Sulfur-platinum complex as well as preparation method and application thereof
By preparing a sulfoplatinum complex, the problem of decreased activity of platinum homogeneous catalysts in hydrosilylation reactions was solved, achieving high yield and high selectivity catalytic effects, suitable for hydrosilylation reactions.
Patent Information
- Application Number
- CN202511144700.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-15
- Publication Date
- 2025-11-28
AI Technical Summary
Existing platinum homogeneous catalysts are prone to precipitation during hydrosilylation, leading to decreased activity and the generation of numerous side reactions and impurities, which affects the selectivity, rate, and efficiency of the reaction.
A thioplatinum complex was prepared by forming a stable complex with divalent platinum via a thiol group. Specific steps, including thiol vinyl addition reaction, reaction with potassium chloroplatinate, and purification, were used to form a highly active and selective catalyst.
The yield and selectivity of the catalyst were improved. The resulting sulfoplatinum complex exhibited high activity and selectivity in the hydrosilylation reaction, with a yield greater than 95% and a selectivity exceeding 80%.
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Abstract
Description
TECHNICAL FIELD
[0001] The application relates to a preparation method of a noble metal complex, in particular to a sulfur-platinum complex and a preparation method and application thereof, and belongs to the field of hydrosilylation catalysts. BACKGROUND
[0002] Hydrosilylation is an important reaction for generating various organosilicon compounds, and the most common catalyst in such reactions is a platinum homogeneous catalyst such as Karstedt catalyst. The Karstedt catalyst is zero-valent platinum which is coordinated with vinyl groups, and is easy to cause platinum precipitation at high temperatures, resulting in activity reduction.
[0003] Hydrosilylation is generally accompanied by a large amount of byproduct or impurity generation. There is a need to improve the selectivity, rate and efficiency of the above-mentioned hydrosilylation reaction from the economic and environmental aspects by improving the production level with fixed basic equipment, reducing the amount of waste storage and reducing the cost required for waste treatment, and reducing the unit cost of the hydrosilylation product by improving the profit, reducing the price or simplifying the byproduct removal step. Good catalytic activity and selectivity are very important for a hydrosilylation catalyst. SUMMARY
[0004] The purpose of the present application is to provide a sulfur-platinum complex and a preparation method and application thereof, aiming to solve the problems presented in the background.
[0005] In a first aspect, the present application provides a sulfur-platinum complex, and the structural formula of the sulfur-platinum complex is [R(CH2)2(CH3)2SiO(SiO) n Si(CH3)2(CH2)2R]2PbCl2, wherein n is any integer from 0 to 10, and R is a mercapto group.
[0006] Further, the R includes one of ethylthio group, ethylenedithio group, 1-propylthio group and 1,3-propylenedithio group.
[0007] In a second aspect, the present application provides a preparation method of a sulfur-platinum complex, which comprises the following steps:
[0008] Step one, performing mercapto-vinyl addition reaction on low-chain end-vinyl silicone oil and mercaptan under the condition of a photoinitiator or a thermal initiator to obtain low-chain silicone oil capped with sulfur.
[0009] Step two, dissolving potassium chloroplatinite and water under a protective atmosphere by heating, then adding the low-chain silicone oil capped with sulfur obtained in step one, and performing reaction at a reflux temperature to obtain a crude product of a platinum-sulfur complex.
[0010] Step three, purifying the crude product obtained in step two to obtain a sulfur-platinum complex.
[0011] Further, the preparation method of the sulfur-platinum complex, wherein the low-chain end-vinyl silicone oil in step one has a structure of ViMe2SiO(SiO) n SiMe2Vi, wherein n is any integer from 0 to 10, and the mercaptan includes one of ethanethiol, ethanedithiol, 1-propanethiol, and 1,3-propanedithiol.
[0012] Further, the preparation method of the sulfur-platinum complex, wherein the ratio of the number of moles of the vinyl groups in the low-chain end-vinyl silicone oil to the number of moles of the mercapto groups in the mercaptan in step one is 1.0-1.05, and the amount of the initiator added is 0.35 wt%-3.5 wt% of the total amount of the low-chain end-vinyl silicone oil and the mercaptan.
[0013] Further, the preparation method of the sulfur-platinum complex, wherein the thermal initiator in step one includes one of azobisisobutyronitrile, azobisisoheptyl nitrile, and dimethyl azobisisobutyrate, the reaction temperature of the thermal initiator is 80-120℃, and the reaction time is 2-4 hours.
[0014] Further, the preparation method of the sulfur-platinum complex, wherein the photo initiator in step one includes one of benzoyl peroxide, benzpinacol, benzophenone, and isooctyl p-dimethylaminobenzoate, the reaction condition of the photo initiator is room temperature, and the ultraviolet light irradiation time is 3-7 hours.
[0015] Further, the preparation method of the sulfur-platinum complex, wherein the protective atmosphere in step two includes nitrogen or an inert gas, the inert gas includes argon, the temperature of the heating and dissolving is 60-80℃, the temperature of the reaction is 80-105℃, the reaction time is 2-4 hours, the ratio of the number of moles of platinum in the potassium chloroplatinite to the number of moles of the mercapto groups in the mercaptan-containing end-capped silicone oil is 1:1-1.1, and the amount of water added is 20-55 times the mass of the potassium chloroplatinite.
[0016] Further, the preparation method of the sulfur-platinum complex, wherein the method for purifying the crude product in step three includes: adding a solvent to the crude product obtained in step two to perform extraction, separating the organic phase, removing the solvent from the organic phase under reduced pressure, and vacuum drying.
[0017] Further, the preparation method of the sulfur-platinum complex, wherein the solvent includes one of dichloromethane, dichloroethane, and n-hexane.
[0018] Further, the preparation method of the sulfur-platinum complex, wherein the temperature for removing the solvent under reduced pressure and the temperature for vacuum drying are both 50-75℃.
[0019] In a third aspect, the present application provides an application of the sulfur-platinum complex or the sulfur-platinum complex prepared by the preparation method in a hydrosilylation reaction.
[0020] Beneficial effects: the sulfur platinum complex species described in the application, the divalent platinum and the sulfur in the mercapto form stable complexes through hybridization energy, such complexes have good compatibility with organosilicon, higher yield (more than 95%) and higher selectivity (>80%) compared with the Karstedt catalyst, higher activity, and wide application prospect in hydrosilylation. DETAILED DESCRIPTION
[0021] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.
[0022] Embodiment one
[0023] The embodiment provides a preparation method of a sulfur platinum complex, comprising the following steps:
[0024] (1) 65.2 g of vinyl bis-capped and 40.34 g of ethanethiol are added with 0.5 g of azobisisobutyronitrile, and the temperature is kept at 90-100 DEG C for 3 hours, and then cooled to obtain a sulfur-capped disiloxane;
[0025] (2) 7.28 g of potassium chloroplatinite and 145 g of pure water are dissolved in a four-necked flask with a condensation reflux device under nitrogen protection at 60 DEG C, and then 9.5 g of the sulfur-capped disiloxane obtained in step (1) is added, and the temperature is raised to 90 DEG C for 2 h, and then the temperature is lowered to room temperature to obtain a crude product.
[0026] (3) 60 mL of dichloromethane is added to the crude product obtained in step (2), and the liquid is separated to obtain an organic phase, and the extraction is repeated three times, and then the organic phase is removed at 60 DEG C, and then dried at 65 DEG C under vacuum to obtain 13.83 g of a product with the structure [C2H4S(CH2)2(CH3)2SiOSi(CH3)2(CH2)2SC2H4]2PbCl2.
[0027] Embodiment two
[0028] (1) 54.12 g of vinyl bis-capped and 1-propyl mercaptan 33.48 g are added with 0.8 g of benzophenone, and the temperature is kept at room temperature for 5 hours under ultraviolet light to obtain a sulfur-capped disiloxane;
[0029] (2) In a four-necked flask with condenser reflux apparatus, 5.31 g of potassium chloroplatinite and 115 g of pure water were dissolved at 80°C under nitrogen protection, then 6.73 g of the sulfur-terminated disiloxane obtained in step (1) was added, the temperature was raised to 95°C and reacted for 3.5 h, then the temperature was lowered to room temperature to obtain the crude product.
[0030] (3) The crude product obtained in step (2) was added with 80 mL of dichloroethane, and the organic phase was obtained by standing and separating, which was extracted three times repeatedly. The organic phase was dried by removing the solvent at 75°C, and then dried under vacuum at 75°C to obtain 9.98 g of the product [C3H6S(CH2)2(CH3)2SiOSi(CH3)2(CH2)2SC3H6]2PbCl2.
[0031] Example Three
[0032] (1) 92.5 g of 5-chain vinyl-terminated silicone oil and 23.55 g of ethanedithiol were added with 1.2 g of azobisisoheptanenitrile, and the temperature was maintained at 85-95°C for 3 hours to obtain a sulfur-terminated 5-chain siloxane;
[0033] (2) In a four-necked flask with condenser reflux apparatus, 3.35 g of potassium chloroplatinite and 65 g of pure water were dissolved at 75°C under argon protection, then 3.83 g of the sulfur-terminated 5-chain siloxane obtained in step (1) was added, the temperature was raised to 95°C and reacted for 2.5 h, then the temperature was lowered to room temperature to obtain the crude product.
[0034] (3) The crude product obtained in step (2) was added with 30 mL of n-hexane, and the organic phase was obtained by standing and separating, which was extracted three times repeatedly. The organic phase was dried by removing the solvent at 70°C, and then dried under vacuum at 70°C to obtain 5.77 g of the product [C2H5S2(CH2)2(CH3)2SiO(SiO)5Si(CH3)2(CH2)2S2C2H5]2PbCl2.
[0035] Example Four
[0036] (1) 83.4 g of 10-chain vinyl-terminated silicone oil and 17.83 g of ethanethiol were added with 0.9 g of benzpinacol, and the temperature was maintained at room temperature for 5 h under ultraviolet light to obtain a sulfur-terminated 10-chain siloxane;
[0037] (2) In a four-necked flask with condenser reflux apparatus, 4.25 g of potassium chloroplatinite and 75 g of pure water were dissolved at 80°C under nitrogen protection, then 5.34 g of the sulfur-terminated 10-chain siloxane obtained in step (1) was added, the temperature was raised to 90°C and reacted for 3 h, then the temperature was lowered to room temperature.
[0038] (3) 45 mL of dichloromethane was added to the crude product obtained in step (2), and the mixture was allowed to stand to separate into an organic phase, which was extracted three times. The organic phase was dried by removing the solvent at 75°C, and then dried under vacuum at 75°C to obtain 8.98 g of a product having the structure [C2H4S(CH2)2(CH3)2SiO(SiO) 10 Si(CH3)2(CH2)2SC2H4]2PbCl2product.
[0039] Example 5
[0040] The products of Examples 1-4 and the Karstedt catalyst were subjected to performance testing, and the products of Examples 1-4 and the Karstedt catalyst were used to catalyze the addition reaction of allyl glycidyl ether and triethoxysilane.
[0041] In a 100 ml three-necked flask, 23.9 g of allyl glycidyl ether and the product of Example 1-4 or the Karstedt catalyst (10 ppm of platinum based on the total mass of the reactants) were charged, and the temperature was raised to 65°C. 32.8 g of triethoxysilane was added dropwise with stirring, and the temperature was raised to 85°C and maintained for 3 h after the dropwise addition was completed within 60 min. After the reaction was completed, the temperature was lowered to room temperature, and the filtrate was subjected to vacuum distillation. The mass of the product was measured to calculate the yield, and the selectivity of the addition product was calculated by gas chromatography. According to the two positions of the peaks of the α-addition product and the β-addition product in the gas chromatogram, the selectivity was calculated as the peak area value α / (α+β) x 100%.
[0042] The results are shown in Table 1
[0043] Table 1 Performance test results
[0044] As can be seen from the test results in Table 1, the sulfur-platinum complex obtained in the present application has a higher yield (more than 95%) and higher selectivity (>80%) than the Karstedt catalyst, and has high activity, which has broad application prospects for silicon hydride reactions.
[0045] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application shall be included in the protection scope of the present application.
Claims
1. A thioplatinum complex, characterized in that: The structural formula of the thioplatinum complex is [R(CH2)2(CH3)2SiO(SiO)]. n Si(CH3)2(CH2)2R]2PbCl2, Where n = any integer from 0 to 10, and R is a thiol group.
2. The thioplatinum complex according to claim 1, characterized in that: The R includes one of ethylthio, ethylenedithio, 1-propanethio, and 1,3-propanedithio.
3. The method for preparing the thioplatinum complex according to claim 1 or 2, characterized in that: Includes the following steps: Step 1: React low-chain terminus vinyl silicone oil and thiol under photoinitiator or thermal initiator conditions to obtain sulfur-terminated low-chain terminus silicone oil; Step 2: Dissolve potassium chloroplatinate in water under a protective atmosphere by heating, then add the sulfur-terminated low-chain silicone oil obtained in Step 1, and react at reflux temperature to obtain the crude product of platinum-sulfur complex. Step 3: Purify the crude product obtained in Step 2 to obtain the thioplatinum complex.
4. The preparation method according to claim 3, characterized in that: The low-chain terminus end vinyl silicone oil structure described in step one is as follows: ViMe2SiO(SiO) n SiMe2Vi, where n = any integer from 0 to 10, and the thiol includes one of ethanethiol, ethylenedithiol, 1-propanethiol, and 1,3-propanedithiol.
5. The preparation method according to claim 3, characterized in that: The ratio of the number of moles of vinyl groups in the low-chain terminal vinyl silicone oil to the number of moles of mercapto groups in the thiol is 1.0-1.05, and the amount of initiator added is 0.35 wt%-3.5 wt% of the total amount of low-chain terminal vinyl silicone oil and thiol.
6. The preparation method according to claim 3, characterized in that: The thermal initiator in step one includes one of azobisisobutyronitrile, azobisisoheptanenitrile, and dimethyl azobisisobutyrate. The reaction temperature of the thermal initiator is 80℃-120℃, and the reaction time is 2-4 hours. The photoinitiator includes one of benzoyl peroxide, dimethyl benzoate, benzophenone, and isooctyl p-dimethylaminobenzoate. The reaction conditions of the photoinitiator are room temperature and ultraviolet light irradiation time of 3-7 hours.
7. The preparation method according to claim 3, characterized in that: The protective atmosphere in step two includes nitrogen or an inert gas. The heating and dissolution temperature is 60-80℃, the reaction temperature is 80-105℃, and the reaction time is 2-4 hours. The ratio of the number of moles of platinum in potassium chloroplatinate to the number of moles of mercapto groups in sulfur-containing end-capped silicone oil is 1:1-1.1, and the mass of water added is 20-55 times the mass of potassium chloroplatinate.
8. The preparation method according to claim 3, characterized in that: The method for purifying the crude product in step three includes: adding a solvent to the crude product obtained in step two for extraction, separating the liquid to obtain an organic phase, removing the solvent from the organic phase under reduced pressure, and drying it under vacuum.
9. The preparation method according to claim 8, characterized in that: The solvent includes one of dichloromethane, dichloroethane, and n-hexane; the temperature for removing the solvent under reduced pressure and the temperature for vacuum drying are both 50-75°C.
10. The application of the thioplatinum complex according to claim 1 or 2, or the thioplatinum complex prepared by any one of claims 3-9, in hydrosilylation reactions.