz, CDCl3) δ -62.27.

Example 3 – Preparation of Phenyl(4-((11-(tri-n-octanoylsilyl)undecyl)oxy)phenyl)iodonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate The tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (1.0 mmol) was added to a solution of Intermediate Example 9 (1 mmol) dissolved in anhydrous diethyl ether. (Yield > 50%.) ¹H NMR (500 MHz, CDCl3) δ 7.73 (s, 8H), 7.66 (t, J = 7.5 Hz, 1H), 7.62 – 7.54 (m, 4H), 7.50 (s, 4H), 7.47 – 7.40 (m, 2H), 6.94 (d, J = 9.2 Hz, 2H), 3.97 (t, J = 6.6 Hz, 2H), 1.83 – 1.75 (m, 2H), 1.47 – 1.39 (m, 2H), 1.36 – 1.23 (m, 50H), 0.88 (t, J = 6.9 Hz, 1H), 0.51 – 0.44 (m, 8H). Example 4 – Preparation of (3,5-Bis(dimethyl(2-(tri-n-octanoylsilyl)ethyl)silyl)-4- methoxyphenyl)(phenyl)iodonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (1.0 mmol) was added to a solution of Intermediate Example 10 (1 mmol) dissolved in anhydrous diethyl ether. (Yield > 50%) ¹H NMR (400 MHz, CDCl3) δ 7.74 (bs, 8H), 7.67 (m, 2H), 7.61 – 7.57 (m, 3H), 7.49 (bs, 4H), 7.43 (td, J = 8.2, 1.6 Hz, 2H), 3.76 (s, 3H), 1.31 – 1.23 (m, 72H), 0.93 – 0.82 (m, 18H), 0.73 – 0.63 (m, 4H), 0.49 (dt, J = 10.9, 4.1 Hz, 12H), 0.40 – 0.30 (m, 4H), 0.28 (s, 12H). ¹³C NMR (101 MHz, CDCl₃) δ 175.46, 161.83 (dd, J = 99.5, 49.8 Hz), 142.93, 142.13, 134.76, 134.31, 134.25, 133.65, 133.63, 133.61, 129.15 (q, J = 29.7 Hz), 125.76, 123.05, 120.34, 117.57 (p, J = 4.0 Hz), 110.98, 107.47, 65.87, 33.91, 31.93, 29.33, 29.30, 29.28, 23.88, 22.67, 15.21, 14.08, 11.91, -2.90. ¹⁹F NMR (376 MHz, CDCl3) δ -62.29. Compatibility Measurements The example and comparative PAGs (Examples 1-4 and Comparative Examples 1 and 2, 0.5 wt%) were mixed with M^CEPDnM^CEP (99.5 wt%) using a dental mixer at 3000 rpm for 3 min. If the mixture formed a clear solution and remained homogeneous (miscible) after 3 d without precipitation or phase separation, it was deemed compatible; if the mixture formed a hazy solution after mixing, it was deemed incompatible. Mixtures of the example and comparative example PAGs were prepared with PAG (0.5 wt%) and M^CEPDnM^CEP (99.5 wt%) or M^CEPD495M^Vi. A 1-mm thick film was coated on an aluminum panel from each formulation, then irradiated with 365 nm UV LED light for 10 s (UV dose: 0.5 J/cm²). Table 1 illustrates compatibility and short time curability of example and comparative example PAGs. “n” refers to the degree of polymerization (dp) of the epoxy-functionalized polymer. Comp.1 and Comp.2 refer to the comparative PAGs, which have the following structures:

Table 1 – Compatibility and Cure Data for PAGs and Epoxy-Functionalized Polyorganosiloxanes PAG Ex. M^CEPD_nM^CEP dp M^CEPD_nM^Vi dp Compatibility UV cure? The d ight epoxy-functionalized polyorganosiloxanes and high UV catalytic activity by virtue of curing over 10 s (0.5 J/cm²). In contrast, PAGs unfunctionalized with alkylsilanes were incompatible with the polyorganosiloxanes and did not cure over during the irradiation cycle.

Claims

Claims: 1. A composition comprising an epoxy-functionalized polyorganosiloxane and a compound of Formula 1: OR where R is either C₁-C₆-alkyl or -Y-CH₂CH₂-Si(R³)₃; R¹ and R² are each independently H, C1-C6-alkyl or -X-Z-CH2CH2Si(R³)3; where each R³ is independently C1-C12-alkyl, C1-C12-alkoxy, -OSi(C1-C6-alkyl), or phenyl; X is Si(CH₃)₂ or CH₂; Y is a divalent C₁-C₁₂-hydrocarbyl group; Z is a bond or a divalent C1-C12-hydrocarbyl group; and each M⁻ is a borate, phosphate, arsenate, or antimonate anion; with the proviso that when R is -Y-CH2CH2-Si(R³)3, R¹ and R² are each independently H or C₁-C₆-alkyl; and with the further proviso that when R is C₁-C₆-alkyl, at least one of R¹ and R² is -X-Z-CH2CH2-Si(R³)3. 2. The composition of Claim 1 wherein the epoxy-functionalized polyorganosiloxane is a compound of Formula 2: where x is 2 to 1000; y is from 0 to 10; p =1 and r = 1, or p = 0 and r = 0; each R′ is independently H, methyl, OH, vinyl, or an epoxy-functionalized fragment; and R′′ is an epoxy- functionalized fragment; with the proviso that when y is 0, at least one R′ is an epoxy- functionalized fragment; when each R′ is H, methyl, OH, or vinyl, y is from 1 to 10; and when one R′ is an epoxy-functionalized fragment, and the other R′ is H, methyl, OH, or vinyl, p =1 and r = 1; wherein the compound of Formula 1 is represented by the following structure: OR R² R¹ . 3. The composition of either of Claims R is C₁-C₆-alkyl, and one or both of R¹ and R² is Si(CH3)2-Z-CH2CH2Si(R³)3; where each M⁻ is a borate, phosphate, or antimonate anion. 4. The composition of Claim 3 wherein M⁻ is SbF6^⁻, PF6^⁻, B[C6H3(CF3)2]4^⁻, or B(C6F5)4^⁻; each R is methyl; each R³ is independently C₁-C₁₂-alkyl; Z is a bond; and y is 0 or 1. 5. The composition of Claim 4 wherein each R′ is a 2-(3,4-epoxycyclohexyl) ethyl group, a 3-glycidoxy propyl group, or a 3-epoxy propyl group. 6. The composition of Claim 5 wherein each R′ is a 2-(3,4-epoxycyclohexyl) ethyl group; x is in the range of from 100 to 1000; and y is 0. 7. The composition of either of Claims 1 or 2 where R is -Y-CH2CH2-Si(R³)3; where each M⁻ is a borate, phosphate, or antimonate anion. 8. The composition of Claim 7 wherein M⁻ is SbF₆ ^⁻, PF₆ ^⁻, B[C₆H₃(CF₃)₂]₄ ^⁻, or B(C₆F₅)₄ ^⁻; R¹ and R² are each independently H, methyl, ethyl, n-propyl, or n-butyl; and each R³ is independently C₁-C₁₂-alkyl; wherein y is 0 or 1. 9. The composition of Claim 8 wherein each R′ is a 2-(3,4-epoxycyclohexyl) ethyl group, a 3-glycidoxy propyl group, or a 3-epoxy propyl group; and R¹ and R² are H. 10. The composition of Claim 9 wherein R′ is a 2-(3,4-epoxycyclohexyl) ethyl group; x is in the range of from 100 to 1000; and y is 0. 11. The composition of Claim 4 wherein one of the R′ groups is a 2-(3,4-epoxycyclohexyl) ethyl group, the other R′ group is vinyl; p = 1, r = 1, and y is 0. 12. The composition of either of Claims 1 or 2, wherein the compound of Formula 1 is selected from the group consisting of:

.