High radiation resistance antibacterial organic glass and preparation method thereof

Abstract

This invention discloses a high-radiation-shielding and antibacterial plexiglass and its preparation method. The steps are as follows: methyl methacrylate, modified nano-tantalum oxide, organic lead salt, superdispersant, and antibacterial agent are added to a reaction vessel, heated and stirred to dissolve, and then an initiator is added. After high-temperature prepolymerization, low-temperature polymerization, and high-temperature post-treatment, the high-radiation-shielding and antibacterial plexiglass is obtained. Compared with the prior art, the high-radiation-shielding and antibacterial plexiglass prepared by this invention has high strength and good toughness. The plexiglass contains both tantalum and lead, and antibacterial materials are introduced to compensate for the defect of "weak absorption region of Pb", which has a good shielding effect against X-rays and strong antibacterial properties.

Description

Technical Field

[0001] This invention relates to the field of radiation-resistant acrylic glass technology, and in particular to a high radiation-resistant and antibacterial acrylic glass and its preparation method. Background Technology

[0002] With the rapid development of modern science and technology, various high-energy rays are increasingly widely used in military, communications, medicine, industry, agriculture, and daily life. However, while bringing convenience and enjoyment, these rays also pose certain harms to humanity, and are widely recognized as the fourth major public hazard after air pollution, water pollution, and noise pollution. Electromagnetic radiation is a major contributing factor to cardiovascular disease, diabetes, and cancer mutations, directly affecting children's tissue and bone development, leading to decreased vision and reduced liver hematopoietic function. Frequent exposure to radioactive rays can cause skin burns, hair loss, eye pain, decreased white blood cell count, and even multiple myeloma. Therefore, research into radiation protection materials is receiving increasing attention.

[0003] Current research indicates that lead-containing acrylic glass offers the best radiation protection performance and is therefore the most widely used. However, lead-containing acrylic glass has a "weak absorption region for Pb," resulting in less than ideal protection against ionizing radiation with X-ray peak tube voltages between 40.0 and 88.0 keV. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a high-radiation-shielding and antibacterial plexiglass and its preparation method. This plexiglass has high strength and good toughness, contains both tantalum and lead, and incorporates antibacterial materials to compensate for the deficiency in the "weak absorption region of Pb," thus exhibiting good shielding effect against X-rays and strong antibacterial effect.

[0005] To achieve this technical objective, the present invention adopts the following solution:

[0006] A method for preparing high radiation-resistant and antibacterial plexiglass includes the following steps:

[0007] S1. Weigh out 60-80 Wt.% methyl methacrylate, 1-10 Wt.% modified nano tantalum oxide, 10-30 Wt.% organic lead salt, 0.1-1 Wt.% superdispersant and 0.1-1 Wt.% antibacterial agent respectively, add them to the reaction vessel, and heat and stir until each substance is dissolved;

[0008] S2. Add an initiator to the reactor, heat the reactor, and carry out a prepolymerization reaction in the reactor;

[0009] S3. After vacuum degassing of the product in step S2, inject it into the mold and place the mold in the drying room.

[0010] S4. Increase the temperature of the drying oven to carry out the polymerization reaction, and then perform high-temperature post-treatment after the polymerization reaction.

[0011] S5. Cool the product from step S4 to room temperature and demold to obtain high radiation protection and antibacterial plexiglass.

[0012] Furthermore, the modified nano tantalum oxide is prepared by slowly pouring the coupling agent into an acetone solution at room temperature, adding nano tantalum oxide, and then drying the mixture at 65°C for 60 hours after thorough mechanical stirring to obtain the modified nano tantalum oxide.

[0013] Furthermore, the volume ratio of the coupling agent to acetone is 1:5~8.

[0014] Furthermore, the preparation method of nano tantalum oxide is as follows: tantalum ethoxide and toluene are mixed in a mass ratio of 1:4~8 and placed in a hydrothermal reactor containing deionized water. The mixture is heated to 240°C, maintained for 24 hours, and then cooled. After washing three times with deionized water and ethanol respectively, the mixture is dried under vacuum at 50°C for 48 hours to obtain nano tantalum oxide.

[0015] Furthermore, the coupling agent is one or both of silane coupling agent KH-570 or silane coupling agent Z-6011.

[0016] Furthermore, the organic lead salt is at least one of lead methacrylate, lead acrylate, and lead octanoate.

[0017] Furthermore, the superdispersant is a polyacrylate type superdispersant, more specifically, the superdispersant is UNIQSPERSE615S; the antibacterial agent is a nano-silver antibacterial agent.

[0018] Furthermore, the initiator is one of azobisisobutyronitrile (AIBN) or dilauryl peroxide (LPO), and the amount of the initiator accounts for 0.01 to 0.30 wt. of the total reaction system.

[0019] Furthermore, in step S2, the prepolymerization reaction temperature is 70±5℃, and the reaction time is 15~20min.

[0020] The vacuum degassing time in step S3 is 20~30 min;

[0021] In step S4, the polymerization reaction temperature is 50±5℃ and the reaction time is 12±0.5h;

[0022] In step S4, the high-temperature post-treatment process involves maintaining the temperature at 80±5℃ for 3±0.5h, and then raising the temperature to 110±5℃ and maintaining it for 2±0.5h.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] (1) The high radiation protection and antibacterial organic glass prepared by the present invention makes up for the defect of “weak absorption region of Pb”, has a good shielding effect on X-rays, and can play a comprehensive protection role.

[0025] (2) The high radiation protection and antibacterial organic glass prepared by the present invention exhibits high strength and toughness and has good mechanical properties.

[0026] (3) The high radiation protection and antibacterial organic glass prepared by the present invention has an antibacterial rate of over 90% and has a strong antibacterial effect. Attached Figure Description

[0027] Figure 1 The X-ray shielding efficiency of high radiation-proof and antibacterial plexiglass prepared with different contents of tantalum oxide according to the present invention. Detailed Implementation

[0028] To fully understand the purpose, features and effects of the present invention, the present invention will be described in detail through the following specific embodiments, but the present invention is not limited thereto.

[0029] First, nano-tantalum oxide was prepared: 10g of tantalum ethoxide and 45g of toluene were mixed and placed in a hydrothermal reactor containing 900ml of deionized water. The mixture was heated to 240℃ and maintained for 24h. After cooling, the mixture was washed three times with deionized water and ethanol, and then dried under vacuum at 50℃ for 48h to obtain nano-tantalum oxide.

[0030] Preparation of modified nano tantalum oxide: At room temperature, 10 ml of coupling agent was slowly poured into 60 ml of acetone solution, 5 g of nano tantalum oxide was added, and the mixture was thoroughly stirred mechanically and then dried at 65 °C for 60 h to obtain modified nano tantalum oxide. Example 1

[0031] Weigh out 71.8 wt.% distilled methyl methacrylate (MMA), 2.0 wt.% modified nano tantalum oxide (Ta2O5), 25 wt.% lead methacrylate (Pb(MA)2), 1.0 wt.% antibacterial agent, and 0.1 wt.% polyacrylate-type superdispersant (UNIQSPERSE 615S), place them in a reactor, heat and stir, add 0.1 wt.% azobisisobutyronitrile (AIBN), prepolymerize at 70℃ for 20 min, cool to 30℃ and degas under vacuum for 30 min, filter, and pour into molds. Then place the mold in an oven and polymerize at 50℃ for 12 h, followed by high-temperature post-treatment at 80℃ for 3 h and 110℃ for 2 h, then allow to cool naturally and demold to obtain high-radiation-resistant and antibacterial acrylic glass. Example 2

[0032] Weigh out 69.8 wt.% distilled methyl methacrylate (MMA), 4.0 wt.% modified nano tantalum oxide (Ta2O5), 25 wt.% lead methacrylate (Pb(MA)2), 1.0 wt.% antibacterial agent, and 0.1 wt.% polyacrylate-type superdispersant (UNIQSPERSE 615S), place them in a reactor, heat and stir, add 0.1 wt.% azobisisobutyronitrile (AIBN), prepolymerize at 70℃ for 20 min, cool to 30℃ and degas under vacuum for 30 min, filter, and pour into molds. Then place the mold in an oven for low-temperature polymerization at 50℃ for 12 h, followed by high-temperature post-treatment at 80℃ for 3 h and 110℃ for 2 h, then allow to cool naturally and demold to obtain high-radiation-resistant and antibacterial acrylic glass. Example 3

[0033] Weigh out 64.8 wt.% distilled methyl methacrylate (MMA), 4.0 wt.% modified nano tantalum oxide (Ta2O5), 30 wt.% lead methacrylate (Pb(MA)2), 1.0 wt.% antibacterial agent, and 0.1 wt.% polyacrylate-type superdispersant (UNIQSPERSE 615S), place them in a reactor, heat and stir, add 0.1 wt.% azobisisobutyronitrile (AIBN), prepolymerize at 70℃ for 20 min, cool to 30℃ and degas under vacuum for 30 min, filter, and pour into molds. Then place the mold in an oven for low-temperature polymerization at 50℃ for 12 h, followed by high-temperature post-treatment at 80℃ for 3 h and 110℃ for 2 h, then allow to cool naturally and demold to obtain high-radiation-resistant and antibacterial acrylic glass. Example 4

[0034] Weigh out 67.8 wt.% distilled methyl methacrylate (MMA), 6.0 wt.% modified nano tantalum oxide (Ta2O5), 25 wt.% lead methacrylate (Pb(MA)2), 1.0 wt.% antibacterial agent, and 0.1 wt.% polyacrylate-type superdispersant (UNIQSPERSE 615S), place them in a reactor, heat and stir, add 0.1 wt.% azobisisobutyronitrile (AIBN), prepolymerize at 70℃ for 20 min, cool to 30℃ and degas under vacuum for 30 min, filter, and pour into molds. Then place the mold in an oven for low-temperature polymerization at 50℃ for 12 h, followed by high-temperature post-treatment at 80℃ for 3 h and 110℃ for 2 h, then allow to cool naturally and demold to obtain high-radiation-resistant and antibacterial acrylic glass. Example 5

[0035] Weigh out 65.8 wt.% distilled methyl methacrylate (MMA), 8.0 wt.% modified nano tantalum oxide (Ta2O5), 25 wt.% lead methacrylate (Pb(MA)2), 1.0 wt.% antibacterial agent, and 0.1 wt.% polyacrylate-type superdispersant (UNIQSPERSE 615S), place them in a reactor, heat and stir, add 0.1 wt.% azobisisobutyronitrile (AIBN), prepolymerize at 70℃ for 20 min, cool to 30℃ and degas under vacuum for 30 min, filter, and pour into a mold. Then place the mold in an oven for low-temperature polymerization at 50℃ for 12 h, followed by high-temperature post-treatment at 80℃ for 3 h and 110℃ for 2 h, then allow to cool naturally and demold to obtain high-radiation-resistant and antibacterial acrylic glass. Example 6

[0036] Weigh out 76.7 wt.% distilled methyl methacrylate (MMA), 2.0 wt.% modified nano tantalum oxide (Ta2O5), 10 wt.% lead methacrylate, 10 wt.% lead acrylate, 0.1 wt.% antibacterial agent, and 1 wt.% polyacrylate-type superdispersant (UNIQSPERSE 615S), place them in a reactor, heat and stir, add 0.2 wt.% dilauryl peroxide (LPO), prepolymerize at 70℃ for 20 min, cool to 30℃ and degas under vacuum for 30 min, filter, and pour into molds. Then place the mold in an oven for low-temperature polymerization at 50℃ for 12 h, followed by high-temperature post-treatment at 80℃ for 3 h and 110℃ for 2 h, allow to cool naturally, and demold to obtain high-radiation-resistant and antibacterial acrylic glass. Example 7

[0037] Weigh out 78.8 wt.% distilled methyl methacrylate (MMA), 4.0 wt.% modified nano tantalum oxide (Ta2O5), 8 wt.% lead acrylate, 8 wt.% lead octanoate, 0.5 wt.% antibacterial agent, and 0.5 wt.% polyacrylate-type superdispersant (UNIQSPERSE 615S), place them in a reactor, heat and stir, add 0.2 wt.% dilauryl peroxide (LPO), prepolymerize at 70℃ for 20 min, cool to 30℃ and degas under vacuum for 30 min, filter, and pour into molds. Then place the mold in an oven and polymerize at 50℃ for 12 h, followed by post-treatment at 80℃ for 3 h and 110℃ for 2 h, then allow to cool naturally and demold to obtain high radiation-resistant and antibacterial acrylic glass. Example 8

[0038] Weigh out 62.8 wt.% distilled methyl methacrylate (MMA), 11.0 wt.% modified nano tantalum oxide (Ta2O5), 25 wt.% lead methacrylate (Pb(MA)2), 1.0 wt.% antibacterial agent, and 0.1 wt.% polyacrylate-type superdispersant (UNIQSPERSE 615S), place them in a reactor, heat and stir, add 0.1 wt.% azobisisobutyronitrile (AIBN), prepolymerize at 70℃ for 20 min, cool to 30℃ and degas under vacuum for 30 min, filter, and pour into molds. Then place the mold in an oven for low-temperature polymerization at 50℃ for 12 h, followed by high-temperature post-treatment at 80℃ for 3 h and 110℃ for 2 h, then allow to cool naturally and demold to obtain high-radiation-resistant and antibacterial acrylic glass. Comparative Example 1

[0039] Weigh 69.9 wt.% distilled methyl methacrylate (MMA) and 30 wt.% lead methacrylate (Pb(MA)2), place them in a reactor, heat and stir. Add 0.1 wt.% azobisisobutyronitrile (AIBN), prepolymerize at 70℃ for 20 min, then cool to 30℃ and degas under vacuum for 30 min. Filter and pour into molds. Then place the mold in an oven for low-temperature polymerization at 50℃ for 12 h, followed by high-temperature post-treatment at 80℃ for 3 h and 110℃ for 2 h. After natural cooling and demolding, the final product is radiation-shielding acrylic glass. Comparative Example 2

[0040] Weigh out 66.8 wt.% distilled methyl methacrylate (MMA), 8.0 wt.% modified nano tantalum oxide (Ta2O5), 25 wt.% lead methacrylate (Pb(MA)2), and 0.1 wt.% polyacrylate-type superdispersant (UNIQSPERSE 615S), place them in a reactor, heat and stir, add 0.1 wt.% azobisisobutyronitrile (AIBN), prepolymerize at 70℃ for 20 min, then cool to 30℃ and degas under vacuum for 30 min, filter, and pour into molds. Then place the mold in an oven for low-temperature polymerization at 50℃ for 12 h, followed by high-temperature post-treatment at 80℃ for 3 h and 110℃ for 2 h, then allow to cool naturally and demold to obtain high-radiation-resistant acrylic glass. Comparative Example 3

[0041] Weigh out 73.8 wt.% distilled methyl methacrylate (MMA), 25 wt.% lead methacrylate (Pb(MA)2), 1.0 wt.% antibacterial agent, and 0.1 wt.% polyacrylate-type superdispersant (UNIQSPERSE 615S), place them in a reactor, heat and stir, add 0.1 wt.% azobisisobutyronitrile (AIBN), prepolymerize at 70℃ for 20 min, then cool to 30℃ and degas under vacuum for 30 min, filter, and pour into molds. Then place the mold in an oven for low-temperature polymerization at 50℃ for 12 h, followed by high-temperature post-treatment at 80℃ for 3 h and 110℃ for 2 h, then allow to cool naturally and demold to obtain high-radiation-resistant and antibacterial acrylic glass.

[0042] The performance of the plexiglass obtained in each embodiment and the comparative example was tested, and the test results are shown in Table 1.

[0043] The shielding rate test was conducted according to GBZT 147-2002 Test of Attenuation Performance of X-ray Protective Materials; the test conditions were: X-ray tube voltage of 80KV and total filtration of 0.25mmAl.

[0044] The antibacterial rate test was conducted according to ISO 22196-2011, the standard for testing antimicrobial properties of plastic products; the test strain was Escherichia coli.

[0045]

[0046] The above experimental results show that tantalum oxide can compensate for the defect of "weak absorption region of Pb" in lead-based radiation shielding acrylic glass. At the same time, acrylic glass containing lead and tantalum has a good shielding effect and can play a high protective role. In addition, with the addition of antibacterial agents, the acrylic glass of the present invention has strong antibacterial properties. Figure 1 The X-ray shielding efficiency of high radiation-shielding and antibacterial plexiglass prepared with different contents of tantalum oxide in Examples 1, 2, 4, 5 and Comparative Example 3 is shown. Figure 1 It can be seen that the X-ray shielding efficiency of plexiglass increases with the increase of tantalum oxide content.

[0047] Finally, it should be noted that the above-listed embodiments are merely preferred embodiments of the present invention. Of course, those skilled in the art can make modifications and variations to the present invention. If such modifications and variations fall within the scope of the claims of the present invention and their equivalents, they should be considered as being within the protection scope of the present invention.

Claims

1. A method for preparing high-radiation-resistant and antibacterial plexiglass, characterized in that, Includes the following steps: S1. Weigh out 60-80 Wt.% methyl methacrylate, 1-10 Wt.% modified nano tantalum oxide, 10-30 Wt.% organic lead salt, 0.1-1 Wt.% superdispersant and 0.1-1 Wt.% antibacterial agent respectively, add them to the reaction vessel, and heat and stir until each substance is dissolved; S2. Add an initiator to the reactor, heat the reactor, and carry out a prepolymerization reaction in the reactor; S3. After vacuum degassing of the product in step S2, inject it into the mold and place the mold in the drying room. S4. Increase the temperature of the drying oven to carry out the polymerization reaction, and then perform high-temperature post-treatment after the polymerization reaction. S5. Cool the product from step S4 to room temperature and demold to obtain high radiation protection and antibacterial plexiglass.

2. The method for preparing high radiation-resistant and antibacterial plexiglass according to claim 1, characterized in that, The modified nano tantalum oxide was prepared by slowly pouring the coupling agent into an acetone solution at room temperature, adding nano tantalum oxide, and then drying the mixture at 65°C for 60 hours after thorough mechanical stirring to obtain the modified nano tantalum oxide.

3. The method for preparing high radiation-resistant and antibacterial plexiglass according to claim 2, characterized in that, The volume ratio of coupling agent to acetone is 1:5~8.

4. The method for preparing high radiation-resistant and antibacterial plexiglass according to claim 2, characterized in that, The preparation method of nano tantalum oxide is as follows: tantalum ethoxide and toluene are mixed and placed in a hydrothermal reactor containing deionized water, heated to 240°C, maintained for 24 hours and then cooled. After washing three times with deionized water and ethanol respectively, it is dried under vacuum at 50°C for 48 hours to obtain nano tantalum oxide. The mass ratio of tantalum ethoxide to toluene is 1:4~8.

5. The method for preparing high radiation-resistant and antibacterial plexiglass according to claim 2, characterized in that, The coupling agent is one or both of silane coupling agent KH-570 or silane coupling agent Z-6011.

6. The method for preparing high radiation-resistant and antibacterial plexiglass according to claim 1, characterized in that, The organic lead salt is at least one of lead methacrylate, lead acrylate, and lead octanoate.

7. The method for preparing high radiation-resistant and antibacterial plexiglass according to claim 1, characterized in that, The superdispersant is a polyacrylate-based superdispersant; the antibacterial agent is a nano-silver antibacterial agent.

8. The method for preparing high radiation-resistant and antibacterial plexiglass according to claim 1, characterized in that, The initiator is one of azobisisobutyronitrile or dilauryl peroxide, and the amount of initiator accounts for 0.01 to 0.30 wt. of the total reaction system.

9. The method for preparing high radiation-resistant and antibacterial plexiglass according to claim 1, characterized in that, In step S2, the prepolymerization reaction temperature is 70±5℃, and the reaction time is 15~20min. The vacuum degassing time in step S3 is 20~30 min; In step S4, the polymerization reaction temperature is 50±5℃ and the reaction time is 12±0.5h; In step S4, the high-temperature post-treatment process involves maintaining the temperature at 80±5℃ for 3±0.5h, and then raising the temperature to 110±5℃ and maintaining it for 2±0.5h.

10. High radiation protection and antibacterial plexiglass prepared by the method according to any one of claims 1 to 8.

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