The scientific and technological fields to which the project belongs are catalytic materials and polymer materials. The new generation of single-site polyolefin catalysts such as metallocene catalysts (hereinafter referred to as "metallocene catalysts") are considered to be the future of the development of the polyolefin industry due to their unique structure and adjustable ligand groups. Western countries and their multinational companies have formed a technological monopoly on this, which restricts the development of my country's polyolefin industry. With the support of the Ministry of Science and Technology of the People's Republic of China, the Shanghai City Science and Technology Commission, and the Shanghai City Economic and Information Commission, this project has broken through a series of process technical problems in the development and industrialization of core components of metallocene catalysts and achieved key results:
(i)Invented a new synthesis method for a series of metallocene cocatalysts-asymmetric perfluorophenyl borate products, and broke through the engineering preparation problem, successfully filling the domestic gap in this type of product. (ii)It breaks through the technical bottleneck of industrial preparation of the core components of the series of metallocene main catalysts-indanone/indane compounds with directional substitution structures and hindered bridged cyclopentadiene compounds, and achieves localized batch preparation. (iii)Metallocene compounds containing heteroatoms or heterocyclic side chains were designed and synthesized, and based on this, a new metallocene catalyst system for ethylene polymerization was constructed.
Based on an in-depth analysis of the structural characteristics of key components of metallocene catalysts, the project is application-oriented and innovates in key technologies. It adopts a new strategy of series reaction of Grignard reagents, a new low-temperature vacuum azeotropic dehydration technology, and one-step aromatic esters. New catalytic cyclization technologies, hydrolysis-decarboxylation-cyclization short-process processes, new technologies for preparing thermosensitive indene compounds by efficient polymerization inhibition and low-temperature catalytic coupled dehydration, and preparation technologies for metallocene compounds containing heteroatoms, etc. The development and industrialization of a series of core component products of metallocene catalysts have been completed. Apply for 8 China invention patents, of which 5 have been authorized, 3 standards have been formulated, and 1 single crystal has been registered in the Cambridge Crystal Database. Based on ISIS software, the first domestic product database covering more than 1000 core components and related basic compounds of metallocene catalysts has been established, providing rich molecular modulation modules for the development of new generation polyolefin catalysts. The project technology has been widely recognized by domestic and foreign companies and experts in related fields, achieving localized preparation and batch export, breaking the long-standing foreign monopoly on the industrial preparation technology and product supply of the core component compounds of metallocene catalysts, and filling the gap in domestic similar industrialization has laid a solid foundation for my country to master an independent metallocene catalyst preparation technology system.
The project has established an annual output of 100 tons/year, and the products have achieved stable production. They have been successfully applied in domestic and foreign companies such as Grice and Sinopec Lead in the United States. The results show that the project products can meet the needs of metallocene polyolefin catalyst production, and the overall performance has reached the international advanced level. The social and economic benefits of this project are good. In the past three years, the new output value of related products of this project has been 206 million yuan, the new profits and taxes have been 91.71 million yuan, and the foreign exchange earned by exports has been US$18.4429 million, realizing indirect economic benefits of approximately 77 million yuan. The metallocene catalyst has high polymerization efficiency, high polymer strength and low ash content, improving the environmental protection performance of polyolefin products. This project plays an important role in improving the international influence of the industry, improving the quality of my country's polyolefin products, and saving resources.