A marine shark repellent and method of making same

Abstract

The present application relates to a kind of offshore shark repellent and its preparation method, belong to shark repellent material technical field.The present application discloses that modified porous silica is compounded with microcapsule to obtain shark repellent.Porous silica is carrier, and the material of avoiding is attached in pore to form modified porous silica;With polymethyl methacrylate as wall material, the material of avoiding is wrapped in microcapsule to obtain microcapsule.Modified porous silica and the material of avoiding of microcapsule are released in water in succession, so that shark repellent has the effect of durability.A variety of materials of avoiding from smell shield and smell avoidance dual effect enhances the effect of driving shark.The present application can prepare the pollution-free offshore shark repellent with durability and good shark repellent effect.

Description

Technical Field

[0001] This invention belongs to the field of shark repellent materials technology, and relates to a marine shark repellent and its preparation method. Background Technology

[0002] As maritime transportation, marine scientific research, and marine resource development activities increasingly extend into the deep blue sea, various emergency, scientific research, and support missions are increasing, raising the probability of shark attacks on underwater workers and personnel who fall into the water from ships and aircraft. Sharks hunt using sight, smell, and hearing, with their sense of smell being the most sensitive, able to detect the slightest scent of blood from several kilometers away. A shark attack can cause extensive and severe tissue damage, even leading to disability or death. Therefore, personnel working at sea need to wear appropriate shark repellent products to ensure the safety of those who have fallen into the water and are awaiting rescue. Depending on the principle of shark repellency, commonly used products include chemical shark repellents and electro-pulse shark repellent devices. Currently, most portable shark repellents used by the military and civilians are chemical shark repellents. While these offer some protection to personnel, they pose a threat to sharks and marine life in the areas where they are used, and can also cause some pollution to the ecological environment. Summary of the Invention

[0003] This invention relates to a marine shark repellent and its preparation method, belonging to the technical field of shark repellent materials. The invention discloses a shark repellent obtained by compounding modified porous silica with microcapsules. Porous silica serves as a carrier, with repellent materials attached to the pores to form modified porous silica; polymethyl methacrylate is used as the wall material, and the repellent materials are encapsulated in microcapsules to obtain microcapsules. The modified porous silica and the repellent materials in the microcapsules are released sequentially in water, giving the shark repellent a long-lasting effect. Multiple repellent materials enhance the shark repellency through both odor blocking and odor repellency. This invention can prepare a pollution-free marine shark repellent with a long-lasting effect and excellent shark repellency.

[0004] The objective of this invention can be achieved through the following technical solutions:

[0005] A marine shark repellent comprises the following raw materials in parts by weight: 50-60 parts modified porous silica, 40-50 parts microcapsules, and 3-5 parts binder.

[0006] Furthermore, the modified porous silica is prepared by heating and mixing the repellent material a, adding porous silica and stirring, and then drying to obtain the modified porous silica.

[0007] Furthermore, the repellent material a is composed of glycerol, methyl nonyl ketone, peppermint oil and santalol in a mass ratio of 1:2:5-6:5-6, and the mass ratio of the repellent material to porous silica is 2-3:1.

[0008] Furthermore, the microcapsules are prepared as follows:

[0009] A: Citric acid is dissolved in deionized water to form the aqueous phase, and the oil phase is a mixture of n-hexadecane, repellent material b, methyl methacrylate, and azobisisobutyronitrile.

[0010] B: The aqueous phase and oil phase are mixed and emulsified at high speed to form a fine emulsion. The mixture is heated and nitrogen gas is introduced. After stirring and reacting, microcapsule emulsion is obtained.

[0011] C: Add the microcapsule emulsion to saturated calcium chloride, filter, wash with anhydrous ethanol to remove excess repellent material b and n-hexadecane, and dry at low temperature to obtain microcapsules.

[0012] Further, in step A, the solid-liquid ratio of citric acid to deionized water is 3-4:10 g / mL, the mass ratio of n-hexadecane, repellent material b, methyl methacrylate, and azobisisobutyronitrile is 7:3:10:0.1, the mass ratio of the aqueous phase to the oil phase is 4:1, and the repellent b is composed of peppermint oil and capsaicin in a mass ratio of 1:1.

[0013] Furthermore, in step B, the high-speed stirring speed and time are 2000 r / min and 20-30 min, respectively; the heating refers to heating to 60-70℃; and the stirring reaction speed and time are 200 r / min and 5-6 h, respectively.

[0014] Furthermore, in step C, the volume ratio of the microcapsule emulsion to saturated calcium chloride is 1:1, and the low-temperature drying temperature is 40-45℃.

[0015] Furthermore, the preparation method of the marine shark repellent is as follows: mix all raw material components, granulate and extrude to obtain the shark repellent.

[0016] Furthermore, the binder is plant-based amylose with a moisture content of 40-55%.

[0017] The beneficial effects of this invention are:

[0018] 1. Modified porous silica is formed by attaching repellent materials to the pores of porous silica as a carrier; microcapsules are obtained by encapsulating the repellent materials in polymethyl methacrylate as the wall material. The repellent materials in the modified porous silica and microcapsules are released sequentially in water, giving the shark repellent its persistence.

[0019] 2. Multiple repellent materials enhance the shark-repelling effect through both odor blocking and odor repellency, while the raw materials are all environmentally friendly and biodegradable, causing no pollution to the environment. Detailed Implementation

[0020] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features and effects of the present invention, in conjunction with embodiments, is provided below.

[0021] Example 1

[0022] A marine shark repellent comprises the following raw materials in parts by weight: 50 parts modified porous silica, 40 parts microcapsules, and 3 parts binder.

[0023] The modified porous silica is prepared by heating and mixing the repellent material a, adding porous silica and stirring, and then drying to obtain the modified porous silica.

[0024] The repellent material a is composed of glycerol, methyl nonyl ketone, peppermint oil and santalol in a mass ratio of 1:2:5:5, and the mass ratio of the repellent material to porous silica is 2:1.

[0025] The microcapsules are prepared as follows:

[0026] A: Citric acid is dissolved in deionized water to form the aqueous phase, and the oil phase is a mixture of n-hexadecane, repellent material b, methyl methacrylate, and azobisisobutyronitrile.

[0027] B: The aqueous phase and oil phase are mixed and emulsified at high speed to form a fine emulsion. The mixture is heated and nitrogen gas is introduced. After stirring and reacting, microcapsule emulsion is obtained.

[0028] C: Add the microcapsule emulsion to saturated calcium chloride, filter, wash with anhydrous ethanol to remove excess repellent material b and n-hexadecane, and dry at low temperature to obtain microcapsules.

[0029] In step A, the solid-liquid ratio of citric acid to deionized water is 3:10 g / mL, the mass ratio of n-hexadecane, repellent material b, methyl methacrylate, and azobisisobutyronitrile is 7:3:10:0.1, the mass ratio of the aqueous phase to the oil phase is 4:1, and the repellent b is composed of peppermint oil and capsaicin in a mass ratio of 1:1.

[0030] The capsaicin was purchased from Jiangsu Enming Biotechnology Co., Ltd. (2444-46-4).

[0031] In step B, the high-speed stirring speed and time are 2000 r / min and 20 min, respectively; the heating refers to heating to 60°C; and the stirring reaction speed and time are 200 r / min and 5 h, respectively.

[0032] In step C, the volume ratio of microcapsule emulsion to saturated calcium chloride is 1:1, and the low-temperature drying temperature is 40°C.

[0033] The preparation method of the marine shark repellent is as follows: mix all raw material components, granulate and extrude to obtain the shark repellent.

[0034] The binder is plant-based amylose with a moisture content of 40%.

[0035] Example 2

[0036] A marine shark repellent comprises the following raw materials in parts by weight: 55 parts modified porous silica, 45 parts microcapsules, and 4 parts binder.

[0037] The modified porous silica is prepared by heating and mixing the repellent material a, adding porous silica and stirring, and then drying to obtain the modified porous silica.

[0038] The repellent material a is composed of glycerol, methyl nonyl ketone, peppermint oil and santalol in a mass ratio of 1:2:5:6, and the mass ratio of the repellent material to porous silica is 3:1.

[0039] The microcapsules are prepared as follows:

[0040] A: Citric acid is dissolved in deionized water to form the aqueous phase, and the oil phase is a mixture of n-hexadecane, repellent material b, methyl methacrylate, and azobisisobutyronitrile.

[0041] B: The aqueous phase and oil phase are mixed and emulsified at high speed to form a fine emulsion. The mixture is heated and nitrogen gas is introduced. After stirring and reacting, microcapsule emulsion is obtained.

[0042] C: Add the microcapsule emulsion to saturated calcium chloride, filter, wash with anhydrous ethanol to remove excess repellent material b and n-hexadecane, and dry at low temperature to obtain microcapsules.

[0043] In step A, the solid-liquid ratio of citric acid to deionized water is 3:1 g / mL, the mass ratio of n-hexadecane, repellent material b, methyl methacrylate, and azobisisobutyronitrile is 7:3:10:0.1, the mass ratio of the aqueous phase to the oil phase is 4:1, and the repellent b is composed of peppermint oil and capsaicin in a mass ratio of 1:1.

[0044] The capsaicin was purchased from Jiangsu Enming Biotechnology Co., Ltd. (2444-46-4).

[0045] In step B, the high-speed stirring speed and time are 2000 r / min and 25 min, respectively; the heating refers to heating to 60°C; and the stirring reaction speed and time are 200 r / min and 5 h, respectively.

[0046] In step C, the volume ratio of microcapsule emulsion to saturated calcium chloride is 1:1, and the low-temperature drying temperature is 45°C.

[0047] The preparation method of the marine shark repellent is as follows: mix all raw material components, granulate and extrude to obtain the shark repellent.

[0048] The binder is plant-based amylose with a moisture content of 50%.

[0049] Example 3

[0050] A marine shark repellent comprises the following raw materials in parts by weight: 60 parts modified porous silica, 50 parts microcapsules, and 5 parts binder.

[0051] The modified porous silica is prepared by heating and mixing the repellent material a, adding porous silica and stirring, and then drying to obtain the modified porous silica.

[0052] The repellent material a is composed of glycerol, methyl nonyl ketone, peppermint oil and santalol in a mass ratio of 1:2:6:6, and the mass ratio of the repellent material to porous silica is 3:1.

[0053] The microcapsules are prepared as follows:

[0054] A: Citric acid is dissolved in deionized water to form the aqueous phase, and the oil phase is a mixture of n-hexadecane, repellent material b, methyl methacrylate, and azobisisobutyronitrile.

[0055] B: The aqueous phase and oil phase are mixed and emulsified at high speed to form a fine emulsion. The mixture is heated and nitrogen gas is introduced. After stirring and reacting, microcapsule emulsion is obtained.

[0056] C: Add the microcapsule emulsion to saturated calcium chloride, filter, wash with anhydrous ethanol to remove excess repellent material b and n-hexadecane, and dry at low temperature to obtain microcapsules.

[0057] In step A, the solid-liquid ratio of citric acid to deionized water is 4:1 g / mL, the mass ratio of n-hexadecane, repellent material b, methyl methacrylate, and azobisisobutyronitrile is 7:3:10:0.1, the mass ratio of the aqueous phase to the oil phase is 4:1, and the repellent b is composed of peppermint oil and capsaicin in a mass ratio of 1:1.

[0058] The capsaicin was purchased from Jiangsu Enming Biotechnology Co., Ltd. (2444-46-4).

[0059] In step B, the high-speed stirring speed and time are 2000 r / min and 30 min, respectively; the heating refers to heating to 70°C; and the stirring reaction speed and time are 200 r / min and 6 h, respectively.

[0060] In step C, the volume ratio of microcapsule emulsion to saturated calcium chloride is 1:1, and the low-temperature drying temperature is 45°C.

[0061] The preparation method of the marine shark repellent is as follows: mix all raw material components, granulate and extrude to obtain the shark repellent.

[0062] The binder is plant-based amylose with a moisture content of 55%.

[0063] Comparative Example 1

[0064] Based on Example 2, a marine shark repellent agent is provided, which comprises the following raw materials in parts by weight: 55 parts of repellent material a, 45 parts of microcapsules, and 4 parts of binder.

[0065] The repellent material a is composed of glycerol, methyl nonyl ketone, peppermint oil and santalol in a mass ratio of 1:2:5:6.

[0066] The microcapsules are prepared as follows:

[0067] A: Citric acid is dissolved in deionized water to form the aqueous phase, and the oil phase is a mixture of n-hexadecane, repellent material b, methyl methacrylate, and azobisisobutyronitrile.

[0068] B: The aqueous phase and oil phase are mixed and emulsified at high speed to form a fine emulsion. The mixture is heated and nitrogen gas is introduced. After stirring and reacting, microcapsule emulsion is obtained.

[0069] C: Add the microcapsule emulsion to saturated calcium chloride, filter, wash with anhydrous ethanol to remove excess repellent material b and n-hexadecane, and dry at low temperature to obtain microcapsules.

[0070] In step A, the solid-liquid ratio of citric acid to deionized water is 3:1 g / mL, the mass ratio of n-hexadecane, repellent material b, methyl methacrylate, and azobisisobutyronitrile is 7:3:10:0.1, the mass ratio of the aqueous phase to the oil phase is 4:1, and the repellent b is composed of peppermint oil and capsaicin in a mass ratio of 1:1.

[0071] The capsaicin was purchased from Jiangsu Enming Biotechnology Co., Ltd. (2444-46-4).

[0072] In step B, the high-speed stirring speed and time are 2000 r / min and 25 min, respectively; the heating refers to heating to 60°C; and the stirring reaction speed and time are 200 r / min and 5 h, respectively.

[0073] In step C, the volume ratio of microcapsule emulsion to saturated calcium chloride is 1:1, and the low-temperature drying temperature is 45°C.

[0074] The preparation method of the marine shark repellent is as follows: mix all raw material components, granulate and extrude to obtain the shark repellent.

[0075] The binder is plant-based amylose with a moisture content of 50%.

[0076] Comparative Example 2

[0077] Based on Example 2, a marine shark repellent agent is provided, which comprises the following raw materials in parts by weight: 100 parts of modified porous silica and 4 parts of binder.

[0078] The modified porous silica is prepared by heating and mixing the repellent material a, adding porous silica and stirring, and then drying to obtain the modified porous silica.

[0079] The repellent material a is composed of glycerol, methyl nonyl ketone, peppermint oil and santalol in a mass ratio of 1:2:5:6, and the mass ratio of the repellent material to porous silica is 3:1.

[0080] The preparation method of the marine shark repellent is as follows: mix all raw material components, granulate and extrude to obtain the shark repellent.

[0081] The binder is plant-based amylose with a moisture content of 50%.

[0082] Comparative Example 3

[0083] Based on Example 2, the methyl nonyl ketone in the repellent material a was removed and replaced with an equal mass of peppermint oil, while other conditions remained the same as in Example 2.

[0084] Comparative Example 4

[0085] Based on Example 2, the peppermint oil in the repellent material a was removed and replaced with an equal mass of methyl nonyl ketone, while other conditions remained the same as in Example 2.

[0086] Comparative Example 5

[0087] Based on Example 2, the santalol in the repellent material a was removed and replaced with an equal mass of peppermint oil, while other conditions remained the same as in Example 2.

[0088] Comparative Example 6

[0089] Based on Example 2, a marine shark repellent agent is provided, which comprises the following raw materials in parts by weight: 55 parts modified porous silica, 45 parts microcapsules, and 4 parts binder.

[0090] The modified porous silica is prepared by heating and mixing the repellent material a, adding porous silica and stirring, and then drying to obtain the modified porous silica.

[0091] The repellent material a is composed of glycerol, methyl nonyl ketone, peppermint oil and santalol in a mass ratio of 1:2:5:6, and the mass ratio of the repellent material to porous silica is 3:1.

[0092] The microcapsules are prepared as follows:

[0093] A: Citric acid is dissolved in deionized water to form the aqueous phase, and the oil phase is a mixture of n-hexadecane, repellent material b, methyl methacrylate, and azobisisobutyronitrile.

[0094] B: The aqueous phase and oil phase are mixed and emulsified at high speed to form a fine emulsion. The mixture is heated and nitrogen gas is introduced. After stirring and reacting, microcapsule emulsion is obtained.

[0095] C: Add the microcapsule emulsion to saturated calcium chloride, filter, wash with anhydrous ethanol to remove excess repellent material b and n-hexadecane, and dry at low temperature to obtain microcapsules.

[0096] In step A, the solid-liquid ratio of citric acid to deionized water is 3:1 g / mL, the mass ratio of n-hexadecane, repellent material b, methyl methacrylate, and azobisisobutyronitrile is 7:3:10:0.1, the mass ratio of the aqueous phase to the oil phase is 4:1, and the repellent agent b is capsaicin.

[0097] The capsaicin was purchased from Jiangsu Enming Biotechnology Co., Ltd. (2444-46-4).

[0098] In step B, the high-speed stirring speed and time are 2000 r / min and 25 min, respectively; the heating refers to heating to 60°C; and the stirring reaction speed and time are 200 r / min and 5 h, respectively.

[0099] In step C, the volume ratio of microcapsule emulsion to saturated calcium chloride is 1:1, and the low-temperature drying temperature is 45°C.

[0100] The preparation method of the marine shark repellent is as follows: mix all raw material components, granulate and extrude to obtain the shark repellent.

[0101] The binder is plant-based amylose with a moisture content of 50%.

[0102] Comparative Example 7

[0103] Based on Example 2, a marine shark repellent agent is provided, which comprises the following raw materials in parts by weight: 55 parts modified porous silica, 45 parts microcapsules, and 4 parts binder.

[0104] The modified porous silica is prepared by heating and mixing the repellent material a, adding porous silica and stirring, and then drying to obtain the modified porous silica.

[0105] The repellent material a is composed of glycerol, methyl nonyl ketone, peppermint oil and santalol in a mass ratio of 1:2:5:6, and the mass ratio of the repellent material to porous silica is 3:1.

[0106] The microcapsules are prepared as follows:

[0107] A: Citric acid is dissolved in deionized water to form the aqueous phase, and the oil phase is a mixture of n-hexadecane, repellent material b, methyl methacrylate, and azobisisobutyronitrile.

[0108] B: The aqueous phase and oil phase are mixed and emulsified at high speed to form a fine emulsion. The mixture is heated and nitrogen gas is introduced. After stirring and reacting, microcapsule emulsion is obtained.

[0109] C: Add the microcapsule emulsion to saturated calcium chloride, filter, wash with anhydrous ethanol to remove excess repellent material b and n-hexadecane, and dry at low temperature to obtain microcapsules.

[0110] In step A, the solid-liquid ratio of citric acid to deionized water is 3:1 g / mL, the mass ratio of n-hexadecane, repellent material b, methyl methacrylate, and azobisisobutyronitrile is 7:3:10:0.1, the mass ratio of the aqueous phase to the oil phase is 4:1, and the repellent agent b is peppermint essential oil.

[0111] In step B, the high-speed stirring speed and time are 2000 r / min and 25 min, respectively; the heating refers to heating to 60°C; and the stirring reaction speed and time are 200 r / min and 5 h, respectively.

[0112] In step C, the volume ratio of microcapsule emulsion to saturated calcium chloride is 1:1, and the low-temperature drying temperature is 45°C.

[0113] The preparation method of the marine shark repellent is as follows: mix all raw material components, granulate and extrude to obtain the shark repellent.

[0114] The binder is plant-based amylose with a moisture content of 50%.

[0115] 1. Performance Testing

[0116] Three representative marine aquaculture fish species—flounder, scorpionfish, and spotted seabream—were selected as research subjects. The selection criteria were: flounder is a representative species of benthic fish, scorpionfish a representative species of swimming fish, and spotted seabream a representative species of tropical fish. Healthy and vigorous juvenile fish were selected. Flounder and scorpionfish were purchased from Qingdao Beibao Marine Technology Co., Ltd. in Shandong Province, and spotted seabream from Laizhou Mingbo Aquatic Products Co., Ltd. in Shandong Province. The average sizes of the flounder, scorpionfish, and spotted seabream used in the experiment were (125.32±2.38), (95.62±6.24), and (146.42±5.87) g / fish, respectively. After purchase, the juveniles were transported to the aquarium laboratory and temporarily held for 7 days. A circular tank with a diameter of 2 m and a depth of 1.5 m was used for both temporary holding and the experiment, with continuous aeration. The fish were used in the experiment after their condition stabilized. The shark repellents prepared in Examples 1-3 and Comparative Examples 1-7 were subjected to vitality and toxicity tests on three representative marine aquaculture fish species. Specifically: For the vitality test, six fish of each species were placed in a tank, and 100g of shark repellent was added to one end of the tank. The vitality of the fish was observed at 0h, 0.5h, and 24h. After the toxicity test, the experimental fish were dissected, and gills, liver, spleen, heart, and other organs were removed and cut into 1cm pieces. 3 Small pieces were fixed in Davidson's fixative for 24 hours, then the fixative was replaced with 70% anhydrous ethanol. The samples were then dehydrated in anhydrous ethanol gradients, cleared with xylene, embedded in paraffin, sectioned (5 μm), stained with hematoxylin and eosin (HE), and mounted with neutral resin. The samples were then observed and photographed under a microscope to analyze the toxic effects of the shark repellent on the tissues and organs of three marine fish species. The test results are shown in Table 1.

[0117] Table 1 Test Results

[0118]

[0119]

[0120] As shown in Table 1, all indicators of toxicity testing in Examples 1-3 and Comparative Examples 1-7 were normal. In Examples 1-3, the activity of the three types of fish initially decreased, and after half an hour, they experienced difficulty breathing and surfaced. After 24 hours, they developed eye congestion. In Comparative Example 1, no porous silica was used to load repellent a; repellent a was directly added to the water. The fish quickly sensed it and surfaced, but after 24 hours, they developed eye congestion and sank to the bottom. In Comparative Example 2, no microcapsules were used, and the activity of the fish recovered somewhat after 24 hours. In Comparative Examples 3-7, removing any component from the repellent resulted in minimal impact on the activity of the fish after 24 hours. Therefore, the shark repellent prepared in this invention has long-lasting properties. The multiple repellent materials enhance the shark repellency effect through both odor shielding and odor repellency. Furthermore, the raw materials are all environmentally friendly and biodegradable, causing no pollution to the environment.

[0121] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A marine shark repellent, characterized in that, The marine shark repellent comprises the following raw materials in parts by weight: 50-60 parts modified porous silica, 40-50 parts microcapsules, and 3-5 parts binder; The modified porous silica is prepared by heating and mixing the repellent material a, adding porous silica and stirring, and then drying to obtain the modified porous silica. The microcapsules are prepared as follows: A: Citric acid is dissolved in deionized water to form the aqueous phase, and the oil phase is a mixture of n-hexadecane, repellent material b, methyl methacrylate, and azobisisobutyronitrile. B: The aqueous phase and oil phase are mixed and emulsified at high speed to form a fine emulsion. The mixture is heated and nitrogen gas is introduced. After stirring and reacting, microcapsule emulsion is obtained. C: Add the microcapsule emulsion to saturated calcium chloride, filter, wash with anhydrous ethanol to remove excess repellent material b and n-hexadecane, and dry at low temperature to obtain microcapsules; The binder is plant-based amylose with a moisture content of 40-55%; The repellent material a is composed of glycerol, methyl nonyl ketone, peppermint oil and santalol in a mass ratio of 1:2:5-6:5-6, and the mass ratio of the repellent material a to porous silica is 2-3:

1. In step A, the solid-liquid ratio of citric acid to deionized water is 3-4 g / mL, the mass ratio of n-hexadecane, repellent material b, methyl methacrylate, and azobisisobutyronitrile is 7:3:10:0.1, the mass ratio of the aqueous phase to the oil phase is 4:1, and the repellent b is composed of peppermint oil and capsaicin in a mass ratio of 1:

1. In step B, the high-speed stirring speed and time are 2000 r / min and 20-30 min, respectively; the heating refers to heating to 60-70℃; and the stirring reaction speed and time are 200 r / min and 5-6 h, respectively. In step C, the volume ratio of microcapsule emulsion to saturated calcium chloride is 1:1, and the low-temperature drying temperature is 40-45℃.

Images