CN111620376B - High-activity delta-shaped flower-shaped manganese dioxide for vulcanizing polysulfide sealant and preparation method thereof - Google Patents
High-activity delta-shaped flower-shaped manganese dioxide for vulcanizing polysulfide sealant and preparation method thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2262—Oxides; Hydroxides of metals of manganese
Abstract
The invention discloses high-activity delta-shaped manganese dioxide for vulcanizing polysulfide sealant and a preparation method thereof. Spherical manganese carbonate is used as a precursor template, potassium permanganate is used as an oxidant, and a small amount of metal salt is added and then subjected to high-temperature hydrothermal reaction in a reaction kettle for a plurality of hours to obtain flower-shaped delta-type manganese dioxide. When the flower-shaped delta-shaped manganese dioxide is used for vulcanizing polysulfide sealant, the vulcanization rate is 3 times that of the manganese dioxide sold in the market, and the flower-shaped delta-shaped manganese dioxide has better mechanical properties. In addition, the preparation method has few waste gas, waste liquid and waste residue, and has extremely low pollution.
Description
Technical Field
The invention relates to the field of inorganic chemical materials, in particular to high-activity delta-shaped manganese dioxide for vulcanizing polysulfide sealant and a preparation method thereof.
Background
The polysulfide sealant is the most commonly used sealing material on an aircraft, and is a double-component, A-component is a base paste, and B-component is a vulcanizing agent. The most commonly used sulfiding agent at present is active manganese dioxide. The production process of manganese dioxide for domestic sulfur sealing mainly includes liquid phase reaction of potassium permanganate and soluble bivalent manganese salt. However, the method can produce toxic gas and acid waste liquid, even if soda ash is adopted, the treatment effect is poor, the cost is high, the energy consumption is high, and the pollution is serious. And the manganese dioxide produced by the method is beta-type manganese dioxide, and has low vulcanization efficiency when being used for vulcanizing polysulfide sealant. The vulcanization process of polysulfide rubber requires a large active period (i.e., construction period) to be accounted for in the overall vulcanization time, with overall vulcanization rates being as fast as possible.
Disclosure of Invention
The invention provides high-activity delta-type manganese dioxide for vulcanizing polysulfide sealant and a preparation method thereof, aiming at the defects of the prior art.
The invention adopts the following technical scheme:
a preparation method of high-activity delta-shaped manganese dioxide for vulcanizing polysulfide sealant adopts spherical manganese carbonate as a precursor template, potassium permanganate as an oxidant, and a small amount of metal salt is added and then subjected to high-temperature hydrothermal reaction in a reaction kettle for a plurality of hours to obtain the delta-shaped manganese dioxide.
The preparation method comprises the steps of weighing potassium permanganate, manganese carbonate and a small amount of metal salt according to a proportion, transferring the potassium permanganate, the manganese carbonate and the small amount of metal salt into a polytetrafluoroethylene reaction kettle, adding a proper amount of water, placing the reaction kettle into a baking oven, keeping the temperature between 60 ℃ and 180 ℃, reacting for 4h to 18h, cooling to room temperature, carrying out suction filtration on the obtained precipitate to obtain a black manganese dioxide solid filter cake and clear filtrate, washing the filter cake for a plurality of times, placing the filter cake into the baking oven, and drying at 60 ℃ to obtain black manganese dioxide powder; and placing the manganese dioxide powder into a ball mill, adding a small amount of silane coupling agent, and ball-milling to obtain the high-activity delta-shaped flower-shaped manganese dioxide.
According to the preparation method, the mass ratio of the potassium permanganate to the manganese carbonate is 1:0.8-1:3.
In the preparation method, the metal salt is one or more of sodium silicate, sodium chloride, sodium metaaluminate, calcium carbonate, magnesium carbonate, sodium chloride, ferric chloride, zinc sulfate, cobalt nitrate and nickel chloride.
According to the preparation method, the addition amount of the metal salt is 1-4wt% of the total mass of the raw materials.
According to the preparation method, the silane coupling agent is one or more of KH-550, KH-560, KH-570, KH-580, KH-590, KH-902, KH-903, KH-792, DL-602, A-150, A-151, A-171, A-172, A-1100, A-187, A-174, A-1891, A-189 and A-1120.
According to the preparation method, the addition amount of the silane coupling agent is 0.2-2 wt% of the mass of the manganese dioxide powder.
The high-activity delta-type manganese dioxide for vulcanizing the polysulfide sealant prepared by any one of the preparation methods is the delta-type manganese dioxide.
The invention has the following advantages:
1. spherical manganese carbonate is used as a template agent to react with potassium permanganate to obtain spherical delta-type manganese dioxide, because spherical manganese carbonate is insoluble in water and slowly nucleates when reacting with potassium permanganate to generate manganese dioxide, potassium ions in the potassium permanganate can be fully embedded into tunnels of the manganese dioxide to play a supporting role, so that spherical delta-type manganese dioxide is generated. However, spherical manganese dioxide is easy to agglomerate, the activity of the spherical manganese dioxide can be influenced, and the morphology of the manganese dioxide can be regulated and controlled by adding a certain amount of special metal cations. The manganese dioxide prepared by the method is flower-shaped delta-type manganese dioxide, is not easy to agglomerate, solves the problem, and has better vulcanizing property.
2. MnO formed 2 Is flower-shaped, is not easy to agglomerate, and has the vulcanization rate which is 3 times that of a commercial product.
3. The preparation method has few waste gas, waste liquid and waste residue, and has low pollution.
Drawings
FIG. 1 is a Scanning Electron Micrograph (SEM) of spherical manganese carbonate;
FIG. 2 is an X-ray diffraction pattern (XRD) of manganese dioxide prepared in example 1;
FIG. 3 is a Scanning Electron Micrograph (SEM) of manganese dioxide prepared in example 1;
FIG. 4 is an X-ray diffraction pattern (XRD) of manganese dioxide prepared in example 2;
FIG. 5 is a Scanning Electron Micrograph (SEM) of manganese dioxide prepared in example 2;
FIG. 6 is an X-ray diffraction pattern (XRD) of manganese dioxide prepared in example 3;
FIG. 7 is a Scanning Electron Micrograph (SEM) of manganese dioxide prepared in example 3;
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
3.30g of potassium permanganate and 4.23g of manganese carbonate are weighed and placed in a 100ml hydrothermal reaction kettle, 70ml of water is added, the mixture is heated to a certain temperature (a certain temperature between 60 ℃ and 180 ℃) and reacted for 4 hours to 18 hours, the mixture is cooled to room temperature, the obtained precipitate is filtered by suction to obtain a black manganese dioxide solid filter cake and clear filtrate, the filter cake is washed with water for a plurality of times, and the filter cake is placed in an oven and dried at 60 ℃ to obtain 4.79g of black manganese dioxide powder. 4.79g of manganese dioxide powder is placed in a ball mill, 0.06g of silane coupling agent KH550 is added, and the active manganese dioxide is obtained after ball milling. The pH of the filtrate was measured with a pH meter and found to be 7.3. As can be seen from FIG. 2, the XRD diffraction peaks of the obtained manganese dioxide correspond to those of standard card PDF (86-0666) and are delta-MnO 2, and the manganese dioxide obtained is spherical and clustered together without adding metal salt as can be seen by electron microscopy of FIG. 3.
Example 2
3.30g of potassium permanganate and 4.23g of manganese carbonate are weighed and placed in a 100ml hydrothermal reaction kettle, 0.18g of metal salt sodium silicate is added, 70ml of water is added, the mixture is heated to 60 ℃, after the reaction is carried out for 18 hours, the mixture is cooled to room temperature, the obtained precipitate is filtered by suction, a black manganese dioxide solid filter cake and clear filtrate are obtained, the filter cake is washed with water for a plurality of times, and the filter cake is placed in an oven and dried at 60 ℃ to obtain 4.79g of black manganese dioxide powder. 4.79g of manganese dioxide powder is placed in a ball mill, 0.06g of silane coupling agent KH550 is added, and the active manganese dioxide is obtained after ball milling. The pH of the filtrate was measured with a pH meter and found to be 7.3. As can be seen from FIG. 4, the XRD diffraction peaks of the obtained manganese dioxide correspond to those of the standard card PDF (86-0666) and are delta-MnO 2, and the manganese dioxide obtained after the metal salt is added is in a flower shape through electron microscope scanning in FIG. 5.
Example 3
Weighing 3.30g of potassium permanganate and 4.23g of manganese sulfate, placing the potassium permanganate and the manganese sulfate into a 100ml hydrothermal reaction kettle, adding 70ml of water, heating to a certain temperature (a certain temperature between 60 ℃ and 180 ℃) and reacting for 4-18 hours, cooling to room temperature, carrying out suction filtration on the obtained precipitate to obtain a black manganese dioxide solid filter cake and clear filtrate, washing the filter cake for a plurality of times, putting the filter cake into an oven, and drying at 60 ℃ to obtain 4.13g of black manganese dioxide powder. 4.13g of manganese dioxide powder is placed in a ball mill, 0.06g of silane coupling agent KH550 is added, and the active manganese dioxide is obtained after ball milling. The pH value of the filtrate is 1.7 by using a pH meter, and the acidity is very strong. As can be seen from FIG. 6, the XRD diffraction peaks of the obtained manganese dioxide correspond to those of the standard card PDF #24-0735, and are beta-MnO 2, and the obtained manganese dioxide is rod-shaped as can be seen by electron microscopy scanning of FIG. 7.
Example 4
3g of the active manganese dioxide obtained in the above examples 1, 2 and 3, 2.1g of dibutyl phthalate, 0.05g of accelerator TMTD and 0.03g of accelerator D are ground to prepare paste-like vulcanizing agents A, B, C, and the paste-like vulcanizing agents A, B, C are respectively mixed with the polysulfide sealant base paste, and the indoor temperature is controlled at 23-26 ℃ and the humidity is 50%, so that the vulcanizing performance and the mechanical performance of the paste-like vulcanizing agents are measured. Grinding 3g of commercial Allatin and microphone manganese dioxide, 2.1g of dibutyl phthalate, 0.05g of accelerator TMTD and 0.03g of accelerator D to prepare a pasty vulcanizing agent D, E, mixing with a polysulfide sealant base paste, and testing the vulcanizing property and mechanical property of the pasty vulcanizing agent; the results of the measurement are shown in Table 1, and it can be seen that the flower-like delta-type manganese dioxide in example 2 has a faster vulcanization rate, three times that of the commercially available manganese dioxide and the beta-rod-shaped manganese dioxide in example 3, and is also higher than the spherical delta-type manganese dioxide in example 1, and the mechanical properties are also more excellent.
Table 1 comparison of properties of example 4
| Vulcanizing agent | Pot life | Non-sticking period | Cure period | Tensile Strength | Elongation at break | 24h hardness |
| A | 32min | 1h | 3h | 1.76Mpa | 280％ | 48 |
| B | 35min | 1h | 2h | 1.82Mpa | 290％ | 48 |
| C | 50min | 4h | 6h | 1.64Mpa | 250％ | 48 |
| D (commercially available 1) | 50min | 4h | 6h | 1.66Mpa | 250％ | 48 |
| E (commercially available 2) | 62min | 4h | 7h | 1.61Mpa | 260％ | 48 |
Note that: the cure period refers to the time required from formulation to shore 30, including the active period (construction period) and the tack free period.
Example 5
Weighing 4.74 g of potassium permanganate and 6.83g of manganese carbonate, placing the potassium permanganate and the 6.83g of manganese carbonate into a 100ml hydrothermal reaction kettle, adding 0.26g of sodium chloride metal salt, adding 70ml of water, heating to 180 ℃, reacting for 4 hours, cooling to room temperature, filtering the obtained precipitate by suction to obtain a black manganese dioxide solid filter cake and clear filtrate, washing the filter cake for multiple times, placing the filter cake into an oven, and drying at 60 ℃ to obtain 6.52g of black manganese dioxide powder. 6.52g of manganese dioxide powder is placed in a ball mill, 0.09g of silane coupling agent KH590 is added, and the active manganese dioxide is obtained after ball milling. The pH of the filtrate was measured with a pH meter and found to be 7.1.
Example 6
5.33g of potassium permanganate and 3.18g of manganese carbonate are weighed and placed in a 100ml hydrothermal reaction kettle, 0.14g of metal salt ferric chloride is added, 70ml of water is added, the mixture is heated to 100 ℃, after the reaction is carried out for 12 hours, the mixture is cooled to room temperature, the obtained precipitate is filtered by suction, a black manganese dioxide solid filter cake and a clear filtrate are obtained, the filter cake is washed by water for a plurality of times, and the filter cake is placed in an oven and dried at 60 ℃ to obtain 3.75g of black manganese dioxide powder. 3.75g of manganese dioxide powder is placed in a ball mill, 0.04g of silane coupling agent KH792 is added, and the active manganese dioxide is obtained after ball milling. The pH of the filtrate was measured with a pH meter and found to be 7.4.
The metal salt is selected from one or more of sodium silicate, sodium chloride, sodium metaaluminate, calcium carbonate, magnesium carbonate, sodium chloride, ferric chloride, zinc sulfate, cobalt nitrate and nickel chloride.
It will be understood that modifications and variations will be apparent to those skilled in the art from the foregoing description, and it is intended that all such modifications and variations be included within the scope of the following claims.
Claims (1)
1. The preparation method of the high-activity delta-shaped manganese dioxide for vulcanizing the polysulfide sealant is characterized by adopting spherical manganese carbonate as a precursor template, adopting potassium permanganate as an oxidant, adding a small amount of metal salt, and then carrying out a hydrothermal reaction for a plurality of hours in a reaction kettle to obtain the delta-shaped manganese dioxide; weighing potassium permanganate, manganese carbonate and a small amount of metal salt according to a proportion, transferring the mixture to a polytetrafluoroethylene reaction kettle, adding a proper amount of water, placing the reaction kettle in an oven, keeping the temperature between 60 ℃ and 180 ℃, reacting for 4-18 hours, cooling to room temperature, carrying out suction filtration on the obtained precipitate to obtain a black manganese dioxide solid filter cake and clear filtrate, washing the filter cake for a plurality of times, placing the filter cake in the oven, and drying at 60 ℃ to obtain black manganese dioxide powder; putting manganese dioxide powder into a ball mill, adding a small amount of silane coupling agent, and obtaining high-activity delta-shaped flower-shaped manganese dioxide after ball milling; the mass ratio of the potassium permanganate to the manganese carbonate is 1:0.8-1:3; the metal salt is sodium silicate; the addition amount of the metal salt is 1-4wt% of the total mass of the raw materials; the silane coupling agent is one or more of KH-550, KH-560, KH-570, KH-580, KH-590, KH-902, KH-903, KH-792, DL-602, A-150, A-151, A-171, A-172, A-1100, A-187, A-174, A-1891, A-189 and A-1120; the addition amount of the silane coupling agent is 0.2-2 wt% of the mass of the manganese dioxide powder.
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