Silicone-Soluble Acylphosphine Oxide Photoinitiators

Abstract

The present invention is a compound of formula I. [Formula 1] JPEG2025510897000029.jpg28170 [In the formula, R 1 -R 4 , m and n are defined herein. The compounds of the present invention are useful as photoinitiators that are soluble in ethylenically unsaturated organopolysiloxanes.

Description

[Technical field]

[0001] The present invention relates to acylphosphine oxide photoinitiators. A continuing challenge in the field of organopolysiloxane curing systems is to design photoinitiators that are compatible with organopolysiloxanes. Photoinitiators with poor compatibility are undesirable as curing agents because they separate from the silicone matrix during storage, resulting in severe haze in the cured product.

[0002] US 10,597,413 B2 (Tan) describes acylphosphine oxides substituted with -CH2-O-Si(OR)3 groups, typical examples of which are the following compounds:

[0003] [ka]

[0004] Tan discloses that these photoinitiators address the long-standing solubility problem, but it is clear that another problem is introduced, namely the susceptibility of the silyl ether bond (CH2-OSi) to acid cleavage, which makes the photoinitiator incompatible with the silicone matrix. Therefore, achieving solubility and maintaining stability would be advantageous in the art of photoinitiation in silicone systems. Summary of the Invention

[0005] The present invention addresses a need in the art by providing compounds of formula I:

[0006] [ka] m is 0, 1, 2, or 3; and n is 0, 1, or 2. R 1 is -phenyl-(R 3 ) n , -C(O)-phenyl-(R 2 )m , -O-C1~C 20 -Alkyl, or -O(CH2CH2O) x -H, where x is 1 to 20; Each R 2 are independently C1-C6-alkyl, C1-C6-alkoxy, -OCH2-phenyl, or R 2 is adjacent to the R 2 together with a 1,3-dioxolane group or a 1,4-dioxane group, Each R 3 is independently C1-C6-alkyl or C1-C6-alkoxy, R 4 teeth, i) -(Si(Me2) p (CH2) q (Si(R 5 2)O) r (X) s -Y, wherein p is 0 or 1, provided that when p is 0, q is 3 to 12, and when p is 1, q is 2 to 12; r is 3 to 300; X is CH2CH2 or CH(CH3); s is 0 or 1, with the proviso that when s is 0, Y is SiMe2H, and when s is 1, Y is Si(OMe)3, SiMe3, Si(OEt)3, SiMe2OMe, SiMe2OEt, Si(OSiMe3)3, SiMe(OSiMe3)2, SiMe2(OSiMe3), or

[0007] [ka] and where the dashed line is the point of attachment from Y to X; Each R 5 is independently C1-C6-alkyl or phenyl; or R 4 teeth ii) -(Si(Me2) p (CH2) t -Z, wherein p is 0 or 1, with the proviso that when p is 0, t is 4, and when p is 1, t is 2; Z is one of the following:

[0008] [ka] In the formula, the dashed line indicates Z to (CH2) t It is the attachment point to DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present invention is a compound represented by formula I:

[0010] [ka] m is 0, 1, 2, or 3; and n is 0, 1, or 2. R 1 is -phenyl-(R 3 ) n , -C(O)-phenyl-(R 2 ) m , -O-C1~C 20 -Alkyl, or -O(CH2CH2O) x -H, where x is 1 to 20; Each R 2 are independently C1-C6-alkyl, C1-C6-alkoxy, -OCH2-phenyl, or R 2 is adjacent to the R 2 together with a 1,3-dioxolane group or a 1,4-dioxane group, Each R 3 is independently C1-C6-alkyl or C1-C6-alkoxy, R 4 teeth, i) -(Si(Me2) p (CH2) q (Si(R 5 2)O) r (X) s -Y, wherein p is 0 or 1, provided that when p is 0, q is 3 to 12, and when p is 1, q is 2 to 12; r is 3 to 300; X is CH2CH2 or CH(CH3); s is 0 or 1, with the proviso that when s is 0, Y is SiMe2H, and when s is 1, Y is Si(OMe)3, SiMe3, Si(OEt)3, SiMe2OMe, SiMe2OEt, Si(OSiMe3)3, SiMe(OSiMe3)2, SiMe2(OSiMe3), or

[0011] [ka] and where the dashed line is the point of attachment from Y to X; Each R 5 is independently C1-C6-alkyl or phenyl; or R 4 teeth ii) -Si(Me2) p (CH2) t -Z, wherein p is 0 or 1, with the proviso that when p is 0, t is 4, and when p is 1, t is 2; Z is one of the following:

[0012] [ka] In the formula, the dashed line indicates Z to (CH2) t It is the attachment point to

[0013] In one embodiment, R 1 is -C(O)-phenyl-(R 2 ) m The preferred R 1 Examples of groups are represented by the following structures:

[0014] [ka]

[0015] In one embodiment, R 4 is -(Si(Me2) p (CH2) q (Si(R 5 2)O) r (X) s -Y, and in another embodiment, each R 5 is methyl. In one embodiment, when p is 0, q is 3 or 4. In another embodiment, when p is 1, q is 2 and r is from 3 or 6 or 10, up to 300 or 200 or 100 or 50.

[0016] Compounds of formula I can be prepared as described in Schemes 1-3. 1 -C(O)-phenyl-(R 2 ) m and R 4 When is in the para position of the benzene ring, compounds of formula I can be prepared according to Scheme 1. The reaction conditions for each step are given in the experimental section.

[0017] [ka] In the formula, when p is 0, q' is 1 to 10, and when p is 1, q' is 0 to 10.

[0018] Or, R 1 -C(O)-phenyl-(R 2 ) m Compounds of the invention can be prepared by reacting the final intermediate with either compound A or B.

[0019] [ka] In the formula, X is CH2CH2 or CH(CH3).

[0020] When p is 1, the first compound in Scheme 1 can be prepared in a first step by contacting dibromobenzene, particularly p-dibromobenzene, with vinyldimethylsilyl chloride in the presence of n-butyllithium to form the following intermediate:

[0021] [ka] b is 0 to 10.

[0022] When p is 0, the first compound, particularly when q' is 2, can be prepared as described in Li, Y.-L. Song, D.-P. Pan, L. Ma, Z. Li, Y.-S. Polym. Chem. 2019, 10, 6368-6378.

[0023] R 1 -O-C1~C 20 -Alkyl, or -O(CH2CH2O) x When it is —H, compounds of formula I can be prepared according to Scheme 2.

[0024] [ka] In the formula, R is HO-C1 to C 20 -Alkyl, or HO(CH2CH2O) x -H.

[0025] R 1 -phenyl-(R 3 ) n When it is, compounds of formula I can be prepared according to Scheme 3.

[0026] [ka]

[0027] A homogeneous, non-cloudy composition comprising the compound of the present invention and an ethylenically unsaturated organopolysiloxane can be prepared by vigorously mixing the compound with the organopolysiloxane. Examples of suitable ethylenically unsaturated polyorganosiloxanes include diethylenically unsaturated compounds having the formula:

[0028] [ka] In the formula, y is 10 to 10,000, and R 5 is as defined above. Commercially available polyorganosiloxanes include XIAMETER™ RBL-9119 organopolysiloxane and XIAMETER™ RBL-9128 organopolysiloxane (XIAMETER is a trademark of The Dow Chemical Company or its affiliates).

[0029] The concentration of the photoinitiator core typically ranges from 0.1% or 0.2% to 4% or 2% by weight based on the weight of the composition. As used herein, "photoinitiator core" refers to the following fragment of the compound of the invention:

[0030] [ka] It is. EXAMPLES

[0031] Intermediate Example 1 Preparation of (4-(but-3-en-1-yl)phenyl)dichlorophosphane In a glove box, a 500 mL round bottom flask was charged with 1-bromo-4-(but-3-en-1-yl)benzene (17.1 g), dry THF (118 mL), and dry diethyl ether (37 mL). The flask was sealed and transferred to a fume hood. The mixture was stirred under N2 and cooled to -78 °C, then n-butyl lithium (n-BuLi (2.5 M in hexanes, 34.0 mL) was added dropwise to the mixture. The mixture was stirred for 30 min, followed by chlorobis(diethylamino)phosphine (17.9 mL, 85.1 mmol). The mixture was stirred for 20 min and allowed to warm to ambient temperature. The solution was poured into a separatory funnel containing diethyl ether and water. The phases were separated and the aqueous phase was extracted several times with diethyl ether. The combined organic fractions were washed with brine, dried over MgSO4, and concentrated under vacuum.

[0032] The crude oil was transferred to a 1000 mL round bottom flask which was placed in a glove box. The oil was dissolved in dry diethyl ether (100 mL). The mixture was stirred and treated dropwise with HCl (2.0 M in diethyl ether, 162 mL, 324 mmol, 4.00 equiv), precipitating a white solid. After 2 h, the slurry was filtered and the filtrate was concentrated. A colorless oil was isolated (15.9 g, 84%) which was used in the next step without further purification.

[0033] 1 H NMR(500MHz,C6D6)δ7.63-7.40(m,2H),6.86-6.76(m,2H),5.62(ddt,J=18.1,9.5,6.6Hz ,1H),5.00-4.83(m,2H),2.35(dd,J=8.8,6.7Hz,2H),2.06(tdt,J=7.8,6.5,1.5Hz,2H).

[0034] 13 C NMR(126MHz,C6D6)δ146.99,137.73(d,J=51.8Hz),137.14,130.12(d,J=32.1Hz),128.85(d,J=8.3Hz),115.16,35.02,34.73.

[0035] 31P NMR (202MHz, C6D6) δ161.94.

[0036] Intermediate Example Preparation of 2-(4-(but-3-en-1-yl)phenyl)phosphane In a glove box, a 500 mL jar was charged with diethyl ether (100 mL) and LiAlH4 (2.0 M in THF, 19.8 mL, 39.6 mmol, 0.60 equiv). The solution was stirred vigorously and Intermediate Example 1 (15.4 g, 66.1 mmol, 1.00 equiv) in diethyl ether (65 mL) was added dropwise to the solution over 10 min. The mixture was stirred for 30 min, after which solid Glauber's salt (25.5 g, 79.3 mmol, 1.20 equiv) was carefully added. The mixture was stirred for 60 min, the liquid was decanted, filtered through a 0.45 μm syringe filter, and concentrated to give a colorless oil (9.73 g, 90%) which was used in the next step without further purification.

[0037] 1 H NMR(500MHz,C6D6)δ7.33-7.22(m,2H),6.88-6.79(m,2H),5.70(ddt,J=16.9,10.2,6.6Hz,1H),5.02- 4.89(m,2H),3.87(d,J=198.5Hz,2H),2.44(dd,J=8.8,6.7Hz,2H),2.16(tdt,J=7.9,6.6,1.5Hz,2H).

[0038] 13 C NMR(126MHz,C6D6)δ141.77,137.65,134.92(d,J=15.7Hz),134.19(dt,J=26.8,9.8Hz),128.56(d,J=6.2Hz),114.84,35.26,34.96.

[0039] 31 P NMR (202MHz, C6D6) δ-125.28 (tt, J=197.6, 7.3Hz).

[0040] Intermediate Example 3 Preparation of ((4-(but-3-en-1-yl)phenyl)phosphoryl)bis(mesitylmethanone) In a glove box, a solution of Intermediate Example 2 (9.73 g, 59.3 mmol, 1.00 equiv) in dry THF (300 mL) was treated with sodium tert-butoxide (Nat-OBu, 11.4 g, 118 mmol, 2.00 equiv) and then 2,4,6-trimethylbenzoyl chloride (19.8 mL, 118 mmol, 2.00 equiv) was added dropwise to the mixture. The mixture was stirred overnight. Crude 31 P NMR spectroscopic analysis showed that the phosphine was partially consumed. Additional amounts of Nat-OBu (3.99 g) and benzoyl chloride (6.9 mL) were added to the reaction mixture. After 5 h, the mixture was filtered to remove sodium chloride, and the filtrate was removed from the glove box and concentrated in vacuo. The crude residue was dissolved in dichloromethane (200 mL) and the solution was treated with hydrogen peroxide (6.0 mL, 30 wt%). The mixture was stirred overnight at ambient temperature, then treated with aqueous sodium bisulfite (100 mL) and stirred until the organic phase was negative to a peroxide strip test. The phases were separated and concentrated over Celite for chromatography on silica gel (0-50% EtOAc in hexanes). A yellow oil (13 g) containing the product and some other impurities was isolated. A second column purification was performed, after which Intermediate Example 3 (11.3 g) was isolated as a yellow oil.

[0041] 1 H NMR(500MHz,CDCl3)δ7.78(dd,J=10.1,8.1Hz,2H),7.23(dd,J=8.3,3.0Hz,2H),6.78(s,4H),5.77(ddt,J=16 .0,10.7,6.6Hz,1H),5.20-4.61(m,2H),2.74(t,J=7.6Hz,2H),2.39-2.32(m,2H),2.25(s,6H),2.14(s,12H).

[0042] 13C NMR (126MHz, CDCl3) δ216.37(d,J=59.9Hz),147.41(d,J=2.9Hz),140.92,137.12,135.73(d,J=41.8Hz),135.47 ,132.19(d,J=8.3Hz),128.93,128.77(d,J=11.6Hz),122.82(d,J=78.0Hz),115.50,35.32,34.93,21.18,19.60.

[0043] Intermediate Example Preparation of 4-(4-bromophenyl)dimethyl(vinyl)silane A 1000 mL 3-neck round bottom flask equipped with an addition funnel was charged with dry THF (425 mL) and 1,4-dibromobenzene (20.0 g, 84.8 mmol, 1.00 equiv) under a blanket of N2. The mixture was stirred and cooled to -78 °C. n-BuLi solution (2.5 M in hexanes, 35.6 mL, 89.0 mmol, 1.05 equiv) was added dropwise to the dibromobenzene solution over 25 min. Stirring was continued for an additional 50 min after addition of the n-BuLi solution was complete.

[0044] Chlorodimethylvinylsilane (12.9 mL, 93.3 mmol, 1.10 equiv) was added dropwise to the reaction mixture with stirring. The mixture was allowed to warm gradually to room temperature over 1 h, after which the mixture was quenched with aqueous ammonium chloride. The product was extracted several times with ethyl acetate. The combined organic fractions were dried over sodium sulfate and concentrated. The crude oil was purified under vacuum (450 M Torr, 52-60° C.) to give Intermediate Example 4 (18.75 g) as a colorless oil.

[0045] 1 H NMR(400MHz,CDCl3)δ7.53-7.44(m,2H),7.40-7.33(m,2H),6.25(dd,J=20.2,14. 6Hz, 1H), 6.06 (dd, J=14.6, 3.8Hz, 1H), 5.74 (dd, J=20.2, 3.8Hz, 1H), 0.33 (s, 6H).

[0046] 13C NMR (101MHz, CDCl3) δ137.33,137.22,135.42,133.26,130.90,123.83,-3.03.

[0047] Intermediate Example 5 - Preparation of ((4-(dimethyl(vinyl)silyl)phenyl)phosphoryl)bis(mesitylmethanone) In a glove box, a 250 mL round bottom flask was charged with Intermediate Example 4 (4.31 g, 17.9 mmol, 1.00 equiv), dry THF (26 mL), and dry diethyl ether (8 mL). The flask was sealed and transferred to a fume hood. The mixture was stirred under nitrogen and cooled to -78°C. n-BuLi (2.5 M in hexanes, 7.51 mL, 18.8 mmol, 1.05 equiv) was added dropwise. The mixture was stirred for 30 min, after which chlorobis(diisopropylamino)phosphine (5.01 g, 18.8 mmol, 1.05 equiv) was added as a solid. The mixture was stirred and allowed to warm to ambient temperature over 2 h. The solution was poured into a separatory funnel containing diethyl ether and water. The phases were separated and the aqueous phase was extracted several times with diethyl ethyl ether. The combined organic fractions were washed with brine, dried over MgSO4, and concentrated on a rotary evaporator.

[0048] The crude oil was transferred to a 250 mL round bottom flask, which was placed in a glove box. The oil was dissolved in dry diethyl ether (20 mL). The flask was sealed and transferred to a fume hood. The mixture was stirred and cooled to 0° C. under N2. HCl (2.0 M in diethyl ether, 35.7 mL, 71.5 mmol, 4.00 equiv) was then added dropwise, precipitating a white solid. After continued stirring for 2 h, the slurry was filtered and the filtrate was concentrated. The crude residue was mixed with diethyl ether and hexanes and filtered again. The filtrate was concentrated to give a colorless oil (4.59 g). The crude material was used in the next step without further purification.

[0049] In a glove box, a 150 mL jar was charged with diethyl ether (44 mL) and LiAlH4 (2.0 M in THF, 5.23 mL, 10.5 mmol, 0.60 equiv.) under vigorous stirring. The crude material from the previous step (4.59 g, 17.4 mmol, 1.00 equiv.) was added dropwise to the LiAlH4 solution over 5 min. The mixture was stirred for 30 min, after which solid Glauber's salt (6.74 g, 20.9 mmol, 1.20 equiv.) was carefully added. Stirring was continued for 14 h, after which the solution was filtered and the filtrate was concentrated to give 2.71 g of crude product as a colorless oil. The crude material was used in the next step without further purification.

[0050] A solution of the crude material from the previous step (2.71 g) in dry THF (70 mL) was treated with dry Nat-OBu (2.68 g, 27.9 mmol, 2.00 equiv.), followed by the dropwise addition of 2,4,6-trimethylbenzoyl chloride (4.65 mL, 27.9 mmol, 2.00 equiv.). The mixture was stirred for 3 h, and then the mixture was filtered to remove sodium chloride.

[0051] The filtrate was removed from the glove box and concentrated in vacuo. The crude residue was dissolved in dichloromethane (50 mL) and the solution was treated with hydrogen peroxide (1.4 mL, 30 wt%). The mixture was stirred at ambient temperature overnight and then treated with aqueous sodium bisulfite (30 mL). The phases were separated and the organic phase was concentrated in the presence of silica gel to facilitate liquid chromatography on silica gel (0-50% EtOAc in hexanes). Intermediate Example 5 (1.98 g) was isolated as a yellow oil that solidified on standing.

[0052] 1 H NMR(500MHz,CDCl3)δ7.90-7.79(m,2H),7.56(dd,J=8.0,3.3Hz,2H),6.78(s,4H),6.24(dd,J=20.2,14.7H z,1H),6.07(dd,J=14.6,3.6Hz,1H),5.71(dd,J=20.3,3.7Hz,1H),2.25(s,6H),2.14(s,12H),0.35(s,6H).

[0053] 13 C NMR(126MHz,CDCl3)δ215.87(d,J=58.9Hz),144.76(d,J=2.5Hz),140.99,136.91,135.84,135.52,13 3.67(d,J=10.8Hz),133.55,131.01(d,J=7.6Hz),128.95,126.27(d,J=75.6Hz),21.18,19.64,-3.17.

[0054] 31 P NMR (202MHz, CDCl3) δ7.19 (t, J=10.6Hz).

[0055] In the following examples, M'D r M' polysiloxane is H-Si(Me2)O[Si(Me2)O] r -Si(Me2)-H.

[0056] Example 1-M'D 38 Preparation of M' polysiloxane substituted photoinitiators Intermediate Example 3 (0.07 g) was dissolved in dry hexane (3.0 mL) and M'D 38 M' polysiloxane (1.72 g) was mixed in a glove box. The mixture was stirred at 50 °C until the solids were dissolved. Karstedt's catalyst (2 wt% Pt in xylene, 0.03 mL) was added and the mixture was stirred overnight. The consumption of the alkene was 1 Monitored by H NMR spectroscopy, additional Karstedt's catalyst was added until <5% of the alkene remained. Vinyltrimethoxysilane was added to react with the remaining Si-H groups.

[0057] The volatiles were removed by vacuum pump leaving a yellow oil. The product mixture was calculated to contain 4.0 wt% photoinitiator.

[0058] Example 2 - Preparation of M'D7M' Polysiloxane Substituted Photoinitiator The procedure described in Example 1 was followed except that M'D7M' polysiloxane (0.55 g) was used. The product mixture was calculated to contain 15.3 wt % photoinitiator.

[0059] Example 3 -M'D 14 Preparation of M' polysiloxane substituted photoinitiators M'D 14 The procedure described in Example 1 was followed except that M' polysiloxane (0.99 g) was used. The product mixture was calculated to contain 9.1 wt% photoinitiator.

[0060] In Examples 1 to 3, the following products and by-products were identified.

[0061] [ka]

[0062] Example 4 -M'D 38 Preparation of M' polysiloxane substituted photoinitiators Intermediate Example 5 (0.10 g) was dissolved in dry toluene (1.5 mL) and M'D 38 M' polysiloxane (0.60 g) was mixed in a glove box. The mixture was stirred at 80° C. until the solids were dissolved. Karstedt's catalyst (2 wt % Pt in xylene, 0.012 mL) was added to the mixture and stirring was continued for 1 h. The consumption of the alkene was confirmed by 1 The reaction was monitored by H NMR spectroscopy and additional Karstedt's catalyst was added until <5% of the alkene remained. Vinyltrimethoxysilane was added to react with the remaining Si-H groups. Volatiles were removed in vacuo leaving a yellow oil. The product mixture was calculated to contain 14.5 wt% photoinitiator.

[0063] Example 5 - Preparation of M'D7M' Polysiloxane Substituted Photoinitiator The procedure described in Example 4 was followed except that M'D7M' polysiloxane (0.14 g) was used. The product mixture was calculated to contain 43.5% by weight photoinitiator.

[0064] Example 6 -M'D 14 Preparation of M' polysiloxane substituted photoinitiators M'D 14 The procedure described in Example 4 was followed except that M' polysiloxane (0.24 g) was used. The product mixture was calculated to contain 30.0 wt. % photoinitiator. The following products and by-products were identified for Examples 4-6:

[0065] [ka]

[0066] Example 7 - Preparation of Compound A-Substituted Photoinitiators Intermediate Example 5 (0.11 g) was mixed with dry toluene (1.5 mL) under stirring in a glove box at 80° C. until the solid dissolved. Compound A (0.19 mL) was added to the mixture along with Karstedt's catalyst (2 wt % Pt in xylene, 0.06 mL) and the mixture was stirred for 1 hour. The consumption of Intermediate Example 5 was 1 The reaction was monitored by H NMR spectroscopy. Additional catalyst was added until <5 wt% starting material remained. Excess vinyltrimethoxysilane was then added and stirring was continued until the Si-H functionality was completely consumed. The volatiles were removed in vacuo leaving a yellow oil. The product was calculated to contain 18 wt% photoinitiator. The following products were identified:

[0067] [ka]

[0068] Example 8 - Preparation of Compound B-Substituted Photoinitiators The procedure described in Example 7 was followed except that Compound B (0.10 mL) was used. The product was calculated to contain 20% by weight of photoinitiator. The following products were identified:

[0069] [ka]

[0070] Example 9 - Preparation of Compound A-Substituted Photoinitiators Intermediate Example 3 (0.14 g) was mixed with dry hexane (3.0 mL) and dry toluene (1.5 mL) in a glove box at 50° C. with stirring until the solids dissolved. Compound A (1.03 mL) was added to the mixture along with Karstedt's catalyst (2 wt % Pt in xylene, 0.06 mL) and the mixture was stirred for 1 hour. The consumption of Intermediate Example 3 was 1 The reaction was monitored by H NMR spectroscopy. Additional catalyst was added until <5 wt% starting material remained. Excess vinyltrimethoxysilane was then added and stirring was continued until the Si-H functionality was completely consumed. The volatiles were removed in vacuo leaving a yellow oil. The product was calculated to contain 18 wt% photoinitiator. The following products were identified:

[0071] [ka]

[0072] Photoinitiator composition preparation Each of the compounds prepared in Examples 1-9 was mixed with enough XIAMETER® RBL-9119 organopolysiloxane to form a 0.5% by weight mixture relative to the photoinitiator core. The compositions were visually inspected for homogeneity. No samples were observed containing solid particles or phase-separated oil droplets. Thus, all were found to be homogeneous.

[0073] After visual inspection for uniformity, each vial was placed in a robotic imaging station. Photographs were taken at ambient temperature to measure phase clarity. Phase clarity was determined by subtracting the image background, cropping the image, thresholding pixel intensities using an Otsu threshold, and calculating the average intensity over the remaining pixels. Pixel intensity (phase clarity) was reported as a value between 0 (transparent) and 255 (opaque). A pixel intensity of <120 was considered passing clarity.

[0074] [Table 1]

[0075] Compositions prepared from the photoinitiator compounds and photocurable organopolysiloxanes have been found to meet the criteria of homogeneity, transparency, and stability against degradation.

Claims

1. A compound of formula I, 【Chemistry 1】 m is 0, 1, 2, or 3; n is 0, 1, or 2; R １ is -phenyl-(R ３ ) ｎ , —C(O)-phenyl-(R ２ ) ｍ , -O-C １ ~C ２０ -alkyl, or -O(CH ２ CH ２ O) ｘ -H, where x is 1 to 20; Each R ２ is independently １ ~C ６ -Alkyl, C １ ~C ６ -Alkoxy, -OCH ２ -phenyl, or R ２ is adjacent to R on the phenyl ring ２ together with a 1,3-dioxolane group or a 1,4-dioxane group, Each R ３ is independently １ ~C ６ -Alkyl or C １ ~C ６ -alkoxy, R ４ teeth, i)-(Si(Me ２ ) ｐ (CH ２ ) ｑ (Si(R ５ ２ ) O) ｒ (X) ｓ -Y, wherein p is 0 or 1, with the proviso that when p is 0, q is 3 to 12, and when p is 1, q is 2 to 12; r is 3 to 300; X is CH ２ CH ２ or CH(CH ３ ) and s is 0 or 1, provided that when s is 0, Y is SiMe ２ H, and when s is 1, Y is Si(OMe) ３ , SiMe ３ , Si(OEt) ３ , SiMe ２ OMe, SiMe ２ OEt, Si(OSiMe ３ ) ３ , SiMe (OSiMe ３ ) ２ , SiMe ２ (OSiMe ３ ), or 【Chemistry 2】 and where the dashed line is the point of attachment of Y to X; Each R ５ is independently １ ~C ６ - alkyl or phenyl, Or R ４ teeth ii)-(Si(Me ２ ) ｐ (CH ２ ) ｔ -Z, wherein p is 0 or 1, with the proviso that when p is 0, t is 4, and when p is 1, t is 2; Z is one of the following: 【Chemistry 3】 In the formula, the dashed line indicates the linkage from Z to (CH ２ ) ｔ A compound that is a point of attachment to

2. Each R ５ The compound of claim 1 , wherein is methyl.

3. R １ is -C(O)-phenyl-(R ２ ) ｍ and R ４ but -(Si(Me ２ ) ｐ (CH ２ ) ｑ (Si(Me ２ ) O) ｒ (X) ｓ -Y, wherein r is 6 to 200 and s is 1.

4. n is 0, p is 1, q is 2, r is 6 to 50, and Y is Si(OMe) ３ 4. The compound of claim 3,

5. m is 3, and each R ２ is methyl, R １ is represented by the fragment 【Chemistry 4】 5. The compound of claim 4,

6. R １ is -C(O)-phenyl-(R ２ ) ｍ and Z is 【Chemistry 5】 The compound according to claim 1, wherein

7. n is 0, m is 3, and each R ２ is methyl, and each R ５ The compound of claim 5 , wherein is methyl.

8. A composition comprising a solution of a compound of formula I of claim 1 and an ethylenically unsaturated organopolysiloxane.

9. The ethylenically unsaturated organopolysiloxane is represented by the structure: 【Chemistry 6】 y is 10 to 10,000, and each R ５ is independently １ ~C ６ The composition of claim 8, wherein: - alkyl or phenyl.

10. Each R ５ The composition of claim 9 , wherein is methyl.

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