Preparation method of polyether modified silicone oil
By preparing a supported catalyst, the problem of difficult catalyst recovery and poor stability in the preparation of polyether modified silicone oil is solved, and efficient and environmentally friendly polyether modified silicone oil production is achieved, improving product quality and production efficiency.
Patent Information
- Application Number
- CN202510805702.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-17
- Publication Date
- 2025-08-01
AI Technical Summary
In the prior art, the preparation method of polyether modified silicone oil has problems such as difficult catalyst recovery, poor stability, harsh reaction conditions and high environmental pressure, resulting in high production costs, low efficiency and low product purity.
The stable Pt-DMAP complex was formed by using components such as 1-butyl-3-methylimidazole hexafluorophosphate, chloroplatinic acid and 4-dimethylaminopyridine, and combined with ethyl orthosilicate to form a SiO2 network to prepare a supported catalyst. The catalyst was efficiently separated and recycled by a one-pot reaction, avoiding high-temperature and high-pressure operation.
The preparation of polyether modified silicone oil with high conversion (99.8%) and high purity (99.5%) was achieved, with high platinum recovery (<0.2%), which reduced energy consumption by 40%, simplified operating steps, and improved the stability and safety of the catalyst.
Abstract
Description
Technical Field
[0001] The present invention relates to the field of chemical engineering technology, and specifically, to a preparation method of polyether-modified silicone oil. Background Art
[0002] Polyether-modified silicone oil has become a core material in fields such as textile auxiliaries, personal care products, and defoamers due to its unique surface activity, defoaming property, and good compatibility with organic systems. Its performance mainly depends on the balance between the hydrophilicity conferred by the polyether chain segment and the hydrophobicity of the silicone oxygen main chain. Currently, industrial preparation mainly relies on the hydrosilylation reaction of hydrogen-containing silicone oil and allyl polyether, and this process highly depends on the catalytic efficiency of platinum-based catalysts. However, there are significant bottlenecks in the existing technology:
[0003] 1. Difficulty in catalyst recovery: Traditional homogeneous platinum catalysts (such as chloroplatinic acid) are miscible with the product after the reaction and are difficult to separate. Industrially, complex post-treatment steps such as diatomite adsorption, activated carbon treatment, or solvent extraction are often used. This not only leads to the loss of precious metal platinum (low recovery rate), increases production costs, but also introduces the risk of foreign impurities and affects product purity. The subsequent cumbersome separation and purification steps significantly reduce the overall method efficiency.
[0004] 2. Poor catalyst stability and recyclability: Homogeneous platinum catalysts are prone to aggregation and deactivation under reaction conditions, especially at higher temperatures. The reusability is poor, and usually, it can only be recycled several times before the activity significantly decreases, unable to meet the requirements of green chemistry and sustainable production for the long life of the catalyst.
[0005] 3. Method safety and environmental protection pressure: Some improved methods attempt to use supported platinum catalysts or increase the reaction temperature to promote separation. The former often faces problems such as leaching of active components and poor loading, while the latter requires pressure-resistant equipment, increasing safety risks and energy consumption. In addition, the solvent extraction method requires a large amount of organic solvents, and the subsequent recovery and treatment links bring additional costs and environmental burdens.
[0006] Polyether-modified silicone oil is a type of polymer material that combines polyether chain segments and polysiloxane chain segments, having both hydrophilicity and hydrophobicity, with low surface tension, excellent lubricity, antistatic property, and thermal stability, and is widely used in fields such as cosmetics, textile auxiliaries, coatings, personal care products, and industrial defoamers. The designability of its molecular structure enables it to adapt to different application scenarios. For example, by adjusting the length of the polyether chain segment (EO / PO ratio) or the degree of polymerization of the silicone oxygen chain segment, the emulsifying property, viscosity, and compatibility of the product can be customized and optimized. Traditional preparation methods take the hydrosilylation reaction as the core, and catalyze the grafting reaction of hydrogen-containing silicone oil and allyl polyether through platinum-based catalysts. However, this method has significant defects: low catalyst efficiency, harsh reaction conditions, equipment limitations, and environmental protection pressure.
[0007] In summary, there is an urgent need and great application value to develop a preparation technology for polyether-modified silicone oil that combines high activity, easy separation and recovery, excellent cycle stability, and can achieve solvent-free production under mild conditions, in order to improve product quality, reduce production costs, and promote the green transformation of the industry. Solving the core pain point of efficient heterogeneous catalysis and recycling of the catalyst is the key to breaking through the existing technical barriers. Summary of the Invention
[0008] The present invention is an improvement made in response to various deficiencies existing in the prior art, and provides a method for preparing polyether-modified silicone oil. The present invention is achieved through the following technical solutions:
[0009] The present invention discloses a method for preparing polyether-modified silicone oil, comprising the following steps:
[0010] 1) Catalyst preparation: 1-butyl-3-methylimidazolium hexafluorophosphate and chloroplatinic acid are mixed, stirred at 60-80 °C for 1-3 hours, then 4-dimethylaminopyridine solution is added and stirred for another 1-3 hours, tetraethyl orthosilicate is added dropwise, and stirred at 80-100 °C for 2-4 hours. A solid is precipitated by reaction, and then the catalyst is obtained through centrifugal separation, ethanol washing, and vacuum drying at 60-80 °C. The catalyst is a multi-layer composite structure;
[0011] 2) Nitrogen is introduced into a dry reaction kettle to displace air, hydrogen-containing silicone oil, allyl polyether, and the catalyst obtained in step 1) are added, stirring is started, and the temperature is raised for reaction for 1-2 hours;
[0012] 3) After the reaction is completed, the reaction system is naturally cooled to room temperature and then stirring is stopped to obtain a reaction product;
[0013] 4) The reaction product is filtered, and the filtrate is distilled under reduced pressure to remove low-boiling substances to obtain the product polyether-modified silicone oil;
[0014] 5) The filter cake is washed with anhydrous ethanol and dried, and then recycled.
[0015] As a further improvement, in step 1) of the present invention, the mass ratio of 1-butyl-3-methylimidazolium hexafluorophosphate to chloroplatinic acid is 10:1-3.
[0016] As a further improvement, in step 1) of the present invention, the mass ratio of tetraethyl orthosilicate to 1-butyl-3-methylimidazolium hexafluorophosphate is 1:2-5.
[0017] As a further improvement, in step 1) of the present invention, the mass ratio of 4-dimethylaminopyridine: water: ethanol in the 4-dimethylaminopyridine solution is 1:8.65:22.1.
[0018] As a further improvement, in step 1) of the present invention, the mass of 4-dimethylaminopyridine is 1%-3% of the mass of 1-butyl-3-methylimidazolium hexafluorophosphate.
[0019] As a further improvement, in step 2) of the present invention, the reaction temperature is 80-100 °C, and stirring needs to be kept uniform during the reaction.
[0020] As a further improvement, in step 2) of the present invention, the mass ratio of hydrogen-containing silicone oil, allyl polyether and catalyst is 100:200-220:3-9.
[0021] As a further improvement, the result analysis of the polyether-modified silicone oil prepared by the present invention is as follows: the hydrosilylation conversion rate is 99.8%, the purity of the product is 99.5%, the platinum loss rate <0.2%, and the activity of the catalyst remains 97% after 10 cycles of reuse.
[0022] The beneficial effects of the present invention are as follows:
[0023] 1. In the present invention, 4-dimethylaminopyridine (DMAP) is used. The nitrogen atom therein has strong coordination ability, forms a stable Pt-DMAP complex with the platinum precursor, inhibits the aggregation of platinum ions on the surface of the carrier, forms highly dispersed platinum nanoparticles, improves the platinum loading amount, and increases the density of active sites.
[0024] 2. In the present invention, tetraethyl orthosilicate is used. Tetraethyl orthosilicate is added and hydrolyzed and condensed under the catalysis of DMAP to form a silica network inside and around the ionic liquid. The SiO2 network physically confines the platinum nanoparticles and the ionic liquid in its pores or structure, greatly preventing the leaching and loss of the active components (Pt and ionic liquid). The SiO2 network provides a skeleton support for the catalyst, improves the mechanical strength and stability of the catalyst, and enables it to withstand centrifugation, washing and multiple cycles of use. Finally, a supported solid catalyst is formed instead of a homogeneous solution, which greatly facilitates separation and recovery by filtration.
[0025] 3. In the present invention, 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid is used to provide a stable carrier. The obtained catalyst is immiscible with the product, and can be recycled by centrifugation after stratification. Compared with the traditional method that cannot be directly separated, the operation is simple and the platinum recovery rate is high.
[0026] 3. The one-pot reaction is used to replace the traditional multi-step purification method. The operation under normal pressure does not require pressure-resistant equipment, reducing the safety risk. The stratification time of the catalyst and the product is shortened, and the efficiency is improved compared with solvent extraction. The whole process is solvent-free designed, eliminating the solvent recovery link and reducing the operation steps.
[0027] 4. In the present invention, through the coordinated regulation of optimizing the catalyst structure design and reaction parameters, the following breakthroughs are achieved: the reaction temperature is controlled at 80–100 °C (the traditional process requires above 120 °C), the time is shortened to 1–2 hours (traditionally 4–6 hours), and the hydrophilicity of the product is dynamically regulated by the mass ratio. At the same time, the hydrosilylation conversion rate reaches 99.8%, the side reactions are significantly inhibited; the energy consumption is reduced by 40%, and the operation at atmospheric pressure avoids the investment in high-pressure equipment, improving the safety. Detailed implementation manners
[0028] The technical solutions of the present invention will be further described in detail below in conjunction with specific embodiments, but the scope of the present invention is not limited to the embodiments.
[0029] Example 1
[0030] 1) Catalyst preparation: 10 g of 1-butyl-3-methylimidazolium hexafluorophosphate and 1 g of chloroplatinic acid are mixed and stirred at 70 °C for 2 hours. Subsequently, 6.45 g of 4-dimethylaminopyridine solution (the mass ratio of 4-dimethylaminopyridine: water: ethanol is 1:8.65:22.1) is added and stirred for another 2 hours. 5 g of tetraethyl orthosilicate is added dropwise and stirred at 80 °C for 2 hours. Finally, the catalyst is obtained through centrifugal separation, ethanol washing, and vacuum drying at 60 °C.
[0031] 2) Nitrogen is introduced into the dry reaction kettle to displace the air, 540 g of hydrogen-containing silicone oil, 1080 g of allyl polyether, and 16.2 g of catalyst are added, the reaction temperature is 80 °C, the reaction time is 1 hour, and stirring needs to be kept uniform during the reaction.
[0032] 3) After the reaction is completed, the reaction system is naturally cooled to room temperature and then the stirring is stopped.
[0033] 4) The reaction product is filtered, and the filtrate is distilled under reduced pressure to remove low-boiling substances to obtain the product polyether-modified silicone oil.
[0034] 5) The filter cake is washed with anhydrous ethanol and dried, and then recycled.
[0035] Result analysis: The hydrosilylation conversion rate is 99.1%, the purity of the product is 99.1%, the platinum loss rate < 0.5%, and the activity of the catalyst remains 95% after being recycled 10 times.
[0036] Example 2
[0037] 1) Catalyst preparation: 10 g of 1-butyl-3-methylimidazolium hexafluorophosphate and 2 g of chloroplatinic acid were mixed and stirred at 60 °C for 1 hour. Subsequently, 12.9 g of 4-dimethylaminopyridine solution (mass ratio of 4-dimethylaminopyridine: water: ethanol = 1: 8.65: 22.1) was added and stirring continued for 1 hour. 5 g of tetraethyl orthosilicate was added dropwise and stirred at 90 °C for 3 hours. Finally, the catalyst was obtained by centrifugal separation, ethanol washing and vacuum drying at 70 °C.
[0038] 2) Nitrogen was introduced into a dry reaction kettle to displace air, and 290 g of hydrogen-containing silicone oil, 609 g of allyl polyether and 17.4 g of catalyst were added. The reaction temperature was 90 °C and the reaction time was 1.5 hours. Stirring was required to be kept uniform during the reaction.
[0039] 3) After the reaction was completed, the reaction system was naturally cooled to room temperature and then stirring was stopped.
[0040] 4) The reaction product was filtered, and the filtrate was distilled under reduced pressure to remove low-boiling substances to obtain the product polyether-modified silicone oil.
[0041] 5) The filter cake was washed with anhydrous ethanol and dried, and then recycled.
[0042] Result analysis: The hydrosilylation conversion rate was 99.8%, the purity of the product was 99.5%, the platinum loss rate was <0.2%, and the activity of the catalyst remained 97% after 10 cycles of reuse.
[0043] Example 3
[0044] 1) Catalyst preparation: 10 g of 1-butyl-3-methylimidazolium hexafluorophosphate and 3 g of chloroplatinic acid were mixed and stirred at 80 °C for 3 hours. Subsequently, 19.35 g of 4-dimethylaminopyridine solution (mass ratio of 4-dimethylaminopyridine: water: ethanol = 1: 8.65: 22.1) was added and stirring continued for 3 hours. 5 g of tetraethyl orthosilicate was added dropwise and stirred at 100 °C for 4 hours. Finally, the catalyst was obtained by centrifugal separation, ethanol washing and vacuum drying at 80 °C.
[0045] 2) Nitrogen was introduced into a dry reaction kettle to displace air, and 206.7 g of hydrogen-containing silicone oil, 454.7 g of allyl polyether and 18.6 g of catalyst were added. The reaction temperature was 100 °C and the reaction time was 2 hours. Stirring was required to be kept uniform during the reaction.
[0046] 3) After the reaction was completed, the reaction system was naturally cooled to room temperature and then stirring was stopped.
[0047] 4) The reaction product was filtered, and the filtrate was distilled under reduced pressure to remove low-boiling substances to obtain the product polyether-modified silicone oil.
[0048] 5) The filter cake was washed with anhydrous ethanol and dried, and then recycled.
[0049] Result analysis: The conversion rate of hydrosilylation is 99.3%, the purity of the product is 99.2%, the platinum loss rate is <0.7%, and the activity of the catalyst remains 93% after 10 cycles of reuse.
[0050] Control Example 1
[0051] 1-Butyl-3-methylimidazolium hexafluorophosphate was not added, and other conditions were the same as those in Example 2. The result analysis is as follows: The conversion rate of hydrosilylation is 78%, the purity of the product is 72%, the platinum loss rate is 12%, and the activity of the catalyst is <90% after 10 cycles of reuse.
[0052] Control Example 2
[0053] 1-Butyl-3-methylimidazolium hexafluorophosphate was replaced with tetrabutylammonium bromide, and other conditions were the same as those in Example 2. The result analysis is as follows: The conversion rate of hydrosilylation is 77%, the purity of the product is 77%, the platinum loss rate is 15%, and the activity of the catalyst is <90% after 10 cycles of reuse.
[0054] Control Example 3
[0055] 4-Dimethylaminopyridine was not added, and other conditions were the same as those in Example 2. The result analysis is as follows: The conversion rate of hydrosilylation is 75%, the purity of the product is 76%, the platinum loss rate is 13%, and the activity of the catalyst is <90% after 10 cycles of reuse.
[0056] Control Example 4
[0057] Tetraethyl orthosilicate was not added, and other conditions were the same as those in Example 2. The result analysis is as follows: The conversion rate of hydrosilylation is 72%, the purity of the product is 70%, the platinum loss rate is 21%, and the activity of the catalyst is <90% after 10 cycles of reuse.
[0058] It can be seen that compared with Example 2, the synergistic effect of 1-butyl-3-methylimidazolium hexafluorophosphate, 4-dimethylaminopyridine and tetraethyl orthosilicate in Control Examples 1-4 significantly improves the catalytic performance. The three work together to achieve: ultra-high conversion rate and purity, extremely low platinum loss rate, and excellent catalyst recycling stability.
[0059] Control Example 5
[0060] 1) Nitrogen was introduced into the dry reaction kettle to displace the air, 200 g of hydrogen-containing silicone oil, 525 g of allyl polyether and 3.6 g of chloroplatinic acid were added, the reaction temperature was 120 °C, and the reaction time was 5 hours.
[0061] 2) After the reaction was completed, the reaction system was naturally cooled to room temperature and then the stirring was stopped.
[0062] 3) adding diatomaceous earth and stirring for 50 minutes to absorb the residual catalyst, filtering to obtain a clarified filtrate, and removing low-boiling substances by vacuum distillation to obtain the product polyether-modified silicone oil.
[0063] It can be seen that the catalyst used in Control Example 5 is different from that in Example 2, and the required reaction temperature is higher and the reaction time is longer. The analysis of the results shows that the hydrosilylation conversion rate is 80%, the product purity is 78%, and the platinum loss rate is 20%.
[0064] Finally, it should be noted that the above examples are merely specific implementation examples of the present invention. Obviously, the present invention is not limited to the above examples and is subject to numerous variations. All variations that can be directly derived or conceived by a person of ordinary skill in the art from the disclosure of the present invention should be considered within the scope of protection of the present invention.
Claims
1. A preparation method of polyether-modified silicone oil, characterized in that, It includes the following steps: 1) Catalyst preparation: 1-butyl-3-methylimidazolium hexafluorophosphate and chloroplatinic acid are mixed and stirred at 60 - 80 °C for 1 - 3 hours. Subsequently, 4-dimethylaminopyridine solution is added and stirring continues for 1 - 3 hours. Tetraethyl orthosilicate is added dropwise and stirred at 80 - 100 °C for 2 - 4 hours. A solid precipitates from the reaction, and then the catalyst is obtained through centrifugal separation, ethanol washing, and vacuum drying at 60 - 80 °C. The catalyst is a multi-layer composite structure; 2) Nitrogen is introduced into a dry reaction kettle to displace air. Hydrogen-containing silicone oil, allyl polyether, and the catalyst obtained in step 1) are added, and stirring is started. The temperature is raised for reaction for 1 - 2 hours; 3) After the reaction ends, the reaction system is naturally cooled to room temperature and then stirring is stopped to obtain a reaction product; 4) The reaction product is filtered. After the filtrate is distilled under reduced pressure to remove low-boiling substances, the product polyether-modified silicone oil is obtained; 5) The filter cake is washed with absolute ethanol and dried, and then recycled; 2. The preparation method of the polyether-modified silicone oil according to claim 1, characterized in that, In step 1), the mass ratio of 1-butyl-3-methylimidazolium hexafluorophosphate to chloroplatinic acid is 10:1 - 3; 3. The preparation method of the polyether-modified silicone oil according to claim 2, characterized in that, In step 1), the mass ratio of tetraethyl orthosilicate to 1-butyl-3-methylimidazolium hexafluorophosphate is 1:2 - 5; 4. The preparation method of the polyether-modified silicone oil according to claim 3, characterized in that, In step 1), in the 4-dimethylaminopyridine solution, the mass ratio of 4-dimethylaminopyridine:water:ethanol is 1:8.65:22.1; 5. The preparation method of the polyether-modified silicone oil according to claim 4, wherein, In step 1), the mass of 4-dimethylaminopyridine is 1% - 3% of the mass of 1-butyl-3-methylimidazolium hexafluorophosphate; 6. The preparation method of the polyether-modified silicone oil according to claim 1 or 2 or 3 or 4, characterized in that, In step 2), the reaction temperature is 80 - 100 °C, and stirring needs to be kept uniform during the reaction; 7. The preparation method of the polyether-modified silicone oil according to claim 6, characterized in that, In step 2), the mass ratio of hydrogen-containing silicone oil, allyl polyether, and the catalyst is 100:200 - 220:3 - 9; 8. The preparation method of the polyether-modified silicone oil according to claim 1 or 2 or 3 or 4 or 7, characterized in that, The result analysis of the prepared polyether-modified silicone oil is as follows: The silicon hydrosilylation conversion rate is 99.8%, the purity of the product is 99.5%, the platinum loss rate < 0.2%, and the activity of the catalyst remains 97% after 10 cycles of reuse.