Copper oxide and cuprous oxide belong to traditional mineral-derived pesticides, which have the functions of killing insects, sterilizing, fertilizer, wood preserving, and regulating plant growth in the field of pesticides. Although copper has a long history as a fungicide and insecticide in the field of pesticides, traditional inorganic copper oxide has a series of problems such as slow absorption and poor effect. At this stage, the research on copper mainly focuses on nano-copper and photodegradation. Pesticides, organic copper, etc.

Analysis of the development route of copper oxide technology

1 Technological evolution in the field of fertilizer

Copper is an indispensable trace element for plant growth. Although the demand is small, it plays a pivotal role. As early as 1931, GB356195A proposed to compound copper oxide with other compounds to provide fertilizers, pesticides or herbicides. In the following years, copper oxide was mostly used as a copper fertilizer in a total nutrient culture solution. By 1991, CN1053051A proposed to compound a variety of nutrient elements and rare earths to form rare earth fertilizers, which can be used as culture substrates and provide a variety of nutrient elements. In 1997, CN1165802A proposed a multi-functional compound fertilizer technology, according to the need to compound fertilizer components such as copper oxide with other agents (such as fungicides, herbicides, soil amendments, etc.) to obtain different functions. One year later, CN1196345A proposed an organic-inorganic formula fertilizer. The corresponding fertilizer was formulated according to the results of soil determination and the types and requirements of nutrient elements required. This is a fertilizer supply for soil needs and has an epoch-making significance. In 2010, CN101671207A proposed to compound photosynthesis promoters, growth regulators, fungicides and micro-fertilizers to prevent and control plant diseases while promoting plant photosynthesis, promoting plant growth and increasing yield. By 2015, CN105061084A proposed a controlled-release fertilizer, which applied the controlled-release technology to the combination of fertilizer and fungicide/biocide, which can delay the release of active ingredients, play a long-term effect, and to a certain extent improve the effectiveness of the drug. Utilization rate, reduce application amount.

2 Technology evolution in the field of fungicides

As early as 1938, GB484115A proposed the combination of copper oxide and zeolite to prepare a dry powdered fungicide. Then in 1958, GB788668A proposed a technical plan for compounding streptomycin and copper oxide to prevent bacteria. In 2004, with the development of nanomaterials, US20040067159A1 proposed a technical solution of combining copper nanoparticles with other biocides to improve the adhesion of the effective ingredients of the medicament to the plant surface and improve the control effect. In the same year, CN1552456A also proposed the use of Cu2+ as an antibacterial catalyst. Subsequently, technical solutions for the antibacterial compounding of copper oxide, cuprous oxide and various compounds, such as terpene derivatives, mineral salts (US6849276B1), copper free radical compounds (KR100752528B1), and microbial spores (US20110033436A1), appeared. In 2011, CN101933525A proposed a technical plan for preparing a photocatalytic bactericide by compounding nano-cuprous oxide-copper oxide. In 2015, CN104542707A proposed a technical plan to combine nano-copper oxide with pesticide thiram to achieve synergistic effect and sterilization and photocatalytic degradation.

3 Technical evolution in the field of pesticides

Copper oxide is an inorganic copper insecticide well known in the art. In 1949, GB620600A used copper oxide as a sensitizer for insecticidal fumigation compositions. In 1951, FR970319A proposed that the combination of copper oxide and a substance that can produce ammonia can effectively control plant pests. In 1990, CN1041354A proposed a combination of copper salts, insecticides, nutrient elements and plant growth regulators to provide a multi-effect disease control agent. In 2007, KR100752528B1 proposed a technical plan to combine copper free radical compounds with copper oxide/copper hydroxide to prepare insecticides. Subsequently, a technical scheme for combining microbial spores and copper salts to slow down drug resistance and improve control efficacy has emerged.

4 Technical evolution in the field of plant growth regulators

In 1991, CN1051112A proposed that copper oxide can be used as a plant growth regulator while being used as a micro-fertilizer. In 1996, US5575112A proposed a combination of binders and insoluble inorganic copper compounds to regulate the growth of plant roots. Data showed that copper oxide would affect root length, root fresh weight and other indicators. This is the first time there is evidence to directly show that copper oxide can regulate the growth of roots. Root growth.

in conclusion

Due to its low toxicity, safety, wide sterilization spectrum and few residues, copper fungicides are effective against fungi and bacteria, and are environmentally safe. In the production of pollution-free fruits, copper fungicides are listed as recommended agents, especially ferric sulfate, Copper preparations such as copper oxychloride, copper oxide and cuprous oxide. However, copper fungicides are not completely safe and reliable. Abuse and misuse can also cause phytotoxicity in fruit trees, rampant pest mites, and soil pollution. In addition, some fungi, especially the brown rot fungi, are highly copper-tolerant. The copper-tolerant mechanism is closely related to the production of oxalic acid. Oxalic acid will have an effect on copper ions, produce insoluble crystals, and inactivate the antibacterial effect of copper. Thereby reducing the antibacterial toxicity of copper. Therefore, how to improve the control effect of drugs and reduce drug resistance has become an urgent problem to be solved.

In recent years, due to the development of nano-materials, nano-copper oxide also has certain applications in the field of pesticides. Nanomaterials are easier to be absorbed by plants due to their small particle size, which is conducive to the improvement of drug efficacy. In addition, degradable pesticides have also received increasing attention. Low-toxic, high-efficiency, residue-free, and environmentally friendly pesticides have increasingly become the goal pursued by people. Nano-copper oxide has photocatalytic degradation properties. Using this feature, compounding inorganic copper oxide with other fungicides/insecticides can effectively reduce drug residues and improve efficacy, which will become a development trend.

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