Preparation Of Micro/Nano Copper Peroxide And Its Application In Antibacterial And Antifouling Coating Fields

Metal peroxides（MP）are composed of metal ions and peroxy radical(O₂^2-),which an produce metal ions and hydroxyl radicals（·OH）with high oxidation activity under weak acidic conditions.Copper peroxide（CuO₂）,as a metal peroxide,has played an important role in biomedicine field in recent years.CuO₂ will produce·OH under weak acid conditions.·OH can cause oxidative stress of bacteria and tumors in the biological environment and thus apoptosis through its high oxidation activity.Therefore,CuO₂has potential antibacterial and antitumor advantages.In this essay,based on the chemical structure characteristics of CuO₂,we design and explore the research of CuO₂ in the fields of antibacterial and antifouling coating,introduce CuO₂ into different kinds of resin coating,prepare marine antifouling coating and indoor antibacterial coating.The specific contents are as follows:（1）A novel self-activated marine antifouling coating based on self-polishing zinc-methacrylate containing CuO₂.Marine biological fouling is the biological fouling formed by the adsorption,growth and reproduction of marine microorganisms,plants and animals on the surface immersed in seawater.The core component of antifouling coating is antifouling agent.After nearly a century of development,Cu₂O antifouling agent was the most mature and widely used at home and abroad.This kind of antifouling coating introduced large amounts of Cu²⁺into the ocean and cause great damage to marine ecology.In this work,a novel self-activated marine antifouling coating was constructed by preparing Flake-shaped-CuO₂,Line-shaped-CuO₂ and Sphere-shaped-CuO₂,and introducing them into self-polishing zinc-methacrylate resin.When marine microorganisms attach to the coating and form a protective biofilm,the weak acidic environment of the biofilm stimulates CuO₂ particles to produce Cu²⁺and H₂O₂.CuO₂further catalyzes H₂O₂ to produce·OH.The highly toxic·OH and Cu²⁺destroy the biofilm produced by microorganisms through synergistic antibacterial action,preventing further formation of marine fouling.The biotoxicity of Cu²⁺and·OH also makes it difficult for contaminated organisms to survive and multiply in the ocean.When the CuO₂ particles on the surface of the coating are consumed,the self-polishing zinc-methacrylate resin will self-degrade under the shear stress of seawater in order to ensure that CuO₂ particles could be exposed form zinc-methacrylate.In this work,we carried out research and development of micro/nano CuO₂ as well as the preparation of self-activated marine antifouling coating.The antibacterial performance of coating,algae inhibition performance,marine field antifouling performance,Cu²⁺release rate was characterized.The results showed that the antibacterial performance of the self-activated marine antifouling coating remained stable for a long time,and the algal inhibition performance of the coating could reach more than 50%within five days.The release concentration of Cu²⁺of Sphere-shaped-CuO₂,Line-shaped-CuO₂ and Flake-shaped-CuO₂ self-activated marine antifouling coating reaches 1.6 mg/L,1.7 mg/L and18.4 mg/L within 16 days,respectively.The marine field test of Sphere-shaped-CuO₂and Flake-shaped-CuO₂ self-activated marine antifouling coating can achieve 300 days antifouling performance.In this work,a novel self-activated marine antifouling coating containing CuO₂ as the main antifouling agent is used to provide a marine antifouling strategy of reactive oxygen species（ROS）-metal ions synergistically for marine antifouling.（2）Reactivatable indoor antibacterial coating based on graphene oxide（GO）loaded with CuO₂.In the indoor closed environment of cruise ships,submarines,warships and other maritime ships,the protection of bacteria and microorganisms is particularly important.Human exhalation will carry a large number of microorganisms,which is easy to cause cross infection in a narrow environment.Therefore,indoor antibacterial coating is an important strategy and effective means to prevent the spread of bacteria and microorganisms.In this work,a reactivated indoor antibacterial coating（S/L-CuO₂-GO-PAE-PU）based on GO loaded CuO₂ was designed.S/L-CuO₂-GO-PAE-PU antibacterial coating was prepared by loading CuO₂ on GO surface and introduced polyaspartic ester polyurea（PAE-PU）resin.The main components of human exhalation are CO₂ and H₂O.CO₂ dissolves in water to form carbonic acid,which presents weak acidity.Meanwhile,human sweat also presents weak acidity.When human sweat touches indoor antibacterial coating,or human breath carrying bacteria touches antibacterial coating,CuO₂ on the surface of coating can produce Cu²⁺and ROS under the condition of weak acid,carrying out synergic antibacterial effect.However,with the consumption of CuO₂,its antibacterial properties will decrease or even become ineffective.In this work,CuO₂ is loaded on GO surface and introduced into PAE-PU resin.When CuO₂ is decomposed,ROS and Cu²⁺will be produced.Cu²⁺has weak antibacterial property,but Cu²⁺can be combined with GO through"cation-π"effect,and the resulting GO-Cu²⁺has excellent antibacterial property.The results showed that the bioaerosol antibacterial properties of S/L-CuO₂-GO-PAE-PU reached 90%and 80%,respectively.This work provides a novel idea for the development of long-lasting and environmental-friendly intelligent antibacterial coating.