Preparation method of water-based platinum catalyst
The preparation of water-soluble platinum catalysts by reacting a water-soluble stabilizer with a platinum salt has been solved, and the problems of excessive use of organic solvents and harsh reaction conditions in the prior art have been achieved, environmentally friendly and efficient platinum catalyst production has been achieved, and its compatibility and stability in rubber has been improved, and the vulcanization reaction efficiency and long-term activity have been significantly improved.
Patent Information
- Application Number
- CN202510457841.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-14
- Publication Date
- 2025-07-11
AI Technical Summary
The existing platinum catalyst preparation method uses a large number of organic solvents, the reaction conditions are harsh, and the catalyst recovery is difficult, making it difficult to meet the needs of environmentally friendly and efficient production.
A water-soluble stabilizer is used to react with a platinum salt to prepare a water-soluble platinum catalyst. The reaction of polysiloxane and a polymer with hydroxy functional groups is used to form a block copolymer. The appropriate mass ratio of platinum salt, reducing agent and water is selected, and the reaction conditions are controlled. Organic solvents are not used during the preparation process.
The environmentally friendly and efficient production of platinum catalysts is achieved, the compatibility with unvulcanized rubber is improved, the vulcanization reaction time is significantly shortened, the stability and long-term activity of the catalyst are enhanced, and the catalytic efficiency is maintained.
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Abstract
Description
Technical Field
[0001] The present invention relates to the field of catalysts, and particularly to a preparation method of an aqueous platinum catalyst. Background Art
[0002] Currently, the common preparation methods of platinum catalysts mainly include the solution method and the solid-phase method. In the solution method, a platinum salt is dissolved in an organic solvent and then reacted with a reducing agent to form a platinum catalyst. The solid-phase method prepares the catalyst through a solid-state reaction. However, these methods have problems such as the use of a large amount of organic solvents, harsh reaction conditions, and difficult catalyst recovery, and it is difficult to meet the requirements of environmental protection and high-efficiency production, so there is still room for improvement. Summary of the Invention
[0003] In order to make the production process of platinum catalysts more environmentally friendly and efficient, the present application provides a preparation method of an aqueous platinum catalyst.
[0004] The preparation method of an aqueous platinum catalyst provided by the present application adopts the following technical scheme: A preparation method of an aqueous platinum catalyst, comprising the following steps: Step 1), adding a stabilizer to water, heating to 50 - 60 °C, and stirring evenly to obtain a stabilizer solution; Step 2), adding a platinum salt to the stabilizer solution and stirring evenly to obtain a reaction solution; Step 3), adding a reducing agent to the reaction solution, controlling the reaction temperature at 30 - 40 °C, reacting for 1 - 2 hours, cooling and filtering to obtain an aqueous platinum catalyst; The stabilizer is a block copolymer obtained by reacting a polysiloxane with a polymer having a hydroxyl functional group; The reducing agent is one of an alcohol compound, a borohydride, formic acid, tartaric acid, ascorbic acid, hydrazine hydrate or citric acid.
[0005] By adopting the above technical scheme, a water-soluble platinum catalyst is prepared by reacting a water-soluble stabilizer with a platinum salt. During the production process, no organic solvent needs to be added, and the process difficulty is relatively low, making the production process of platinum catalysts more environmentally friendly and efficient.
[0006] In addition, since the stabilizer is a block copolymer obtained by reacting a polysiloxane with a polymer having a hydroxyl functional group, the compatibility of the platinum catalyst in unvulcanized rubber is relatively high, the efficiency of the catalytic vulcanization reaction is significantly improved, the rubber vulcanization time can be significantly shortened, and the stability of the platinum catalyst can be significantly improved, so that the platinum catalyst can still maintain a high activity after long-term storage, effectively slowing down the decrease in the activity of the platinum catalyst and making the quality of the platinum catalyst better.
[0007] Preferably, the mass ratio of the platinum salt, reducing agent, stabilizer, and water is 1-3:2-5:5-10:82-92.
[0008] By adopting the above technical solution, by specifically selecting the mass ratio of the platinum salt, reducing agent, stabilizer, and water, the quality of the platinum catalyst is better, the catalytic vulcanization effect is better, and the stability is higher.
[0009] Preferably, the stabilizer is a block copolymer obtained by reacting polyethylene glycol diacrylate with polyvinyl siloxane.
[0010] By adopting the above technical solution, by specifically selecting the stabilizer as a block copolymer obtained by reacting polyethylene glycol diacrylate with polyvinyl siloxane, the stabilizer has a better effect of improving the compatibility between the platinum catalyst and the unvulcanized rubber and improving the stability of the platinum catalyst, and the prepared platinum catalyst has a higher quality.
[0011] Preferably, the preparation method of the stabilizer is as follows: Mix polyethylene glycol diacrylate and polyvinyl siloxane, add DMPA photoinitiator, and stir and react under ultraviolet light irradiation to obtain the stabilizer.
[0012] By adopting the above technical solution, by adding DMPA photoinitiator and stirring and reacting under ultraviolet light irradiation, the reaction efficiency of the stabilizer is higher, and the prepared stabilizer has a better quality.
[0013] Preferably, the mass ratio of the polyethylene glycol diacrylate to the polyvinyl siloxane is 1:1-2.
[0014] By adopting the above technical solution, by specifically selecting the mass ratio of the polyethylene glycol diacrylate to the polyvinyl siloxane, the prepared stabilizer has a better effect of improving the performance of the platinum catalyst.
[0015] Preferably, in the preparation method of the stabilizer, after adding the DMPA photoinitiator, stir and react under ultraviolet light irradiation at room temperature.
[0016] By adopting the above technical solution, by reacting at room temperature, the energy consumption is reduced, and it has a higher economic value.
[0017] Preferably, in the preparation method of the stabilizer, stir for 1-2 h under ultraviolet light irradiation to complete the reaction.
[0018] By adopting the above technical solution, by stirring for 1-2 h, the reaction is ensured to be sufficient, and the prepared stabilizer has a better effect of improving the performance of the platinum catalyst.
[0019] Preferably, the platinum salt is one of chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, platinum(II) chloride, platinum(IV) chloride, diethylamineplatinum(II) chloride, platinum(II) nitrate, ammonium tetrachloroplatinate.
[0020] By adopting the above technical solution, the prepared platinum catalyst has better catalytic effect and can well match the preparation process of the platinum catalyst, making the process difficulty lower and the quality of the prepared platinum catalyst better.
[0021] In summary, the present application has the following beneficial effects: 1. Since the present application prepares a water-soluble platinum catalyst by reacting a water-soluble stabilizer with a platinum salt, no organic solvent needs to be added during the production process, and the process difficulty is lower, making the production process of the platinum catalyst more environmentally friendly and efficient.
[0022] 2. In the present application, it is preferably that the stabilizer is a block copolymer obtained by reacting a polysiloxane with a polymer having a hydroxyl functional group, so that the platinum catalyst has higher compatibility in the unvulcanized rubber, the efficiency of catalyzing the vulcanization reaction is significantly improved, the rubber vulcanization time can be significantly shortened, and the stability of the platinum catalyst can be significantly improved, so that the platinum catalyst can still maintain a high activity after long-term storage, and the reduction of the activity of the platinum catalyst can be effectively slowed down, making the quality of the platinum catalyst better.
[0023] 3. In the present application, it is preferably to specifically select the mass ratio of the platinum salt, the reducing agent, the stabilizer and water, so that the quality of the platinum catalyst is better, the catalytic vulcanization effect is better, and the stability is higher. Detailed implementation mode
[0024] The following further elaborates on the present application in conjunction with examples.
[0025] Example 1 A preparation method of an aqueous platinum catalyst, characterized in that it comprises the following steps: Step 1), adding 5 kg of stabilizer and 92 kg of water into a reaction kettle, heating to 50 °C, with a rotation speed of 120 r / min, stirring for 10 min, and stirring evenly to obtain a stabilizer solution.
[0026] Step 2), adding 1 kg of platinum salt to the stabilizer solution, with a rotation speed of 120 r / min, stirring for 5 min to obtain a reaction solution.
[0027] Step 3), adding 2 kg of reducing agent to the reaction solution, controlling the reaction temperature at 30 °C, with a rotation speed of 30 r / min, continuously stirring and reacting for 1 h, cooling to room temperature and filtering to obtain an aqueous platinum catalyst.
[0028] The stabilizer is a block copolymer obtained by reacting polyethylene glycol diacrylate with polyvinyl siloxane.
[0029] The preparation method of the stabilizer is as follows: Put 10 kg of polyethylene glycol diacrylate and 10 kg of polyvinyl siloxane into a stirring kettle, with a rotation speed of 30 r / min, stir for 10 min, add DMPA photoinitiator, and stir and react for 1 h under ultraviolet light irradiation to obtain the stabilizer.
[0030] The polyethylene glycol diacrylate is purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd. The polyvinyl siloxane is purchased from Jiangxi BlueStar Silicone Co., Ltd. The DMPA photoinitiator is purchased from Wuhan Kemike Biopharmaceutical Technology Co., Ltd. The ultraviolet lamp is purchased from the LED UV system customized by Zhongshan Lidan Yuan Printing Equipment Co., Ltd., the wavelength of the ultraviolet light is 365 nm, and the irradiation light intensity is 300 mW / cm 2 .
[0031] The platinum salt is chloroplatinic acid and is purchased from Shenyang Zhongse Rare and Precious Metal New Materials Co., Ltd.
[0032] The reducing agent is methanol and is purchased from Tianjin Fuyu Jinxi Chemical Co., Ltd.
[0033] Example 2 A preparation method of an aqueous platinum catalyst, characterized by comprising the following steps: Step 1), add 7.5 kg of stabilizer and 87 kg of water into a reaction kettle, heat to 55 °C, with a rotation speed of 120 r / min, stir for 10 min, and stir evenly to obtain a stabilizer solution.
[0034] Step 2), add 2 kg of platinum salt to the stabilizer solution, with a rotation speed of 120 r / min, stir for 5 min to obtain a reaction solution.
[0035] Step 3), add 3.5 kg of reducing agent to the reaction solution, control the reaction temperature at 35 °C, with a rotation speed of 30 r / min, continuously stir and react for 1.5 h, cool to room temperature and filter to obtain the aqueous platinum catalyst.
[0036] The stabilizer is a block copolymer obtained by reacting polypropylene glycol pentanedioate with polyvinyl siloxane.
[0037] The preparation method of the stabilizer is as follows: Put 10 kg of polypropylene glycol pentanedioate and 15 kg of polyvinyl siloxane into a stirring kettle, with a rotation speed of 30 r / min, stir for 10 min, add DMPA photoinitiator, and stir and react for 1.5 h under ultraviolet light irradiation to obtain the stabilizer.
[0038] The polypropylene glycol pentanedioate is purchased from Wuhan Kemike Biopharmaceutical Technology Co., Ltd. Polyvinyl siloxane was purchased from Jiangxi Lanxing Xinghuo Silicone Co., Ltd. DMPA photoinitiator was purchased from Wuhan Kemik Biopharmaceutical Technology Co., Ltd. The UV lamp is purchased from Zhongshan Lidanyuan Printing Equipment Co., Ltd., a customized LED UV system with a UV wavelength of 365nm and an irradiation intensity of 300mW / cm 2 .
[0039] The platinum salt was potassium chloroplatinate, which was purchased from Shanghai Jizhi Biochemical Technology Co., Ltd.
[0040] The reducing agent was tartaric acid, which was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.
[0041] Example 3 A method for preparing an aqueous platinum catalyst, characterized in that it comprises the following steps: Step 1), add 10 kg of stabilizer and 82 kg of water into a reactor, heat to 60° C., rotate at 120 r / min, stir for 10 min, stir evenly, and obtain a stabilizer solution.
[0042] Step 2), add 3 kg of platinum salt to the stabilizer solution, rotate at 120 r / min, and stir for 5 min to obtain a reaction solution.
[0043] Step 3), add 5 kg of reducing agent to the reaction solution, control the reaction temperature at 40° C., the rotation speed at 30 r / min, continue stirring the reaction for 2 h, cool to room temperature, filter, and obtain an aqueous platinum catalyst.
[0044] The stabilizer is a block copolymer obtained by reacting polyvinyl alcohol and polyvinyl siloxane.
[0045] The preparation method of the stabilizer is as follows: 10 kg of polyvinyl alcohol and 20 kg of polyvinyl siloxane were put into a stirring kettle at a speed of 30 r / min and stirred for 10 min. DMPA photoinitiator was added and stirred for reaction under ultraviolet light for 2 h to obtain a stabilizer.
[0046] Polyvinyl alcohol was purchased from Jiangsu Pulex Biotechnology Co., Ltd. Polyvinyl siloxane was purchased from Jiangxi Lanxing Xinghuo Silicone Co., Ltd. DMPA photoinitiator was purchased from Wuhan Kemik Biopharmaceutical Technology Co., Ltd. The UV lamp is purchased from Zhongshan Lidanyuan Printing Equipment Co., Ltd., a customized LED UV system with a UV wavelength of 365nm and an irradiation intensity of 300mW / cm 2 .
[0047] The platinum salt was platinum chloride, which was purchased from Shanghai Jizhi Biochemical Technology Co., Ltd.
[0048] The reducing agent is ascorbic acid, purchased from Qianyan Chemical Technology (Wuhan) Co., Ltd.
[0049] Example 4 A preparation method of an aqueous platinum catalyst, characterized in that it comprises the following steps: Step 1), add 7.5 kg of stabilizer and 87 kg of water into the reaction kettle, heat to 55 °C, rotate at 120 r / min, stir for 10 min, stir evenly to obtain a stabilizer solution.
[0050] Step 2), add 2 kg of platinum salt to the stabilizer solution, rotate at 120 r / min, stir for 5 min to obtain a reaction solution.
[0051] Step 3), add 3.5 kg of reducing agent to the reaction solution, control the reaction temperature at 35 °C, rotate at 30 r / min, continuously stir and react for 1.5 h, cool to room temperature and filter to obtain an aqueous platinum catalyst.
[0052] The stabilizer is a block copolymer obtained by reacting polyvinylpyrrolidone and polymethylsiloxane.
[0053] The preparation method of the stabilizer is as follows: Put 10 kg of polyvinylpyrrolidone and 15 kg of polymethylsiloxane into the stirring kettle, rotate at 30 r / min, stir for 10 min, add DMPA photoinitiator, and stir and react for 1.5 h under ultraviolet light irradiation to obtain a stabilizer.
[0054] Polyvinylpyrrolidone was purchased from Qianyan Chemical Technology (Wuhan) Co., Ltd. Polymethylsiloxane was purchased from Jiangxi Blue Star Silicone Co., Ltd. DMPA photoinitiator was purchased from Wuhan Kemike Biopharmaceutical Technology Co., Ltd. The ultraviolet lamp was purchased from an LED UV system customized by Zhongshan Lidan Yuan Printing Equipment Co., Ltd., the wavelength of the ultraviolet light is 365 nm, and the irradiation light intensity is 300 mW / cm 2 .
[0055] The platinum salt is platinum (II) chloride ethylenediamine complex, purchased from Shanghai Jiji Biochemical Technology Co., Ltd.
[0056] The reducing agent is citric acid, purchased from Beijing Solarbio Science & Technology Co., Ltd.
[0057] Example 5 A preparation method of an aqueous platinum catalyst, characterized in that it comprises the following steps: Step 1): Add 7.5 kg of stabilizer and 87 kg of water into the reaction kettle, heat to 55 °C, rotate at 120 r / min, stir for 10 min, and stir evenly to obtain a stabilizer solution.
[0058] Step 2): Add 2 kg of platinum salt into the stabilizer solution, rotate at 120 r / min, and stir for 5 min to obtain a reaction solution.
[0059] Step 3): Add 3.5 kg of reducing agent into the reaction solution, control the reaction temperature at 35 °C, rotate at 30 r / min, continuously stir and react for 1.5 h, cool to room temperature and filter to obtain an aqueous platinum catalyst.
[0060] The stabilizer is a block copolymer obtained by reacting polyethylene glycol and polyaminosiloxane.
[0061] The preparation method of the stabilizer is as follows: Put 10 kg of polyethylene glycol and 15 kg of polyaminosiloxane into the stirring kettle, rotate at 30 r / min, stir for 10 min, add DMPA photoinitiator, and stir and react under ultraviolet lamp irradiation for 1.5 h to obtain a stabilizer.
[0062] The polyethylene glycol is purchased from Beijing Solarbio Science & Technology Co., Ltd. The polyaminosiloxane is purchased from Jiangxi Bluestar Silicone Co., Ltd. The DMPA photoinitiator is purchased from Wuhan Chemico Biopharmaceutical Technology Co., Ltd. The ultraviolet lamp is purchased from the LED UV system customized by Zhongshan Lidyuan Printing Equipment Co., Ltd., the wavelength of ultraviolet light is 365 nm, and the irradiation light intensity is 300 mW / cm 2
[0063] The platinum salt is platinum nitrate and is purchased from Wuhan Jixin Yibang Biotechnology Co., Ltd.
[0064] The reducing agent is n-butanol and is purchased from Qianyan Chemical Technology (Wuhan) Co., Ltd.
[0065] Comparative Example 1 An oil-type platinum catalyst, purchased from Shanghai Neutron Star Chemical Technology Co., Ltd., model: PC-46.
[0066] Comparative Example 2 An oil-type platinum catalyst, purchased from Heraeus Precious Metals Technology (China) Co., Ltd., model: PT-5000.
[0067] Comparative Example 3 An aqueous platinum catalyst, compared with Example 2, the difference is only that: The stabilizer used was a commercially available water-soluble stabilizer, specifically a polysiloxane-polyethylene glycol block copolymer, purchased from Xi'an Qiyue Biotechnology Co., Ltd., model: Q-0154626.
[0068] Comparative Example 4 An aqueous platinum catalyst, compared with Example 2, the only difference is: The stabilizer is a commercially available water-soluble stabilizer, specifically a polyether-modified silicone oil purchased from Dow Corning Silicones Co., Ltd., model: OFX-0193.
[0069] Experiment 1 The platinum catalyst of each embodiment and comparative example was added to the silicone rubber alone to prepare an unvulcanized rubber sample, and the unvulcanized rubber was tested for T10 and T90 by a vulcanizer.
[0070] Ten unvulcanized rubber specimens were prepared for each embodiment and comparative example, and the average of the ten test data for each embodiment and comparative example was taken.
[0071] Preparation of unvulcanized rubber specimens: Take 10g of platinum catalyst and 990g of silicone rubber, put them into a small internal mixer, mix them evenly, cut them into sheets, and cut them to obtain unvulcanized rubber samples.
[0072] The vulcanizer was purchased from Dongguan CREE Instrument Co., Ltd., model: CREE-6001.
[0073] The platinum catalysts of the embodiments and comparative examples were stored open for 30 days, and the above experiment was conducted again to measure T10 and T90 after storage open for 30 days.
[0074] The specific experimental data of Experiment 1 are shown in Table 1.
[0075] Table 1 According to the data comparison of each embodiment and comparative example in Table 1, it can be obtained that the vulcanization efficiency of each embodiment is significantly higher than that of each comparative example, which proves that the water-based platinum catalyst prepared in each embodiment has better compatibility with silicone rubber and can more effectively improve the vulcanization efficiency.
[0076] In addition, the sulfurization time of each embodiment after storage for 30 days is extended less, while the sulfurization time of each comparative example after storage for 30 days is extended more, which proves that the aqueous platinum catalyst prepared in each embodiment has higher stability, can be stored for a longer period of time without easily causing activity decline, and the quality of the platinum catalyst is better.
[0077] This specific embodiment is only an interpretation of the present application and does not limit the present application. After reading this specification, those skilled in the art may make modifications to this embodiment that do not contribute creatively as needed, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.
Claims
1. A preparation method of an aqueous platinum catalyst, characterized in that: It includes the following steps: Step 1), adding a stabilizer into water, heating to 50 - 60 °C, and stirring evenly to obtain a stabilizer solution; Step 2), adding a platinum salt into the stabilizer solution and stirring evenly to obtain a reaction solution; Step 3), adding a reducing agent into the reaction solution, controlling the reaction temperature at 30 - 40 °C, reacting for 1 - 2 hours, cooling and filtering to obtain an aqueous platinum catalyst; The stabilizer is a block copolymer obtained by the reaction of polysiloxane and a polymer with a hydroxyl functional group; The reducing agent is one of alcohol compounds, borohydrides, formic acid, tartaric acid, ascorbic acid, hydrazine hydrate or citric acid.
2. The preparation method of an aqueous platinum catalyst according to claim 1, wherein: The mass ratio of the platinum salt, reducing agent, stabilizer, and water is 1 - 3: 2 - 5: 5 - 10: 82 - 92.
3. The preparation method of an aqueous platinum catalyst according to claim 1 or 2, characterized in that: The stabilizer is a block copolymer obtained by the reaction of polyethylene glycol diacrylate and polyvinyl siloxane; 4. The preparation method of an aqueous platinum catalyst according to claim 3, characterized in that: The preparation method of the stabilizer is as follows: Mix polyethylene glycol diacrylate and polyvinyl siloxane, add a DMPA photoinitiator, and stir and react under ultraviolet light irradiation to obtain a stabilizer.
5. The preparation method of an aqueous platinum catalyst according to claim 4, characterized in that: The mass ratio of polyethylene glycol diacrylate and polyvinyl siloxane is 1: 1 - 2.
6. The preparation method of an aqueous platinum catalyst according to claim 4, characterized in that: In the preparation method of the stabilizer, after adding the DMPA photoinitiator, stir and react under ultraviolet light irradiation at room temperature.
7. The preparation method of an aqueous platinum catalyst according to claim 4, wherein: In the preparation method of the stabilizer, stir for 1 - 2 h under ultraviolet light irradiation to complete the reaction.
8. The preparation method of an aqueous platinum catalyst according to claim 3, characterized in that: The platinum salt is one of chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, platinum dichloride, platinum chloride, diethylamine platinum chloride, platinum nitrate, ammonium tetrachloroplatinate.