Preparation method of polyether modified silicone oil
By reacting octamethylcyclotetrasiloxane, fluorocyclosiloxane and polymethylhydrosiloxane to generate low-hydrogen silicone oil, and combining it with allyl polyether, silane-grafted nanoparticles and dialkyl dithiophosphate, the problems of single performance and poor storage stability of polyether-modified silicone oil are solved, and high thermal stability and good defoaming performance are achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-03-13
- Publication Date
- 2026-04-10
AI Technical Summary
Existing polyether-modified silicone oils have limited properties and cannot meet the multifunctional additive requirements of complex systems. Furthermore, they are prone to phase separation or performance degradation under high temperature or extreme pH conditions, have poor storage stability, and are prone to stratification or precipitation.
Low-hydrogen silicone oil is generated by reacting octamethylcyclotetrasiloxane, fluorocyclosiloxane and polymethylhydrosiloxane, and then reacted with allyl polyether, silane-grafted nanoparticles and glycidyl methacrylate, and finally combined with dialkyl dithiophosphate to form polyether-modified silicone oil.
The prepared polyether-modified silicone oil has low surface tension, excellent thermal stability and defoaming properties, which improves storage stability and expands its application range.
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Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of polyether modified silicone oil, and particularly relates to a preparation method of polyether modified silicone oil. BACKGROUND
[0002] The rapid development of the polyurethane industry puts forward higher requirements for the performance of foaming aids. As a key component in the production process of polyurethane foam plastic, the uniform foaming agent directly affects the cell structure, uniformity and stability of the foam. Traditional uniform foaming agents (such as fatty acid esters, sulfonates, etc.) are gradually replaced by polyether modified silicone oil with better performance due to their limited emulsifying ability and poor foam stability. Polyether modified silicone oil is a kind of surfactant with unique molecular structure. Its molecular structure contains both hydrophobic siloxane chain segment and hydrophilic polyether chain segment. The polyether chain segment contains a strong polar oxygen atom connected to carbon, which can form a hydrogen bond with water, and has hydrophilic properties and can be dissolved in water. The polysiloxane chain segment has high silicon bond energy and is stable, not hydrophilic or hydrophobic. The non-active hydrocarbon group on the silicone main chain is also not hydrophilic. Therefore, when the two chain segments are connected together, the surface tension of the aqueous solution can be effectively reduced, the uniform mixing of the components can be promoted, and the bubble structure can be stabilized, so that polyurethane foam with fine cells and excellent mechanical properties can be prepared.
[0003] In the prior art, polyether modified silicone oil is mostly modified by a single structure of polyether, resulting in relatively single performance and difficulty in meeting the demand for multifunctional additives in complex systems. In addition, the traditional polyether modified silicone oil is prone to phase separation or performance degradation under high temperature or extreme pH conditions, resulting in insufficient thermal stability and limiting its application in high requirement industrial environments. The traditional polyether modified silicone oil is prone to delamination or precipitation during long-term storage, further affecting its storage stability and defoaming performance. SUMMARY
[0004] The purpose of the present application is to provide a preparation method of polyether modified silicone oil. By reacting octamethylcyclotetrasiloxane, fluorocyclosiloxane and polymethylhydrosiloxane, low hydrogen silicone oil is obtained. The low hydrogen silicone oil in step S1 is reacted with allyl polyether, silane grafted nanoparticles and glycidyl methacrylate to obtain a composite. The composite in step S2 is combined with dialkyldithiophosphate to finally obtain polyether modified silicone oil. The prepared polyether modified silicone oil not only has low surface tension and excellent thermal stability, but also has good defoaming performance, wettability and storage stability, which expands the application range of polyether modified silicone oil, and the overall comprehensive performance is good.
[0005] The technical problem this invention aims to solve is as follows: In the prior art, most polyether-modified silicone oils are modified using polyethers with a single structure, resulting in relatively simple properties that are difficult to meet the needs of multifunctional additives in complex systems. In addition, traditional polyether-modified silicone oils are prone to phase separation or performance degradation under high temperature or extreme pH conditions, resulting in insufficient thermal stability and limiting their application in demanding industrial environments. Furthermore, traditional polyether-modified silicone oils are prone to stratification or precipitation during long-term storage, further affecting their storage stability and defoaming performance.
[0006] The objective of this invention can be achieved through the following technical solutions: A method for preparing a polyether-modified silicone oil includes the following steps: S1: Reaction of octamethylcyclotetrasiloxane, fluorocyclosiloxane and polymethylhydrosiloxane yields low-hydrogen silicone oil; S2: React the low-hydrogen silicone oil from step S1 with allyl polyether, silane-grafted nanoparticles, and glycidyl methacrylate to obtain a composite. S3: Combine the complex from step S2 with dialkyl dithiophosphate to obtain polyether-modified silicone oil.
[0007] Furthermore, step S1 specifically includes: Octamethylcyclotetrasiloxane, fluorocyclosiloxane, polymethylhydrosiloxane and sulfuric acid were mixed evenly and then stirred to react. After the reaction was completed, sodium carbonate was added and stirring was continued. After the reaction was completed, the mixture was cooled to room temperature, filtered, and finally vacuum devolatilized to obtain low-hydrogen silicone oil.
[0008] Further, the mass ratio of the octamethylcyclotetrasiloxane, fluorocyclosiloxane, polymethylhydrosiloxane, sulfuric acid, and sodium carbonate is 23-24:0.8-1.2:4.8-5.2:0.3-0.5:0.4-0.6.
[0009] Furthermore, the fluorocyclosiloxane is composed of trifluoropropylmethylcyclotrisiloxane and tetramethyltri-3-trifluoropropylcyclotetrasiloxane in a mass ratio of 0.6-0.7:0.5-0.6.
[0010] Furthermore, the stirring reaction is carried out at a temperature of 40-50°C for 4-6 hours and at a speed of 300-500 rpm.
[0011] Furthermore, the temperature for continued stirring is 40-50℃, and the time is 2-3 hours.
[0012] Furthermore, the vacuum devolatilization temperature is 140-150℃, and the time is 2-3 hours.
[0013] Furthermore, step S2 specifically includes: The low-hydrogen silicone oil, glycidyl methacrylate, and xylene from step S1 were mixed, and a catalyst was added. The mixture was then stirred and reacted under nitrogen protection. After the reaction was completed, allyl polyether, silane-grafted nanoparticles, and the catalyst were added, and the mixture was stirred and reacted again. After the reaction was completed, the mixture was cooled to room temperature, filtered, and finally vacuum devolatilized to obtain the composite.
[0014] In the above reaction process, the low-hydrogen silicone oil contains Si-H bonds, and the glycidyl methacrylate, allyl polyether, and silane-grafted nanoparticles contain carbon-carbon double bonds. Under the action of a catalyst, the Si-H bonds in the low-hydrogen silicone oil can combine with the carbon-carbon double bonds in the glycidyl methacrylate, allyl polyether, and silane-grafted nanoparticles through a hydrosilylation reaction, thus combining the low-hydrogen silicone oil, glycidyl methacrylate, allyl polyether, and silane-grafted nanoparticles to finally obtain a composite.
[0015] Furthermore, the mass ratio of the low-hydrogen silicone oil, glycidyl methacrylate, xylene, catalyst, allyl polyether, and silane-grafted nanoparticles is 19-21:5-7:9-11:0.01-0.02:5-7:1-2.
[0016] Furthermore, the catalyst is chloroplatinic acid.
[0017] Furthermore, the allyl polyether is polyethylene glycol monoallyl ether.
[0018] Furthermore, the temperature of the stirring reaction is 75-85℃, and the time is 1.5-2.5h.
[0019] Furthermore, the temperature for the continued stirring reaction is 75-85℃, and the time is 1-2 hours.
[0020] Furthermore, the preparation method of the silane-grafted nanoparticles includes the following steps: Nanoparticles were added to toluene and sonicated. Then, a silane coupling agent was added, and the mixture was refluxed and stirred under nitrogen protection. After the reaction was completed, the mixture was centrifuged, washed with toluene, and finally dried under vacuum to obtain silane-grafted nanoparticles.
[0021] During the above reaction, the nanoparticles have hydroxyl groups on their surface. After the silane coupling agent is hydrolyzed, silanol groups are generated, which can combine with the hydroxyl groups on the nanoparticles to graft the silane coupling agent onto the surface of the nanoparticles, finally obtaining silane-grafted nanoparticles.
[0022] Furthermore, the mass ratio of the nanoparticles, toluene, and silane coupling agent is 4.8-5.2:190-210:0.7-0.8.
[0023] Furthermore, the silane coupling agent is vinyltriethoxysilane.
[0024] Furthermore, the nanoparticles are composed of nano-silica and nano-zinc oxide in a mass ratio of 0.7-0.8:0.3-0.4.
[0025] Furthermore, the ultrasonic treatment time is 20-30 minutes.
[0026] Furthermore, the reflux stirring temperature is 75-85℃, and the time is 2.5-3.5h.
[0027] Furthermore, the vacuum drying temperature is 55-65℃, and the time is 8-10 hours.
[0028] Furthermore, step S3 specifically includes: The complex in step S2 was mixed evenly with dialkyl dithiophosphate, and then refluxed and stirred. After the reaction was completed, it was cooled to room temperature, and the unreacted dialkyl dithiophosphate was removed by rotary evaporation to finally obtain polyether modified silicone oil.
[0029] In the above reaction process, the complex has an epoxy group and the dialkyl dithiophosphate has a -SH group. The epoxy group in the complex can react and combine with the -SH group in the dialkyl dithiophosphate, thus combining the complex with the dialkyl dithiophosphate to finally obtain polyether modified silicone oil.
[0030] Furthermore, the mass ratio of the complex to the dialkyl dithiophosphate is 19-21:12-13.
[0031] Furthermore, the dialkyl dithiophosphate is composed of diethyl dithiophosphate and dimethyl dithiophosphate in a mass ratio of 0.6-0.7:0.4-0.5.
[0032] Furthermore, the reflux stirring reaction is carried out at a temperature of 95-105°C for a time of 4.5-5.5 hours.
[0033] Furthermore, the temperature of the rotary evaporation is 70-80°C.
[0034] The beneficial effects of this invention are: (1) In the technical solution of the present invention, low-hydrogen silicone oil is obtained by reacting octamethylcyclotetrasiloxane, fluorocyclosiloxane and polymethylhydrosiloxane; the fluorocyclosiloxane is composed of a mixture of trifluoropropylmethylcyclotrisiloxane and tetramethyltri-3-trifluoropropylcyclotetrasiloxane; both trifluoropropylmethylcyclotrisiloxane and tetramethyltri-3-trifluoropropylcyclotetrasiloxane have trifluoropropyl groups, and the two have a synergistic effect, which can better improve the thermal stability and antioxidant properties of polyether modified silicone oil. Furthermore, fluorocyclosiloxanes have low surface energy, which can significantly reduce the surface tension of polyether-modified silicone oils, giving them better wettability and spreadability in aqueous solutions. Due to their excellent chemical inertness and thermal stability, fluorocyclosiloxanes can maintain stable defoaming performance over a long period and are less prone to failure, further enhancing the defoaming performance of polyether-modified silicone oils. Reacting octamethylcyclotetrasiloxane, fluorocyclosiloxane, and polymethylhydrosiloxane allows for effective combination of the three compounds, and polymethylhydrosiloxane contains… The abundance of Si-H bonds provides reaction sites for subsequent reactions, enabling multifunctional modification of the material. The low-hydrogen silicone oil from step S1 is reacted with allyl polyether, silane-grafted nanoparticles, and glycidyl methacrylate to obtain a composite. The silane-grafted nanoparticles are prepared by grafting vinyltriethoxysilane onto nanoparticles, which not only improves the dispersibility of the nanoparticles but also enhances the compatibility between the nanoparticles and the low-hydrogen silicone oil. The nanoparticles are composed of a mixture of nano-silica and nano-zinc oxide. Nano-silica and nano-zinc oxide have a good synergistic effect, effectively improving the thermal stability, wettability, and mechanical properties of the polyether-modified silicone oil, and also having a positive impact on the defoaming performance and storage stability of the polyether-modified silicone oil. The combination of low-hydrogen silicone oil with allyl polyether, silane-grafted nanoparticles, and glycidyl methacrylate exhibits good binding force, and glycidyl methacrylate provides reaction sites for subsequent reactions, further enhancing the overall performance of the polyether-modified silicone oil.
[0035] (2) In the technical solution of the present invention, the polyether modified silicone oil is finally obtained by combining the complex in step S2 with dialkyl dithiophosphate; wherein, dialkyl dithiophosphate is composed of diethyl dithiophosphate and dimethyl dithiophosphate, which has good extreme pressure lubrication. The two play a synergistic role, which can improve the oxidation resistance and thermal stability of polyether modified silicone oil, delay the oxidative degradation process of the material at high temperature, and effectively extend the service life of polyether modified silicone oil. In addition, dialkyl dithiophosphate helps to reduce the surface tension of polyether modified silicone oil, promotes bubble rupture, thereby enhancing its defoaming performance, and can also improve its storage stability, reduce the occurrence of stratification and precipitation, and realize the multifunctionality of polyether modified silicone oil. The combination of the complex with dialkyl dithiophosphate has good binding force, further reduces the surface tension of polyether modified silicone oil, and improves its thermal stability, defoaming performance and storage stability.
[0036] (3) In the technical solution of the present invention, octamethylcyclotetrasiloxane, fluorocyclosiloxane and polymethylhydrosiloxane are reacted, and then reacted with allyl polyether, silane-grafted nanoparticles and glycidyl methacrylate, and finally combined with dialkyl dithiophosphate to obtain polyether modified silicone oil; the prepared polyether modified silicone oil not only has low surface tension, but also has good thermal stability, defoaming performance and storage stability, which expands its application range and has good overall performance. Detailed Implementation
[0037] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0038] The specific parameters of the raw materials used in this invention are as follows: Trifluoropropylmethylcyclotrisiloxane, CAS No.: 2374-14-3, Product No.: D850677, provided by Shanghai Maclean Biotechnology Co., Ltd.; Tetramethyltri-3-trifluoropropylcyclotetrasiloxane, CAS No.: 429-67-4, Product No.: T348057, provided by Shanghai Aladdin Biotechnology Co., Ltd.; Polymethylhydrosiloxane, CAS No.: 63148-57-2, Product No.: P766838, provided by Shanghai Maclean Biotechnology Co., Ltd.; Polyethylene glycol monoallyl ether, CAS No.: 27274-31-3, Product No.: A856836, provided by Shanghai Maclean Biotechnology Co., Ltd.; Nano silica, specification: 20nm, specific surface area: 200m². 2 / g, provided by Nanjing Baoket New Materials Co., Ltd.; Nano zinc oxide, specification: 30nm, model: PZT-30, provided by Nanjing Baoket New Materials Co., Ltd.; Glycidyl methacrylate, CAS No.: 106-91-2, product number: G810426, provided by Shanghai Maclean Biochemical Technology Co., Ltd.; Diethyl dithiophosphate, CAS No.: 298-06-6, product number: BD126214, provided by Shanghai Bid Pharmaceutical Technology Co., Ltd.; Dimethyl dithiophosphate, CAS No.: 756-80-9, product number: O866333, provided by Shanghai Maclean Biochemical Technology Co., Ltd.
[0039] Example 1 The preparation method of polyether-modified silicone oil includes the following steps: S1: Octamethylcyclotetrasiloxane, fluorocyclosiloxane, polymethylhydrosiloxane, sulfuric acid, and sodium carbonate were mixed evenly according to a mass ratio of 23:0.8:4.8:0.3:0.4. The mixture was stirred at 300 rpm at 40°C for 6 hours. After the reaction was completed, sodium carbonate was added, and the mixture was stirred at 40°C for another 3 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and finally vacuum devolatilized at 140°C for 3 hours to obtain low-hydrogen silicone oil. The fluorocyclosiloxane was composed of trifluoropropylmethylcyclotrisiloxane and tetramethyltri-3-trifluoropropylcyclotetrasiloxane in a mass ratio of 0.6:0.5. S2: The low-hydrogen silicone oil, glycidyl methacrylate, xylene, chloroplatinic acid, polyethylene glycol monoallyl ether, and silane-grafted nanoparticles were mixed in a mass ratio of 19:5:9:0.01:5:1. Chloroplatinic acid was added, and the mixture was stirred at 75°C for 2.5 h under nitrogen protection. After the reaction was completed, polyethylene glycol monoallyl ether, silane-grafted nanoparticles, and chloroplatinic acid (with the same mass as the chloroplatinic acid mentioned above) were added, and the mixture was stirred at 75°C for another 2 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and finally vacuum devolatilized at 140°C for 3 h to obtain the composite. The preparation method of silane-grafted nanoparticles includes the following steps: The nanoparticles, toluene, and vinyltriethoxysilane were mixed in a mass ratio of 4.8:190:0.7. The nanoparticles were added to toluene and sonicated for 20 min (ultrasonic power 100 W, ultrasonic frequency 40 kHz). Then, vinyltriethoxysilane was added, and the mixture was refluxed and stirred in an oil bath at 75 °C for 3.5 h under nitrogen protection. After the reaction was completed, the mixture was centrifuged at 10000 rpm for 10 min, washed three times with toluene (each time the mass of toluene was 10% of the total mass of the toluene), and finally vacuum dried at 55 °C for 10 h to obtain silane-grafted nanoparticles. The nanoparticles were composed of nano-silica and nano-zinc oxide in a mass ratio of 0.7:0.3. S3: The complex and dialkyl dithiophosphate in step S2 were mixed evenly according to a mass ratio of 19:12. The mixture was then refluxed and stirred at 95°C for 5.5 h. After the reaction was completed, the mixture was cooled to room temperature and the unreacted dialkyl dithiophosphate was removed by rotary evaporation at 70°C to obtain polyether modified silicone oil. The dialkyl dithiophosphate was composed of diethyl dithiophosphate and dimethyl dithiophosphate in a mass ratio of 0.6:0.4.
[0040] Example 2 The preparation method of polyether-modified silicone oil includes the following steps: S1: Octamethylcyclotetrasiloxane, fluorocyclosiloxane, polymethylhydrosiloxane, sulfuric acid, and sodium carbonate were mixed evenly according to a mass ratio of 23.5:1:5:0.4:0.5. The mixture was stirred at 400 rpm for 5 hours at 45°C. After the reaction was completed, sodium carbonate was added, and the mixture was stirred at 45°C for another 2.5 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and finally vacuum devolatilized at 145°C for 2.5 hours to obtain low-hydrogen silicone oil. The fluorocyclosiloxane was composed of trifluoropropylmethylcyclotrisiloxane and tetramethyltri-3-trifluoropropylcyclotetrasiloxane in a mass ratio of 0.65:0.55. S2: The low-hydrogen silicone oil, glycidyl methacrylate, xylene, chloroplatinic acid, polyethylene glycol monoallyl ether, and silane-grafted nanoparticles were mixed in a mass ratio of 20:6:10:0.015:6:1.5. Chloroplatinic acid was added, and the mixture was stirred at 80°C for 2 hours under nitrogen protection. After the reaction was completed, polyethylene glycol monoallyl ether, silane-grafted nanoparticles, and chloroplatinic acid (with the same mass as the chloroplatinic acid mentioned above) were added, and the mixture was stirred at 80°C for another 1.5 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and finally vacuum devolatilized at 145°C for 2.5 hours to obtain the composite. The preparation method of silane-grafted nanoparticles includes the following steps: The nanoparticles, toluene, and vinyltriethoxysilane were mixed in a mass ratio of 5:200:0.75. The mixture was then sonicated for 25 min (ultrasonic power 100 W, ultrasonic frequency 40 kHz). Vinyltriethoxysilane was then added, and the mixture was refluxed and stirred in an oil bath at 80 °C for 3 h under nitrogen protection. After the reaction was completed, the mixture was centrifuged at 10,000 rpm for 12 min, washed three times with toluene (each time the mass of toluene was 10% of the total mass of the toluene), and finally vacuum dried at 60 °C for 9 h to obtain silane-grafted nanoparticles. The nanoparticles were composed of nano-silica and nano-zinc oxide in a mass ratio of 0.75:0.35. S3: The complex and dialkyl dithiophosphate in step S2 were mixed evenly according to a mass ratio of 20:12.5. The mixture was then refluxed and stirred at 100°C for 5 hours. After the reaction was completed, the mixture was cooled to room temperature and unreacted dialkyl dithiophosphate was removed by rotary evaporation at 75°C to obtain polyether-modified silicone oil. The dialkyl dithiophosphate was composed of diethyl dithiophosphate and dimethyl dithiophosphate in a mass ratio of 0.65:0.45.
[0041] Example 3 The preparation method of polyether-modified silicone oil includes the following steps: S1: Octamethylcyclotetrasiloxane, fluorocyclosiloxane, polymethylhydrosiloxane, sulfuric acid, and sodium carbonate were mixed evenly according to a mass ratio of 24:1.2:5.2:0.5:0.6. The mixture was then stirred at 500 rpm for 4 hours at 50°C. After the reaction was completed, sodium carbonate was added, and the mixture was stirred at 50°C for another 2 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and finally vacuum-devoured at 150°C for 2 hours to obtain low-hydrogen silicone oil. The fluorocyclosiloxane was composed of trifluoropropylmethylcyclotrisiloxane and tetramethyltri-3-trifluoropropylcyclotetrasiloxane in a mass ratio of 0.7:0.6. S2: The low-hydrogen silicone oil, glycidyl methacrylate, xylene, chloroplatinic acid, polyethylene glycol monoallyl ether, and silane-grafted nanoparticles were mixed in a mass ratio of 21:7:11:0.02:7:2. Chloroplatinic acid was added, and the mixture was stirred at 85°C under nitrogen protection for 1.5 h. After the reaction was completed, polyethylene glycol monoallyl ether, silane-grafted nanoparticles, and chloroplatinic acid (with the same mass as the chloroplatinic acid mentioned above) were added, and the mixture was stirred at 85°C for another 1 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and finally vacuum devolatilized at 150°C for 2 h to obtain the composite. The preparation method of silane-grafted nanoparticles includes the following steps: The nanoparticles, toluene, and vinyltriethoxysilane were mixed in a mass ratio of 5.2:210:0.8. The nanoparticles were added to toluene and sonicated for 30 min (ultrasonic power 100 W, ultrasonic frequency 40 kHz). Then, vinyltriethoxysilane was added, and the mixture was refluxed and stirred in an oil bath at 85 °C for 2.5 h under nitrogen protection. After the reaction was completed, the mixture was centrifuged at 10,000 rpm for 15 min, washed three times with toluene (each time the mass of toluene was 10% of the total mass of the toluene), and finally vacuum dried at 65 °C for 8 h to obtain silane-grafted nanoparticles. The nanoparticles were composed of nano-silica and nano-zinc oxide in a mass ratio of 0.8:0.4. S3: The complex and dialkyl dithiophosphate in step S2 were mixed evenly according to a mass ratio of 21:13. The mixture was then refluxed and stirred at 105°C for 4.5 h. After the reaction was completed, the mixture was cooled to room temperature and the unreacted dialkyl dithiophosphate was removed by rotary evaporation at 80°C to obtain polyether modified silicone oil. The dialkyl dithiophosphate was composed of diethyl dithiophosphate and dimethyl dithiophosphate in a mass ratio of 0.7:0.5.
[0042] Comparative Example 1 The difference between this comparative example and Example 3 is that, in the preparation of polyether modified silicone oil, in step S1, fluorocyclosiloxane is replaced by trifluoropropylmethylcyclotrisiloxane in equal mass, while the remaining steps and raw materials are the same as in Example 3. S1: Octamethylcyclotetrasiloxane, trifluoropropylmethylcyclotrisiloxane, polymethylhydrosiloxane, sulfuric acid, and sodium carbonate were mixed evenly according to a mass ratio of 24:1.2:5.2:0.5:0.6. The mixture was then stirred at 500 rpm for 4 hours at 50°C. After the reaction was completed, sodium carbonate was added, and the mixture was stirred at 50°C for another 2 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and finally vacuum devolatilized at 150°C for 2 hours to obtain low-hydrogen silicone oil.
[0043] Comparative Example 2 The difference between this comparative example and Example 3 is that, in the preparation of polyether modified silicone oil, in step S1, the fluorocyclosiloxane is replaced by an equal mass of tetramethyltri-3-trifluoropropylcyclotetrasiloxane, while the remaining steps and raw materials are the same as in Example 3. S1: Octamethylcyclotetrasiloxane, tetramethyltri-3-trifluoropropylcyclotetrasiloxane, polymethylhydrosiloxane, sulfuric acid, and sodium carbonate were mixed evenly according to a mass ratio of 24:1.2:5.2:0.5:0.6. The mixture was stirred at 500 rpm for 4 hours at 50°C. After the reaction was completed, sodium carbonate was added and the mixture was stirred at 50°C for another 2 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and finally vacuum devolatilized at 150°C for 2 hours to obtain low-hydrogen silicone oil.
[0044] Comparative Example 3 The difference between this comparative example and Example 3 is that, in the preparation of polyether modified silicone oil, in step S2, nanoparticles are replaced with nano-silica of equal mass, while the remaining steps and raw materials are the same as in Example 3. The preparation method of silane-grafted nanoparticles includes the following steps: The nano-silica, toluene, and vinyltriethoxysilane were mixed in a mass ratio of 5.2:210:0.8. The nano-silica was added to toluene and sonicated for 30 min (ultrasonic power 100 W, ultrasonic frequency 40 kHz). Then, vinyltriethoxysilane was added, and the mixture was refluxed and stirred in an oil bath at 85 °C for 2.5 h under nitrogen protection. After the reaction was completed, the mixture was centrifuged at 10,000 rpm for 15 min, washed three times with toluene (each time the mass of toluene was 10% of the total mass of the above toluene), and finally vacuum dried at 65 °C for 8 h to obtain silane-grafted nanoparticles.
[0045] Comparative Example 4 The difference between this comparative example and Example 3 is that, in the preparation of polyether modified silicone oil, in step S2, nanoparticles are replaced with nano zinc oxide of equal mass, while the remaining steps and raw materials are the same as in Example 3. The preparation method of silane-grafted nanoparticles includes the following steps: According to the mass ratio of nano-zinc oxide, toluene, and vinyltriethoxysilane of 5.2:210:0.8, nano-zinc oxide was added to toluene and ultrasonically treated for 30 min (ultrasonic power of 100 W, ultrasonic frequency of 40 kHz). Then, vinyltriethoxysilane was added, and the mixture was refluxed and stirred in an oil bath at 85 °C for 2.5 h under nitrogen protection. After the reaction was completed, the mixture was centrifuged at 10,000 rpm for 15 min, washed three times with toluene (each time the mass of toluene was 10% of the total mass of toluene), and finally vacuum dried at 65 °C for 8 h to obtain silane-grafted nanoparticles.
[0046] Comparative Example 5 The difference between this comparative example and Example 3 is that, in the preparation of polyether modified silicone oil, in step S2, the low-hydrogen silicone oil is reacted with glycidyl methacrylate and polyethylene glycol monoallyl ether, while the remaining steps and raw materials are the same as in Example 3. S2: The low-hydrogen silicone oil, glycidyl methacrylate, xylene, chloroplatinic acid, and polyethylene glycol monoallyl ether were mixed in a mass ratio of 21:8:11:0.02:8. Chloroplatinic acid was added, and the mixture was stirred at 85°C for 1.5 h under nitrogen protection. After the reaction was completed, polyethylene glycol monoallyl ether and chloroplatinic acid (the mass of chloroplatinic acid was the same as that of the chloroplatinic acid mentioned above) were added, and the mixture was stirred at 85°C for another h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and finally vacuum devolatilized at 150°C for 2 h to obtain the composite.
[0047] Comparative Example 6 The difference between this comparative example and Example 3 is that, in the preparation of polyether modified silicone oil, in step S2, the low-hydrogen silicone oil is reacted with silane-grafted nanoparticles and polyethylene glycol monoallyl ether, while the remaining steps and raw materials are the same as in Example 3. S2: The low-hydrogen silicone oil, silane-grafted nanoparticles, xylene, chloroplatinic acid, and polyethylene glycol monoallyl ether were mixed in a mass ratio of 21:8:11:0.02:8. Chloroplatinic acid was added, and the mixture was stirred at 85°C for 1.5 h under nitrogen protection. After the reaction was completed, polyethylene glycol monoallyl ether and chloroplatinic acid (the mass of chloroplatinic acid was the same as that of the chloroplatinic acid mentioned above) were added, and the mixture was stirred at 85°C for another 1 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and finally vacuum devolatilized at 150°C for 2 h to obtain the composite.
[0048] Comparative Example 7 The difference between this comparative example and Example 3 is that, in the preparation of polyether modified silicone oil, in step S3, dialkyl dithiophosphate is replaced by diethyl dithiophosphate in equal mass, while the remaining steps and raw materials are the same as in Example 3. S3: The complex and diethyl dithiophosphate in step S2 were mixed evenly according to a mass ratio of 21:13. The mixture was then refluxed and stirred at 105°C for 4.5 h. After the reaction was completed, the mixture was cooled to room temperature and unreacted diethyl dithiophosphate was removed by rotary evaporation at 80°C to obtain polyether modified silicone oil.
[0049] Comparative Example 8 The difference between this comparative example and Example 3 is that, in the preparation of polyether modified silicone oil, in step S3, dialkyl dithiophosphate is replaced by dimethyl dithiophosphate in equal mass, while the remaining steps and raw materials are the same as in Example 3. S3: The complex and dimethyl dithiophosphate in step S2 were mixed evenly according to a mass ratio of 21:13. The mixture was then refluxed and stirred at 105°C for 4.5 h. After the reaction was completed, the mixture was cooled to room temperature and unreacted dimethyl dithiophosphate was removed by rotary evaporation at 80°C to obtain polyether modified silicone oil.
[0050] The surface tension, thermal stability, defoaming performance and storage stability of the polyether modified silicone oils prepared in Examples 1-3 and Comparative Examples 1-8 were tested.
[0051] Surface tension test: The polyether modified silicone oils prepared in Examples 1-3 and Comparative Examples 1-8 were made into aqueous solutions with a mass fraction of 5%, and the surface tension of the aqueous solutions was measured by a contact angle measuring instrument. Emulsion preparation: Hydrophobic silica and polyether-modified silicone oil prepared in Examples 1-3 and Comparative Examples 1-8 were added to a round-bottom flask at a mass ratio of 1:10. The mixture was heated to 150°C in a stirring oil bath and reacted at a constant temperature for 4 hours. Then the temperature was lowered to 85°C, and emulsifiers Span80 and Tween80 and thickener glyceryl monostearate were added. The mass ratio of Span80, Tween80 and glyceryl monostearate was 2.5:1.2:1. The mixture was stirred at 10000 r / min for 2 minutes at room temperature using a shear dispersion emulsifier. A certain amount of water was added dropwise during high-speed stirring to obtain a white organosilicon emulsion defoamer product with an active ingredient mass fraction of 20%. Thermal stability test: Measure 2g of white silicone emulsion defoamer product and put it into a sealable test tube. Let it stand for 30 minutes in environments of 120℃, 130℃, 140℃, 150℃ and 160℃. After taking it out and letting the temperature drop, observe whether oil floats and record the temperature at which oil floats. Defoaming performance test: Weigh 5g of nonylphenol polyoxyethylene ether and 5g of sodium dodecylbenzenesulfonate and dissolve them in 990mL of water. After mixing, stir until a uniform transparent liquid is obtained, which is the standard foaming solution. Measure 50mL of the standard foaming solution with a graduated cylinder, add 0.1g of white silicone emulsion defoamer, put it in a 50℃ constant temperature water bath, stopper the bottle, and shake the graduated cylinder vertically up and down 30 times at a frequency of 2 times per second and an amplitude of (30-35)cm. Let it stand and start timing with a stopwatch to record the time it takes for the foam to disappear until the liquid surface appears. The unit is seconds (s). Storage stability test: Measure 50 mL of white silicone emulsion defoamer product, let it stand at room temperature for three weeks, and observe whether it separates into layers; The test results are shown in Table 1 below: Table 1 Performance parameters of polyether-modified silicone oils prepared in Examples 1-3 and Comparative Examples 1-8
[0052] As shown in Table 1 above, and comparing Comparative Examples 1-2 and Example 3, in step S1, replacing the fluorocyclosiloxane with trifluoropropylmethylcyclotrisiloxane or tetramethyltri-3-trifluoropropylcyclotetrasiloxane by mass, and finally preparing polyether-modified silicone oil, the test results were worse than those of Example 3. This indicates that the fluorocyclosiloxane composed of trifluoropropylmethylcyclotrisiloxane and tetramethyltri-3-trifluoropropylcyclotetrasiloxane has a synergistic effect, which can effectively improve the thermal stability and antioxidant properties of polyether-modified silicone oil. Furthermore, the fluorocyclosiloxane has a lower surface energy, which can significantly reduce the surface tension of polyether-modified silicone oil, and can also further enhance its defoaming performance and storage stability. Comparing Comparative Examples 3-6 and Example 3, it can be seen that in step S2, replacing the nanoparticles with nano-silica or nano-zinc oxide by the same mass, or reacting low-hydrogen silicone oil with glycidyl methacrylate and polyethylene glycol monoallyl ether, or reacting low-hydrogen silicone oil with silane-grafted nanoparticles and polyethylene glycol monoallyl ether, and finally preparing polyether-modified silicone oil, the test results are worse than those of Example 3. This indicates that the nanoparticles composed of a mixture of nano-silica and nano-zinc oxide have better dispersibility, prevent agglomeration, and can play a synergistic role, effectively improving the thermal stability of polyether-modified silicone oil, and having a good effect on defoaming performance and storage stability. Reacting low-hydrogen silicone oil with allyl polyether, silane-grafted nanoparticles, and glycidyl methacrylate not only has better binding force, but also can better improve the thermal stability and wettability of polyether-modified silicone oil, reduce surface tension, further improve defoaming performance and storage stability, and realize the multifunctionality of polyether-modified silicone oil. Comparing Comparative Examples 7-8 and Example 3, it can be seen that in step S3, replacing dialkyl dithiophosphate with diethyl dithiophosphate or dimethyl dithiophosphate by mass, and finally preparing polyether-modified silicone oil, the test results are worse than those of Example 3. This indicates that dialkyl dithiophosphate, composed of a mixture of diethyl dithiophosphate and dimethyl dithiophosphate, has a synergistic effect, which not only helps to reduce surface tension, but also can better improve the defoaming performance, storage stability and thermal stability of polyether-modified silicone oil.
[0053] As shown in Table 1 above, the polyether-modified silicone oils prepared in Examples 1-3, compared to those prepared in Comparative Examples 1-8, achieved the required performance by reacting octamethylcyclotetrasiloxane, fluorocyclosiloxane, and polymethylhydrosiloxane with allyl polyether, silane-grafted nanoparticles, glycidyl methacrylate, and finally combining with dialkyl dithiophosphate. The polyether-modified silicone oils prepared in Examples 1-8 did not meet the performance requirements. This indicates that the polyether-modified silicone oils prepared in this invention not only have low surface tension, excellent thermal stability and wettability, but also good defoaming properties and storage stability, demonstrating excellent overall performance.
[0054] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
[0055] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined by the present invention, they should all fall within the protection scope of the present invention.
Claims
1. A method for preparing polyether-modified silicone oil, characterized in that, Includes the following steps: S1: Reaction of octamethylcyclotetrasiloxane, fluorocyclosiloxane and polymethylhydrosiloxane yields low-hydrogen silicone oil; S2: React the low-hydrogen silicone oil from step S1 with allyl polyether, silane-grafted nanoparticles, and glycidyl methacrylate to obtain a composite. S3: Combine the complex from step S2 with dialkyl dithiophosphate to obtain polyether-modified silicone oil.
2. The method for preparing a polyether-modified silicone oil according to claim 1, characterized in that, Step S1 is as follows: Octamethylcyclotetrasiloxane, fluorocyclosiloxane, polymethylhydrosiloxane and sulfuric acid were mixed evenly and then stirred to react. After the reaction was completed, sodium carbonate was added and stirring was continued. After the reaction was completed, the mixture was cooled to room temperature, filtered, and finally vacuum devolatilized to obtain low-hydrogen silicone oil.
3. The method for preparing a polyether-modified silicone oil according to claim 2, characterized in that, The fluorocyclosiloxane is composed of trifluoropropylmethylcyclotrisiloxane and tetramethyltri-3-trifluoropropylcyclotetrasiloxane in a mass ratio of 0.6-0.7:0.5-0.
6.
4. The method for preparing a polyether-modified silicone oil according to claim 1, characterized in that, Step S2 is as follows: The low-hydrogen silicone oil, glycidyl methacrylate, and xylene from step S1 were mixed, and a catalyst was added. The mixture was then stirred and reacted under nitrogen protection. After the reaction was completed, allyl polyether, silane-grafted nanoparticles, and the catalyst were added, and the reaction was stirred and reacted again. After the reaction was completed, the mixture was cooled to room temperature, filtered, and finally vacuum devolatilized to obtain the composite.
5. The method for preparing a polyether-modified silicone oil according to claim 4, characterized in that, The allyl polyether is polyethylene glycol monoallyl ether.
6. The method for preparing a polyether-modified silicone oil according to claim 4, characterized in that, The preparation method of the silane-grafted nanoparticles includes the following steps: Nanoparticles were added to toluene and sonicated. Then, a silane coupling agent was added, and the mixture was refluxed and stirred under nitrogen protection. After the reaction was completed, the mixture was centrifuged, washed with toluene, and finally dried under vacuum to obtain silane-grafted nanoparticles.
7. The method for preparing a polyether-modified silicone oil according to claim 6, characterized in that, The nanoparticles are made of nano-silica and nano-zinc oxide in a mass ratio of 0.7-0.8:0.3-0.
4.
8. The method for preparing a polyether-modified silicone oil according to claim 1, characterized in that, Step S3 is as follows: The complex in step S2 was mixed evenly with dialkyl dithiophosphate, and then refluxed and stirred. After the reaction was completed, it was cooled to room temperature, and the unreacted dialkyl dithiophosphate was removed by rotary evaporation to finally obtain polyether modified silicone oil.
9. The method for preparing a polyether-modified silicone oil according to claim 8, characterized in that, The dialkyl dithiophosphate is composed of diethyl dithiophosphate and dimethyl dithiophosphate in a mass ratio of 0.6-0.7:0.4-0.5.