Siloxane-functionalized platinum oxalate complex

Abstract

The present invention relates to a platinum(II) oxalate compound of the following formula. [Case 1] JPEG2026517137000026.jpg42170 In the formula, R 1 , R 2 , and R 3 The term is defined above. The platinum(II) oxalate compounds of the present invention are useful as catalysts in hydrosilylation reactions, particularly in the hydrosilylation of curable siloxanes.

Description

[Technical Field]

[0001] This invention relates to a compound that is a platinum oxalate complex functionalized with a siloxane group, more specifically, a platinum oxalate complex functionalized with a phenyl group substituted with a siloxane group. This compound is useful as a catalyst for hydrosilylation reactions.

[0002] Platinum catalysts are used to promote the hydrosilylation of organohydrogenpolysiloxanes (Si-H-containing siloxanes) using vinyl-functionalized siloxanes. UV-initiated hydrosilylation reactions are particularly desirable due to the low energy input required to initiate the reaction. Currently, two groups of platinum compounds, cyclopentadienyltrialkylplatinum(IV)(C), are used for this purpose. p PtR3) and platinum(II) acetylacetonate (Pt(acac)2) are commercially used.

[0003] The most common C p Cyclopentadienyltrimethylplatinum(IV) and methylcyclopentadienyltrimethylplatinum(IV), which are PtR3 catalysts, have limited solubility in common siloxane polymers and are too volatile for applications requiring thin coatings.

[0004] Pt(acac)2 also has limited solubility in siloxane polymers, C p It promotes hydrosilylation even more slowly than the PtR3 catalyst. Furthermore, formulations containing Pt(acac)2 have relatively low dark stability.

[0005] Therefore, in the field of UV-induced hydrosilylation of polysiloxanes, there is a need to improve the solubility and curing efficiency of platinum-based catalysts. [Overview of the project]

[0006] The present invention addresses the needs in the art by providing a platinum(II) oxalate compound of the following formula.

[0007]

Chem.

[0008]

Chem.

[0009] The compounds of the present invention are useful as catalysts in hydrosilylation reactions, particularly in the UV-induced hydrosilylation of curable siloxanes.

Mode for Carrying Out the Invention

[0010] The present invention relates to a platinum(II) oxalate compound of the following formula.

[0011] [ka] (In the formula, R 1 Phenyl(CH2) n R 4 And n is 3 to 30; each R 2 It is independently, C1-C 10 Alkyl, phenyl, or phenyl (CH2) n R 4 and; each R 3 It is independently, C1-C 10 Alkyl, phenyl, phenyl (CH2) n R 4 is or each R 3 These, together with the phosphorus atoms to which they are bonded, form diphosphines; each R 4 It is one of the following:

[0012] [ka] In the formula, R 5 C1-C 10 Alkyl or phenyl; R 6 C1-C 10 Alkyl, phenyl, or O-Si(CH3)3; each R 7 It is independently, C1-C 10 Alkyl or phenyl; R 7’ C1-C 10 It is alkyl; each R 8 It is independently, C1-C 10 (It is alkyl or phenyl; x is between 2 and 250; the dotted line represents the bond point to the CH2 group.)

[0013] R 5 C1-C 10 Alkyl or C1-C6 alkyl or methyl or phenyl; R 6 C1-C10 Alkyl or C1-C6 alkyl or methyl or phenyl or O-Si(CH3)3; each R 7 It is independently, C1-C 10 Alkyl or C1-C6 alkyl or methyl or phenyl; R 7’ C1-C 10 It is alkyl or C1-C6 alkyl or methyl; n is from 3 or 4, 30 or 20 or 10; each R 8 It is independently, C1-C 10 It is alkyl or C1-C6 alkyl or methyl or phenyl; x is from 2 to 250 or 100 or 50 or 20 or 12.

[0014] Examples of phosphine ligands are shown below.

[0015] [ka] In the formula, each R 1 ' is independently, (CH2) n R 4 That is. R 2 Examples of groups include methyl, ethyl, propyl, n-butyl, n-hexyl, n-octyl, and n-decyl.

[0016] R 3 The groups, together with the phosphine atoms to which they are bonded, can form diphosphines, for example:

[0017] [ka] In the formula, m is 0, 1, 2, 3, 4, or 5.

[0018] The following reaction scheme illustrates the preparation of monophenylsiloxy, bis(phenylsiloxy), and tri(phenylsiloxy)phosphine ligands.

[0019] [ka]

[0020] Mono and bis(phenylsiloxy)diphosphines can be prepared as follows:

[0021] [ka]

[0022] Bromophenylsiloxane starting materials can be prepared by the following scheme.

[0023] [ka]

[0024] The platinum oxalate compounds of the present invention can be prepared by reacting a phosphine ligand with dipotassium platinum(II) oxalate according to the procedure described in International Publication No. 2005 / 051996. The general scheme is as follows.

[0025] [ka] In the formula, L is a phosphine ligand.

[0026] The compounds of the present invention are useful as catalysts to improve the reaction efficiency of vinylsiloxane and silane under UV light at room temperature. Furthermore, the mixture of reagent and catalyst exhibits good to excellent dark stability, i.e., relative stability against undesirable reactions under conditions not exposed to UV light. [Examples]

[0027] Intermediate Example 1 - Preparation of 1-bromo-4-(buta-3-en-1-yl)benzene 4-Bromobenzyl bromide (10.0 g, 40.01 mmol, 1 equivalent) was dissolved in THF (25 mL) and then cooled to 0°C. Allyl magnesium bromide (44 mL, 44.01 mmol, 1 equivalent) was then slowly added by syringe. The solution was warmed to ambient temperature while stirring for 20 hours. The reaction mixture was then carefully quenched with water. To the quenched mixture, brine solution (100 mL) was added and stirred for 10 minutes. The organic phase was washed with brine and dried over MgSO4. The solvent was removed under vacuum to obtain an oily substance. The crude material was then subjected to ISCO column chromatography with silica (100% hexane). The final product was recovered as a colorless oily substance. Yield: 5.08 g, 60.1%. 1 H NMR (400MHz, CDCl3)δ 7.47-7.36(m,1H),7.10-7.02(m,1H),5.93-5.68(m,1H),5.13-4.91(m,1H),2.75-2.61(m,1H),2.42-2.24(m,1H). 13 C NMR(101MHz, CDCl3)δ 140.9,137.7,131.4,130.3,119.7,115.4,35.4,34.9.

[0028] Intermediate Example 2 - 1-(4-(4-bromophenyl)butyl)-1,1,3,3,3-pentamethyldisiloxane ( MM-Si Preparation of Ar-Br

[0029] [ka]

[0030] 1-Bromo-4-(buta-3-en-1-yl)benzene (2 g, 9.47 mmol, 1 equivalent) was added to a 50 mL round-bottom flask along with a magnetic stirring rod and Karstedt catalyst (2-3 drops of 2 wt% Pt solution in xylene). The mixture was heated to 50°C, and 1,1,1,3,3-pentamethyldisiloxane (MM') (1.41 g, 9.47 mmol, 1 equivalent) was added dropwise. The reaction mixture was heated for 2 hours and then cooled to ambient temperature. Phase separation was induced by adding acetonitrile (2 mL) to the mixture. Acetonitrile was decanted from the product, and the solvent addition step and decanting were repeated two more times. The resulting colorless product was further dried under vacuum. Yield: 3.10 g, 91.1%. 1 H NMR(400MHz,CDCl3)δ 7.38(d,J=8.3Hz,2H),7.04(d,J=8.3Hz,2H),2.64-2.48(m,2H),1.66-1.5 6(m,2H),1.41-1.30(m,2H),0.58-0.48(m,2H),0.05(s,9H),0.03(s,6H).

[0031] Intermediate Example 3 - 3-(4-(4-bromophenyl)butyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane ( MDM-Si Preparation of Ar-Br

[0032] [ka]

[0033] 1-Bromo-4-(buta-3-en-1-yl)benzene (2 g, 9.47 mmol, 1 equivalent) was added to a 50 mL glass vial in a fume hood along with a magnetic stirring rod and Karstedt catalyst (4 drops of 2 wt% in xylene). The mixture was heated to 50°C with stirring, and 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD'M, 2.57 mL, 9.47 mmol, 1 equivalent) was added dropwise. The reaction mixture was stirred at 50°C for 22 hours and then cooled to ambient temperature. The mixture was diluted with hexane (4 mL) with stirring. Activated carbon was then added to the mixture with stirring for approximately 1 minute. The mixture was continuously filtered through a 0.45 μm syringe filter, and then through a 0.2 μm syringe filter. The solvent was removed under vacuum. Next, the resulting pale yellow liquid was purged with N2 and stored in a glove box under a 4 Å molecular sieve for 24 hours before use. Yield: 3.99 g, 97.1%. 1 H NMR(500MHz,CDCl3)δ 7.41-7.35 (m,1H),7.04(d,J=8.0Hz,1H),2.56(t,J=7.7Hz,1H),1.61(p,J=7.6Hz,1H) ,1.42-1.30(m,1H),0.53-0.43(m,1H),0.07(d,J=1.0Hz,7H),-0.01(s,1H). 13 C NMR(126MHz, CDCl3)δ 141.9,131.4,130.3,119.4,35.2,34.9,22.8,17.6,2.0,-0.1.

[0034] Intermediate Example 4 - 1-(4-(4-bromophenyl)butyl)-butyl-polymethyldisiloxane ( nBu-PDMS Preparation of Ar-Br (dp=10~12)

[0035] [ka]

[0036] In a fume hood, 1-bromo-4-(buta-3-en-1-yl)benzene (5.08 g, 24.06 mmol, 1 equivalent) was added to a 100 mL round-bottom flask along with a magnetic stirring rod and Karstedt catalyst (4-5 drops of 2 wt% Pt solution in xylene). The mixture was then heated to 50°C with stirring, and MCR-H07 monohydride-terminated polydimethylsiloxane (Gelest, Inc., DP 10-12, 22.7 g, approximately 26.47 mmol, approximately 1.1 equivalents) was added dropwise. The reaction mixture was heated at 50°C for 12 hours and then cooled to ambient temperature. The product was washed with acetonitrile (3 × 25 mL), then dissolved in diethyl ether (4 mL), stirred with activated carbon, and filtered. Volatile substances were removed under vacuum to obtain a viscous liquid product. Yield: 24.4 g, 95.0%. 1 ¹H NMR (400 MHz, CDCl3) δ = 1 H NMR(400MHz,CDCl3)δ 7.38(d,J=8.3Hz,2H),7.04(d,J=8.3Hz,2H),2.62-2.51(m,2H),1.67-1.55(m,2H) ), 1.44-1.23 (m, 6H), 0.92-0.83 (m, 3H), 0.61-0.48 (m, 4H), 0.10-0.01 (overlapping, 72H). 13 C NMR(101MHz, CDCl3)δ 141.9,131.4,130.3,119.4,35.2,35.2,26.5,25.6,23.0,18.2,18.1,14.0,1.3,1.2,0.3.

[0037] Intermediate Example 5- MM-Si Preparation of ArPPh2

[0038] [ka]

[0039] MM-SiAr-Br (2.080 g, 5.79 mmol, 1 equivalent) was added to a vial in a nitrogen glove box along with a magnetic stirring rod and diethyl ether (25 mL). The solution was stored at -25°C for 60 minutes, then transferred to a vial holder maintained at -25°C. A 2.5 M solution of n-BuLi (2.315 mL, 5.79 mmol, 1 equivalent) was added dropwise to the solution, and the mixture was stirred in the cold vial holder for 30 minutes, then returned to a freezer at -25°C for 10 minutes. Ph2PCl (1.28 g, 1.04 mL, 5.79 mmol, 1 equivalent) was added to the reaction mixture at -25°C, and the resulting pale yellow mixture was gradually warmed to ambient temperature while continuing to stir for 24 hours. Volatile substances were removed under vacuum, and the yellow residue was extracted with pentane, filtered, and concentrated to obtain a yellow to orange oily substance. The product was purified using ISCO chromatography with silica (0-50% ethyl acetate in hexane), and the purified material (2.5 g) was then subjected to supercritical CO2 chromatography using a bridged ethylene hybrid (BEH) column with a 25% isopropanol-75% ethyl acetate cosolvent mixture. The cosolvent percentage gradient was increased from 2% to 5% over a 10-minute period (the remainder being CO2). Mass-specified sampling was performed at 465 based on the target compound. 1 H NMR(400MHz,C6D6)δ 7.34-7.01(m,4H),2.62-2.44(m,2H),1.70-1.51(m,2H),1.39-1.24(m,2H),0.61-0.44(m,2H),-0.02(s,9H),-0.03(s,6H). 13 C NMR(101MHz,C6D6)δ 143.9,137.8,137.7,134.0(d,J=19.9Hz),133.8(d,J=19.3Hz),128.8(d ,J=7.4Hz),128.7,128.6(d,J=6.8Hz),35.6,35.1,23.2,18.4,2.1,0.5. 31 P NMR (162 MHz, CDCl3) δ -6.2.

[0040] Intermediate Example 6- MDM-Si Preparation of ArPPh2

[0041] [ka]

[0042] MDM-Si Ar-Br (1.05 g, 2.42 mmol, 1 equivalent) was added to a 40 mL glass vial in a nitrogen glove box along with a magnetic stirring rod and THF (8 mL), and the mixture was heated to 60°C. In a separate 7 mL vial, freshly ground magnesium shavings (approximately 100 mg) were combined with THF (1 mL) and a catalytic amount of iodine (approximately 2 mg) to form a suspension. The suspension was vigorously stirred until it became colorless, and then... MDM-Si The compound was added to the Ar-Br solution. The resulting product (Grignard reagent) was vigorously stirred at 60°C for 6 hours, and then cooled to ambient temperature. 1,4-Dioxane (2 mL) was added to the Grignard reagent, and the mixture was stirred for 10 minutes to produce a colorless solid precipitate. The mixture was then filtered through Celite and concentrated to obtain a viscous liquid. The filtrate was combined with diethyl ether (4 mL) and stored at -25°C for 30 minutes. Separately, diphenylchlorophosphine (0.401 mL, 2.18 mmol, 0.9 equivalents) was combined with diethyl ether (4 mL) and stored at -25°C for 30 minutes. This cooled phosphine solution was then added dropwise to the Grignard reagent solution at -25°C. After the addition was complete, the reaction mixture was slowly heated to ambient temperature while stirring for 20 hours. Volatile substances were removed under vacuum, and the resulting pale yellow material was extracted with dichloromethane (3 × 5 mL), filtered through Celite, and concentrated to obtain a pale yellow liquid. The material was purified by ISCO chromatography in silica using 0-50% dichloromethane (DCM) in hexane. Yield: 0.75 g, 57.5%. 1 H NMR(500MHz,CDCl3)δ 7.39-7.28(m,10H),7.24(t,J=8.8Hz,2H),7.16(d,J=7.7Hz,2H),2.61(t,J=7.7Hz,2H), 1.64(p,J=7.6Hz,2H),1.41-1.33(m,2H),0.58-0.46(m,2H),0.08(s,18H),0.00(s,3H). 1313C NMR (126 MHz, CDCl3) δ 143.9, 137.8, 137.8, 134.1, 133.9, 133.9, 133.8, 133.7, 128.9, 128.8, 128.7, 128.6, 128.5, 35.6, 34.9, 22.9, 17.6, 2.0, -0.1. 31 31P NMR (202 MHz, CDCl3) δ -6.06.

[0043] Intermediate Example 7- nBu-PDMS Preparation of ArPPh2

[0044]

Chemical Structure

[0045] nBu-PDMS The procedure described for the preparation of ArPPh2 was used, except that Ar-Br (1.00 g, 0.80 mmol, 1 equivalent) and diphenylchlorophosphine (0.132 mL, 0.72 mmol, 0.9 equivalent) were used. Yield: 0.660 g, 70.5%. MDM-Si 1H NMR (500 MHz, CDCl3) δ 7.36 - 7.28 (m, 10H), 7.23 (t, J = 7.7 Hz, 2H), 7.16 (d, J = 7.8 Hz, 2H), 2.61 (t, J = 7.8 Hz, 2H), 1.65 (p, J = 7.6 Hz, 2H), 1.46 - 1.21 (overlapped, 8H), 0.89 (t, J = 6.6 Hz, 4H), 0.61 - 0.49 (m, 4H), 0.13 - 0.02 (m, 74H). 1 31P NMR (202 MHz, CDCl3) δ -6.11. 31

[0046] Intermediate Example 8-( MM MM-Si Preparation of (Ar)2PPh MM-Si The procedure was used, except that Ar (1.02 g, 2.84 mmol, 1 equivalent) and phenyldichlorophosphine (0.193 mL, 1.42 mmol, 0.5 equivalent) were used. MDM-SiThe procedure described for the preparation of ArPPh2 was used. The material was purified by ISCO chromatography on silica using a gradient of ethyl acetate in hexanes (0 - 80%). Yield: 0.280 g, 30.0%. 1 1H NMR (500 MHz, CDCl3) δ 1H NMR (400 MHz, CDCl3) δ 7.37 - 7.29 (m, 5H), 7.27 - 7.14 (doublet of multiplets, 8H), 7.19 - 7.14 (m, 1H), 2.71 - 2.46 (m, 4H), 1. - 1.60 (m, 4H), 1.51 - 1.25 (m, 4H), 0.71 - 0.49 (m, 4H), 0.07 (s, 18H), 0.06 (s, 12H). 31 31P NMR (202 MHz, CDCl3) δ -6.87.

[0047] Example 1 - Preparation of Platinum(II) Oxalate - ( MM-Si (ArPPh2)2 K2Pt(C2O4)2(OH2)2 (Pt complex, 0.100 g, 0.22 mmol, 1 equivalent) was suspended in distilled water (2.5 mL) in an amber 7 mL screw cap vial. The mixture was gently heated with stirring and sparged with N2 for a short time until the Pt complex dissolved, giving a yellow solution. Separately, Intermediate Example 5 ( MM-Si0.310 g, 0.67 mmol, 3 equivalents of ArPPh2 were dissolved in 0.5 mL of acetone, and then added dropwise to a stirring aqueous solution of the Pt complex and heated to 85°C. The heterogeneous reaction mixture was then covered and vigorously stirred at 85°C for 24 hours. The resulting two-phase reaction mixture contained a distinct yellow to orange layer (upper) and a nearly colorless layer (lower). The mixture was allowed to cool to ambient temperature and then diluted with DCM (10 mL) and distilled water (10 mL). The mixture was transferred to a 60 mL vial and shaken. The resulting yellow DCM layer and colorless aqueous layer were separated. The aqueous layer was then decanted, the DCM layer was dried over MgSO4 and filtered. The pale yellow filtrate was then concentrated under vacuum to obtain a viscous oil. The oil was combined with hexane (25 mL) and vigorously stirred at ambient temperature for 5 minutes to precipitate and separate a nearly colorless solid. The supernatant was decanted, and the colorless solid was washed with additional hexane (2 × 25 mL). The resulting solid was then dried in vacuum at ambient temperature. Yield: 0.170 g, 63.0%. 1 H NMR(400MHz,CDCl3)δ 7.49-7.28(m,16H),7.23-7.16(m,8H),7.04-6.99(m,4H),2.68-2.49(m,4H),1.6 4-1.53(m,4H),1.47-1.16(m,8H),0.61-0.49(m,4H),0.05(s,18H),0.04(s,12H). 13 C NMR(101MHz,CDCl3)δ 165.9,147.2,134.7,134.7,134.6,134.5,134.4,134.3,131.5,128.7 ,128.7,128.6,128.5,128.5,128.4,35.7,34.8,23.3,18.3,2.1,0.5. 31 P NMR(162MHz, CDCl3)δ 6.99(t,J=1895.8Hz).

[0048] Example 2 - Platinum(II) oxalate - ( MDM-Si Preparation of ArPPh2)2 The preparation and purification of Example 3 involved K2Pt(C2O4)2(OH2)2 (150 mg) and intermediate 6. ( MDM-SiThe preparation of the compound was substantially the same as described in Example 1, except that ArPPh2 (2.5 equivalents) was used. Yield: 0.20 g, 44.0%. 1 H NMR(500MHz,CDCl3)δ 7.46-7.28(m,8H),7.22-7.16(overlap,8H),7.01(d,J=7.8Hz,4H),2.58(t,J=7.8Hz,4H), 1.65-1.53(m,4H),1.44-1.31(m,4H),0.54-0.46(m,4H),0.08(s,36H),0.00(s,6H). 13 C NMR(126MHz,CDCl3)δ 165.9,147.2,134.9-134.52(m),134.4(t,J=5.4Hz),131.5,128.9-128.6(m),128.6-128.4(m),35.7,34.6,23.1,17.6,2.03,-0.10. 31 P NMR(202MHz, CDCl3)δ 6.99(t,J=1891.2Hz).

[0049] Example 3 - Platinum(II) oxalate - ( nBu-PDMS Preparation of ArPPh2)2 The preparation and purification of Example 3 involved K2Pt(C2O4)2(OH2)2 (100 mg) and intermediate 7 ( nBu-PDMS The preparation of the compound was substantially the same as described in Example 1, except that ArPPh2 (2.5 equivalents) was used. Yield: 0.24 g, 41.0%. 1 H NMR(400MHz,CDCl3)δ 7.43-7.28(m,16H),7.23-7.16(m,8H),7.04-6.99(m,4H),2.64-2.48(m,4H),1.67-1.5 8(m,4H),1.41-1.23(m,16H),0.92-0.83(m,8H),0.59-0.50(m,8H),0.12-0.00(m,74H). 31 P NMR(162MHz, CDCl3)δ 7.02(t,J=1888.0Hz).

[0050] Example 4 - Platinum(II) oxalate - ( MM Preparation of Ar2PPh The preparation and purification of Example 4 involved 75 mg of K2Pt(C2O4)2(OH2)2 and 2.2 equivalents of ( MM Except for the use of the Ar)2PPh ligand, the procedure was substantially the same as that described for Example 1. Yield: 0.120 g, 44.4%. 1 H NMR(400MHz,CDCl3)δ 7.49-7.28(m,10H),7.23-7.07(m,8H),7.07-6.90(m,8H),2.81-2.39(m,8H),1. 86-1.46 (m, 8H), 1.46-1.23 (m, 8H), 0.66-0.45 (m, 8H), 0.16--0.10 (overlapping resonance, 60H). 31 P NMR(162MHz, CDCl3)δ 6.32(t,J=1875.7Hz).

[0051] Comparative Example 1: Preparation of Triphenylphosphine Platinum(II) Oxalate Crystalline K2Pt(C2O4)2(OH2)2 (0.120 g, 0.27 mmol, 1 equivalent), a magnetic stirring rod, and distilled water (3-4 mL) were combined in an uncapped amber vial in a fume hood. This mixture was heated with rapid stirring to dissolve the platinum complex. A solution of triphenylphosphine (0.140 g, 0.53 mmol, 2 equivalents) in acetone (3-4 mL) was added to the platinum complex solution, and the mixture was heated to a target temperature of 80°C while continuing to stir. After reaching 80°C, the reaction mixture was stirred at that temperature for 2 hours and then cooled to ambient temperature. The product was then collected on a filter, washed with water (3 × 10 mL), and then suspended in ethanol (approximately 18 mL). The colorless suspension was then heated to a boil to completely solubilize the colorless material. The hot ethanol extract was filtered, and the filtrate was slowly cooled to ambient temperature overnight in a loosely capped amber scintillation vial. The following day, colorless crystals were collected, rinsed with ethanol (2 mL), and dried. The crystals were stored at ambient temperature in the amber scintillation vial. Yield: 115 mg, 53.3%. Identification of the target compound was confirmed by comparison with data reported in Organometallics, 1985, 4,647. 1H NMR (500MHz, CDCl3) δ 7.46-7.35(m), 7.28-7.18(m). 13 C NMR (126MHz, CDCl3)δ 165.7,134.4,131.5,128.5. 31 P NMR (202 MHz, CDCl3) δ 7.7.

[0052] UV Hydrosilylation Test Terminal divinylsiloxane (CAS No.: 68083-19-2, DP=9-10, 0.85 g, 1 equivalent relative to Si-vinyl), terminal monofunctional Si-H siloxane (CAS No.: 1038821-58-7, DP=10-12, 1.86 g, 2 equivalents relative to Si-H), and L2Pt (oxalate) stock solution (where L is a phosphine ligand) were added to an aluminum pan and thoroughly mixed. Aliquots (100 μL) of the mixture were taken out before UV irradiation and combined with 0.5 μL of C6D6 and mesitylene (10 μL) as an external standard. The contents of the aluminum dish were then irradiated for 300 seconds at a time with broadband 200-800 nm light provided by a Uvitron UV chamber set to 100% intensity. After every 300 seconds of irradiation, a measured aliquot (100 μL) of the contents of the aluminum pan was taken out, and the aliquot was combined with 0.5 μL of C6D6 and a measured amount of mesitylene (10 μL) as an external standard to prepare the NMR spectrum sample. This process was used for all vinylsiloxane resonances. 1 The process was repeated until the required amount (determined by 1H NMR spectroscopy) was consumed or the total irradiation time reached 2700 seconds (45 minutes). The conversion percentage was measured by integrating the resonances attributed to the Si-vinyl protons in the siloxane starting material with respect to the aryl protons corresponding to the mesitylene standard.

[0053] PDMS solubility measurement Vinylsiloxane (0.85 g, 1 equivalent relative to Si-vinyl), SiHsiloxane (1.86 g, 2 equivalents relative to Si-H), and L2Pt (oxalate) stock solution were added to an aluminum pan and thoroughly mixed. The entire mixture was visually inspected for phase heterogeneity.

[0054] Dark stability measurement Vinylsiloxane (0.85 g, 1 mmol, 1 equivalent), SiHsiloxane (1.86 g, 2 mmol, 2 equivalents), and a 0.01 M Pt stock solution in dichloromethane (7 μL for 5 ppm Pt catalyst) were added to an amber vial and thoroughly mixed. A 100 μL aliquot was taken from this initial mixture (before any heating), and the C6D6 also contained 10 μL of mesitylene. 1 Prepare and analyze the 1H NMR spectrum sample, and "T o This was recorded as (0 minutes). Next, the mixture of siloxane material and catalyst was divided into two amber-colored vials. The first vial of the two vials was heated in the dark at 50°C for 24 hours, and the second vial was maintained in the dark at ambient temperature for 7 days. After each of these experiments (24 hours at 50°C or 7 days at ambient temperature), NMR spectral samples were prepared. 1 Analysis was performed by 1H NMR spectroscopy (0.5 mL of C6D6, 10 μL of mesitylene). The conversion rate was determined by integrating the Si-vinyl protons of the Si-vinyl starting material with the external aryl protons of mesitylene.

[0055] Table 1 shows PDMS (PDMS sol ) indicates the solubility of the catalyst in the mixture; dark stability of the mixture at ambient temperature for 7 days (dark RT); dark stability of the mixture at 50°C for 24 hours (dark 50°C); UV conversion rate to the desired product at 5 minutes (UV5); and UV conversion rate to the desired product at 15 minutes (UV 15 The concentration of Pt in each test was 5 ppm.

[0056] [Table 1]

[0057] The data show that the use of the Pt(II) oxalate-phenylsiloxane phosphine complex resulted in complete hydrosilylation of silane and vinylsiloxane starting materials within 15 minutes. In contrast, the comparative Pt(II) oxalate-triphenylphosphine complex resulted in incomplete conversion even after 30 minutes of UV exposure at ambient temperature. The tested compounds were also found to exhibit good to excellent PDMS solubility, relatively low volatility, and acceptable dark-stable retention.

Claims

1. The platinum(II) oxalate compound shown in the following formula. 【Chemistry 1】 (wherein, R １ is phenyl(CH ２ ), n is from 3 to 30; each R ｎ R ４ is, and n is from 3 to 30; each R ２ is independently C １ -C １０ alkyl, phenyl, or phenyl(CH ２ ), ｎ R ４ is, and each R ３ is independently C １ -C １０ alkyl, phenyl, phenyl(CH ２ ), ｎ R ４ is, or each R ３ together with the phosphorus atom to which they are attached forms a diphosphine; each R ４ is any of the following; 【Chemistry 2】 In the formula, R ５ C １ -C １０ Alkyl or phenyl; R ６ C １ -C １０ Alkyl or phenyl or O-Si (CH ３ ) ３ and; each R ７ Independently, C １ -C １０ Alkyl or phenyl; R ７’ C １ -C １０ It is alkyl; each R ８ Independently, C １ -C １０ It is alkyl or phenyl; x is 2 to 250; the dotted line is CH ２ (Represents the bond point to the base.)

2. In the formula, R ５ C １ -C ６ Alkyl or phenyl; R ６ C １ -C ６ Alkyl or phenyl or O-Si (CH ３ ) ３ and; each R ７ Independently, C １ -C ６ It is alkyl; R ７’ C １ -C ６ It is alkyl; each R ８ Independently, C １ -C ６ Alkyl or phenyl; the dotted line represents CH ２ The platinum(II) oxalate compound according to claim 1, wherein n represents the bonding site to the group; n is 4 to 20; and x is 2 to 50.

3. In the formula, each R ８ and each R ５ R is independently methyl or phenyl; ６ is methyl, phenyl, or O-Si (CH ３ ) ３ and; each R ７’ The platinum(II) oxalate compound according to claim 2, wherein is methyl; x is 2 to 20.

4. In the formula, P(R １ R ２ R ３ ) or P(R ２ R ２ R ３ ) or both are selected from the group consisting of: 【Transformation 3】 In the formula, each R １ ' is independently, (CH ２ ) ｎ R ４ The platinum(II) oxalate compound according to claim 2.

5. In the formula, P(R １ R ２ R ３ ) or P(R ２ R ２ R ３ ) or both are selected from the group consisting of: 【Chemistry 4】 In the formula, each R １ ' is independently, (CH ２ ) ｎ R ４ The platinum(II) oxalate compound according to claim 3.

6. In the formula, P(R １ R ２ R ３ ) and P(R ２ R ２ R ３ ) forms a diphosphine selected from the following group: 【Transformation 5】 where m is 0, 1, 2, 3, 4, or 5; each R １ ’ is independently (CH ２ ), ｎ R ４ The platinum(II) oxalate compound according to claim 3, which is

7. In the formula, m is 1; each R １ The group is selected from the following: 【Transformation 6】 The dotted lines represent the bonding points to the phenyl ring; each R ７ C is independent １ -C ６ The platinum(II) oxalate compound according to claim 6, wherein it is alkyl.

8. In the formula, each R １’ The group is selected from the following: 【Transformation 7】 The dotted line is the bonding point to the phenyl ring; each R ７ is independently C １ -C ６ alkyl. The platinum(II) oxalate compound according to claim 5.

9. Platinum(II) oxalate ( ＭＭ－Ｓｉ ArPPh ２ ) ２ Platinum(II) oxalate ( ＭＤＭ－Ｓｉ ArPPh ２ ) ２ Platinum(II) oxalate ( ｎＢｕ－ＰＤＭＳ ArPPh ２ ) ２ ; and platinum(II) oxalate (( ＭＭ Ar) ２ PPh) ２ A platinum(II) oxalate compound according to claim 1, selected from the group consisting of the following.

10. A composition comprising a vinyl-functionalized siloxane, a Si-H-containing siloxane, and a catalytic amount of the platinum(II) oxalate compound according to any one of claims 1 to 9.

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