Anti-poisoning platinum catalyst and preparation method thereof

Abstract

The invention relates to the technical field of platinum catalysts, and particularly discloses an anti-poisoning platinum catalyst and a preparation method thereof. The anti-poisoning platinum catalyst comprises the following components in parts by mass: 0.8-1.2 parts of a platinum-containing compound; 0.8 to 1.1 parts of a composite anti-toxic agent; 4.8 to 5.2 parts of a solvent; 1.8 to 2.2 parts of an auxiliary agent; the composite anti-poisoning agent is formed by compounding trimethyl gallium, diethyl aluminum chloride and dicarboxyethyl germanium trioxide. The method has the advantage of improving the anti-poisoning performance of the platinum catalyst.

Description

Technical Field

[0001] The invention relates to the field of platinum catalysts, and in particular to a poisoning-resistant platinum catalyst and a preparation method thereof. Background Art

[0002] Ordinary platinum catalysts do not have anti-poisoning effects and are very sensitive to the silicone curing environment. Due to improper environment, the catalytic activity of platinum catalysts will be suppressed to an extremely low level. Therefore, anti-poisoning behavior is very important during the silicone rubber vulcanization process.

[0003] Typically, anti-poisoning agents are added to platinum catalysts to improve their anti-poisoning ability, but the anti-poisoning ability of existing anti-poisoning platinum catalysts is still poor and difficult to meet production needs. Therefore, there is still room for improvement. Summary of the invention

[0004] In order to improve the anti-poisoning performance of platinum catalysts, the present application provides a poisoning-resistant platinum catalyst and a preparation method thereof.

[0005] In a first aspect, the present application provides a platinum catalyst resistant to poisoning, which adopts the following technical solution: A poisoning-resistant platinum catalyst comprises the following components in parts by weight: 0.8-1.2 parts of platinum compound; 0.8-1.1 parts of composite anti-poisoning agent; Solvent 4.8-5.2 parts; 1.8-2.2 parts of additives; The composite anti-poisoning agent is a compound of trimethylgallium, diethylaluminum chloride and dicarboxyethylgermanium trioxide.

[0006] By adopting the above technical scheme, by adding a composite anti-poisoning agent composed of trimethylgallium, diethylaluminum chloride and dicarboxyethylgermanium trioxide, the anti-poisoning performance of the platinum catalyst can be significantly improved, so that the platinum catalyst can have good catalytic activity even under conditions of high concentrations of N, S, and P series compounds, thereby stably exerting the catalytic effect, allowing the silicone rubber to be smoothly vulcanized, and well meeting the actual production needs.

[0007] Preferably, the mass ratio of trimethylgallium, diethylaluminum chloride and dicarboxyethylgermanium trioxide is 0.1-0.2:0.4-0.5:0.3-0.4.

[0008] By adopting the above technical solution and specifically selecting the mass ratio of trimethylgallium, diethylaluminum chloride, and dicarboxyethylgermanium trioxide, the anti-poisoning performance of the platinum catalyst can be better improved, sulfurization can be successfully completed in extreme environments, and the needs of harsh production conditions can be better met.

[0009] Preferably, the platinum-containing compound is chloroplatinic acid.

[0010] By adopting the above technical solution and specifically selecting chloroplatinic acid, the effect of combining with the composite anti-poisoning agent is better, so that the effect of improving the anti-poisoning performance of the platinum catalyst is better.

[0011] Preferably, the solvent is isopropanol.

[0012] By adopting the above technical solution and specifically selecting isopropanol, the effect of dissolving chloroplatinic acid is better, and the quality of the prepared platinum catalyst is better.

[0013] Preferably, the auxiliary agent is a compound of vinyl double head and sodium bicarbonate.

[0014] By adopting the above technical solution and adding vinyl double heads and sodium bicarbonate, the catalytic effect of the platinum catalyst is made more stable and the quality is better.

[0015] Preferably, the mass ratio of the vinyl double head to sodium bicarbonate is 0.9-1.1:0.9-1.1.

[0016] By adopting the above technical solution and specifically selecting the mass ratio of the vinyl double head and sodium bicarbonate, the effect of improving the stability of the platinum catalyst is better, which helps to further improve the product quality.

[0017] In a second aspect, the present application provides a method for preparing a poisoning-resistant platinum catalyst, using the following technical solution: A method for preparing the above-mentioned poisoning-resistant platinum catalyst comprises the following steps: Step 1), mixing a platinum-containing compound and a solvent until the platinum-containing compound is completely dissolved to obtain a premix; Step 2), adding a composite anti-poisoning agent and an auxiliary agent to the premix, heating the mixture for reaction, and obtaining an anti-poisoning platinum catalyst.

[0018] By adopting the above technical solution, the prepared platinum catalyst has strong anti-poisoning performance and can maintain strong catalytic activity under high concentrations of N, S, and P series compounds, so that silicone rubber can be successfully vulcanized.

[0019] Preferably, in step 2), the temperature is raised to 68-72° C. and the reaction is carried out for 2-3 hours.

[0020] By adopting the above technical solution and reacting at 68-72° C., the composite anti-poisoning agent has a better effect of improving the anti-poisoning performance of the platinum catalyst, and the quality of the prepared platinum catalyst is higher.

[0021] In summary, this application has the following beneficial effects: 1. Since the present application adds a composite anti-poisoning agent composed of trimethylgallium, diethylaluminum chloride and dicarboxyethylgermanium trioxide, the anti-poisoning performance of the platinum catalyst can be significantly improved, so that the platinum catalyst can also have good catalytic activity under conditions of high concentrations of N, S, and P series compounds, thereby stably exerting the catalytic effect, allowing the silicone rubber to be smoothly vulcanized, and well meeting the actual production needs.

[0022] 2. In the present application, it is preferred to specifically select the mass ratio of trimethylgallium, diethylaluminum chloride, and dicarboxyethylgermanium trioxide to improve the anti-poisoning performance of the platinum catalyst, better complete the sulfurization in extreme environments, and better meet the needs of harsh production conditions.

[0023] 3. In the present application, chloroplatinic acid is preferably selected specifically, and the effect of combining with the composite anti-poisoning agent is better, so that the effect of improving the anti-poisoning performance of the platinum catalyst is better. DETAILED DESCRIPTION

[0024] The present application is further described in detail below with reference to the embodiments.

[0025] Example 1 A poisoning-resistant platinum catalyst comprising the following components: Containing platinum compounds, composite anti-poisoning agents, solvents, and additives.

[0026] The platinum-containing compound was chloroplatinic acid, purchased from Shandong Shengcang Chemical Technology Co., Ltd., CAS No.: 16941-12-1.

[0027] The composite anti-poisoning agent is a compound of trimethylgallium, diethylaluminum chloride, and dicarboxyethylgermanium trioxide.

[0028] Trimethylgallium was purchased from Hubei Watson Chemical Technology Co., Ltd., CAS number: 1445-79-0.

[0029] Diethylaluminum chloride was purchased from Nantong Runfeng Petrochemical Co., Ltd., CAS No.: 96-10-6.

[0030] Dicarboxyethyl germanium trioxide was purchased from Wuhan Kemik Biopharmaceutical Technology Co., Ltd., CAS number: 12758-40-6.

[0031] The solvent was isopropanol, purchased from Jinan Xinwo Chemical Co., Ltd., CAS No.: 67-63-0.

[0032] The auxiliary agent is a compound of vinyl double head and sodium bicarbonate.

[0033] The vinyl double head was purchased from Jinan Yunuo Chemical Co., Ltd., CAS number: 2627-95-4.

[0034] Sodium bicarbonate was purchased from Wenzhou Chaocheng Chemical Co., Ltd., CAS No.: 144-55-8.

[0035] The method for preparing a poisoning-resistant platinum catalyst comprises the following steps: Step 1), 0.8 kg of chloroplatinic acid and 4.8 kg of isopropanol are put into a stirring tank at a speed of 60 r / min, and stirred and mixed until the chloroplatinic acid is completely dissolved to obtain a premix.

[0036] Step 2), add 0.1kg trimethylgallium, 0.4kg diethylaluminum chloride, 0.3kg dicarboxyethyl germanium trioxide, 0.9kg vinyl double-end, 0.9kg sodium bicarbonate to the premix, heat to 68°C, stir continuously at a speed of 60r / min, react for 2h, and obtain a poisoning-resistant platinum catalyst.

[0037] Example 2 A poisoning-resistant platinum catalyst comprising the following components: Containing platinum compounds, composite anti-poisoning agents, solvents, and additives.

[0038] The platinum-containing compound was chloroplatinic acid, purchased from Shandong Shengcang Chemical Technology Co., Ltd., CAS No.: 16941-12-1.

[0039] The composite anti-poisoning agent is a compound of trimethylgallium, diethylaluminum chloride, and dicarboxyethylgermanium trioxide.

[0040] Trimethylgallium was purchased from Hubei Watson Chemical Technology Co., Ltd., CAS number: 1445-79-0.

[0041] Diethylaluminum chloride was purchased from Nantong Runfeng Petrochemical Co., Ltd., CAS No.: 96-10-6.

[0042] Dicarboxyethyl germanium trioxide was purchased from Wuhan Kemik Biopharmaceutical Technology Co., Ltd., CAS number: 12758-40-6.

[0043] The solvent was isopropanol, purchased from Jinan Xinwo Chemical Co., Ltd., CAS No.: 67-63-0.

[0044] The auxiliary agent is a compound of vinyl double head and sodium bicarbonate.

[0045] The vinyl double head was purchased from Jinan Yunuo Chemical Co., Ltd., CAS number: 2627-95-4.

[0046] Sodium bicarbonate was purchased from Wenzhou Chaocheng Chemical Co., Ltd., CAS No.: 144-55-8.

[0047] The method for preparing a poisoning-resistant platinum catalyst comprises the following steps: Step 1), 1 kg of chloroplatinic acid and 5 kg of isopropanol are put into a stirring tank at a speed of 60 r / min, and stirred and mixed until the chloroplatinic acid is completely dissolved to obtain a premix.

[0048] Step 2), add 0.15kg trimethylgallium, 0.45kg diethylaluminum chloride, 0.35kg dicarboxyethyl germanium trioxide, 1kg vinyl double-capped end, and 1kg sodium bicarbonate to the premix, raise the temperature to 70°C, stir continuously at a speed of 60r / min, react for 2.5h, and obtain a platinum catalyst resistant to poisoning.

[0049] Example 3 A poisoning-resistant platinum catalyst comprising the following components: Containing platinum compounds, composite anti-poisoning agents, solvents, and additives.

[0050] The platinum-containing compound was chloroplatinic acid, purchased from Shandong Shengcang Chemical Technology Co., Ltd., CAS No.: 16941-12-1.

[0051] The composite anti-poisoning agent is a compound of trimethylgallium, diethylaluminum chloride, and dicarboxyethylgermanium trioxide.

[0052] Trimethylgallium was purchased from Hubei Watson Chemical Technology Co., Ltd., CAS number: 1445-79-0.

[0053] Diethylaluminum chloride was purchased from Nantong Runfeng Petrochemical Co., Ltd., CAS No.: 96-10-6.

[0054] Dicarboxyethyl germanium trioxide was purchased from Wuhan Kemik Biopharmaceutical Technology Co., Ltd., CAS number: 12758-40-6.

[0055] The solvent was isopropanol, purchased from Jinan Xinwo Chemical Co., Ltd., CAS No.: 67-63-0.

[0056] The auxiliary agent is a compound of vinyl double head and sodium bicarbonate.

[0057] The vinyl double head was purchased from Jinan Yunuo Chemical Co., Ltd., CAS number: 2627-95-4.

[0058] Sodium bicarbonate was purchased from Wenzhou Chaocheng Chemical Co., Ltd., CAS No.: 144-55-8.

[0059] The method for preparing a poisoning-resistant platinum catalyst comprises the following steps: Step 1), 1.2 kg of chloroplatinic acid and 5.2 kg of isopropanol are put into a stirring tank at a speed of 60 r / min, and stirred and mixed until the chloroplatinic acid is completely dissolved to obtain a premix.

[0060] Step 2), add 0.2kg trimethylgallium, 0.5kg diethylaluminum chloride, 0.4kg dicarboxyethyl germanium trioxide, 1.1kg vinyl double-capped end, 1.1kg sodium bicarbonate to the premix, heat to 72°C, stir continuously at a speed of 60r / min, react for 3h, and obtain a platinum catalyst resistant to poisoning.

[0061] Comparative Example 1 A platinum catalyst resistant to poisoning, compared with Example 2, the only difference is: In the composite anti-poisoning agent, isopropoxide aluminum is used to replace trimethylgallium in equal amounts.

[0062] Isopropoxide aluminum was purchased from Yangzhou Zhongtianli New Materials Co., Ltd., CAS No.: 555-31-7.

[0063] Comparative Example 2 A platinum catalyst resistant to poisoning, compared with Example 2, the only difference is: In the composite anti-poisoning agent, aluminum triacetylacetonate is used to replace diethylaluminum chloride in equal amounts.

[0064] Aluminum triacetylacetonate was purchased from Hubei Kewode Chemical Co., Ltd., CAS No.: 13963-57-0.

[0065] Comparative Example 3 A platinum catalyst resistant to poisoning, compared with Example 2, the only difference is: In the composite anti-poisoning agent, diisobutylaluminum hydride is used to replace dicarboxyethylgermanium trioxide in equal amounts.

[0066] Diisobutylaluminum hydride was purchased from Hubei Tosoh Chemical Technology Co., Ltd., CAS No.: 1191-15-7.

[0067] Comparative Example 4 A platinum catalyst resistant to poisoning, compared with Example 2, the only difference is: In the composite anti-poisoning agent, isopropoxide aluminum is used to replace trimethylgallium in an equal amount, triacetylacetonate aluminum is used to replace diethylaluminum chloride in an equal amount, and diisobutylaluminum hydride is used to replace dicarboxyethylgermanium trioxide in an equal amount.

[0068] Isopropoxide aluminum was purchased from Yangzhou Zhongtianli New Materials Co., Ltd., CAS No.: 555-31-7.

[0069] Aluminum triacetylacetonate was purchased from Hubei Kewode Chemical Co., Ltd., CAS No.: 13963-57-0.

[0070] Diisobutylaluminum hydride was purchased from Hubei Tosoh Chemical Technology Co., Ltd., CAS No.: 1191-15-7.

[0071] Comparative Example 5 A platinum catalyst resistant to poisoning, compared with Example 2, the only difference is: In the composite anti-poisoning agent, gallium isooctanoate is used in equal amounts to replace trimethylgallium.

[0072] Gallium 2-ethylhexanoate was purchased from Hubei Xingyan New Material Technology Co., Ltd., CAS No.: 67969-68-0.

[0073] Comparative Example 6 A platinum catalyst resistant to poisoning, compared with Example 2, the only difference is: In the composite anti-poisoning agent, trimethylgermanium chloride is used to replace dicarboxyethylgermanium trioxide in equal amounts.

[0074] Trimethylgermanium chloride was purchased from Wuhan Huaxiang Kejie Biotechnology Co., Ltd., CAS number: 1529-47-1.

[0075] Experiment 1 The silicone rubber to be tested was prepared by using the test sample prepared by the anti-poisoning platinum catalyst in each embodiment and comparative example, and the vulcanization time of the silicone rubber to be tested at 25° C. was recorded.

[0076] Preparation of test samples: Take 100g of platinum catalyst, add silicone oil to dilute it, and obtain a 5000PPm sample to be tested.

[0077] Preparation of silicone rubber to be tested: Step 1), 0.8g of the sample to be tested and 100g of 107 silicone rubber were put into a stirring kettle, the speed was 60r / min, and the stirring was performed for 5min to obtain A glue; Step 2), 3g hydrogen-containing silicone oil, 0.2g 1-ethynyl cyclohexanol, and 100g 107 silicone rubber were put into a stirring kettle at a speed of 60r / min and stirred for 5min to obtain rubber B; Step 3), put 50g of A glue and 50g of B glue into a stirring kettle, rotate at 100r / min, stir for 3min, then add 1g of N-methylisopropylamine, 1g of dipropyl disulfide, and 1g of phosphorus trichloride, rotate at 120r / min, stir for 5min, and obtain the silicone rubber to be tested.

[0078] 107 silicone rubber was purchased from Jinan Yingyu Chemical Co., Ltd.

[0079] The hydrogen-containing silicone oil was purchased from Jining Tangyi Chemical Co., Ltd.

[0080] 1-Ethynylcyclohexanol was purchased from Hubei Biaoyue Biotechnology Development Co., Ltd., CAS No.: 78-27-3.

[0081] N-methylisopropylamine was purchased from Jiangsu Plus Biotechnology Co., Ltd., CAS No.: 4747-21-1.

[0082] Dipropyl disulfide was purchased from Wuhan Jixinyibang Biotechnology Co., Ltd., CAS No.: 629-19-6.

[0083] Phosphorus trichloride was purchased from Shandong Maofa Chemical Co., Ltd., CAS number: 7719-12-2.

[0084] After the stirring is completed, start timing and record the room temperature vulcanization time for the silicone rubber to reach the gel state at 25°C.

[0085] Each group of experiments was conducted ten times, and the experimental data were averaged.

[0086] The specific experimental data of Experiment 1 are shown in Table 1.

[0087] Table 1 Room temperature vulcanization time (h) Example 1 3.6 Example 2 3.2 Example 3 3.1 Comparative Example 1 17.8 Comparative Example 2 14.2 Comparative Example 3 15.4 Comparative Example 4 18.1 Comparative Example 5 9.7 Comparative Example 6 10.3 According to the data comparison of each embodiment and comparative example in Table 1, it can be obtained that the room temperature vulcanization time of each embodiment is significantly lower than that of each comparative example. It can be seen that although each comparative example can also be vulcanized, its anti-poisoning effect is far inferior to that of the embodiment.

[0088] Comparative Examples 1-4 add aluminum compounds conventionally used as anti-poison agents, but their anti-poison effects are poor when N, S, and P series compounds exist simultaneously and at high concentrations. In contrast, each embodiment uses a special compound of trimethylgallium, diethylaluminum chloride, and dicarboxyethylgermanium trioxide, so that the platinum catalyst still has strong catalytic activity when N, S, and P series compounds exist simultaneously and at high concentrations, allowing the silicone rubber to successfully complete room temperature vulcanization.

[0089] In Comparative Examples 5-6, trimethylgallium is replaced by an equal amount of gallium compounds, and dicarboxyethylgermanium trioxide is replaced by an equal amount of germanium compounds. Although the room temperature vulcanization time of Comparative Examples 5-6 is shorter than that of Comparative Examples 1-4, it is still significantly longer than that of each embodiment, proving that only the special combination of trimethylgallium, diethylaluminum chloride, and dicarboxyethylgermanium trioxide can make the platinum catalyst have particularly significant anti-poisoning performance.

[0090] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A platinum catalyst resistant to poisoning, characterized in that: The composition includes the following components in parts by weight: 0.8-1.2 parts of platinum compound; 0.8-1.1 parts of composite anti-poisoning agent; Solvent 4.8-5.2 parts; 1.8-2.2 parts of additives; The composite anti-poisoning agent is a compound of trimethylgallium, diethylaluminum chloride and dicarboxyethylgermanium trioxide.

2. The anti-poisoning platinum catalyst according to claim 1, characterized in that: The mass ratio of trimethylgallium, diethylaluminum chloride and dicarboxyethylgermanium trioxide is 0.1-0.2:0.4-0.5:0.3-0.

4.

3. The anti-poisoning platinum catalyst according to claim 1, characterized in that: The platinum-containing compound is chloroplatinic acid.

4. The anti-poisoning platinum catalyst according to claim 1, characterized in that: The solvent is isopropanol.

5. The anti-poisoning platinum catalyst according to claim 1, characterized in that: The auxiliary agent is a compound of vinyl double head and sodium bicarbonate.

6. The anti-poisoning platinum catalyst according to claim 5, characterized in that: The mass ratio of the vinyl double head to sodium bicarbonate is 0.9-1.1:0.9-1.

1.

7. A method for preparing a poisoning-resistant platinum catalyst according to any one of claims 1 to 6, characterized in that: The following steps are involved: Step 1), mixing the platinum-containing compound and the solvent until the platinum-containing compound is completely dissolved to obtain a premix; Step 2), adding a composite anti-poisoning agent and an auxiliary agent to the premix, heating the mixture for reaction, and obtaining an anti-poisoning platinum catalyst.

8. The method for preparing a poisoning-resistant platinum catalyst according to claim 7, characterized in that: In the step 2), the temperature is raised to 68-72° C. and the reaction is carried out for 2-3 hours.