1863, French chemists C.Friedel and J.M.Crafts started from SiCl4 and ZnEt2 and reacted in a closed tube at 160℃ to prepare the first organosilicon compound SiEt4:
2 znet 2+sicl 4 site 4+2 ZnCl 2
In 1872, Ladenburg prepared silane with silicon functional group by reacting ZnEt2 and Si(OEt)3Cl with Na. Two years later, he started with HgPh2 and SiCl4, and made PhSiCl3 in a sealed test tube. In 1885, SiPH4 and others were prepared by nano-condensation (i.e. Wurtz reaction) in A.Polis Until 1903, many chemists made great efforts for the birth of organosilicon chemistry. People used to call this stage the founding period of organosilicon chemistry. British chemist F.S.Kipping made extensive and in-depth research on organosilicon chemistry from 1898 to 1944, and published 57 papers successively. One of his outstanding contributions is the synthesis of hydrolyzable silane with different functions by Grignard reaction, which will become the foundation of silicone industry in the future. The reaction can be as follows:
solvent
3 rmgcl+2 sicl 4 = RSI cl 3+R2 sicl 2+3m gcl 2
During this period, Dirce synthesized organosilicon compounds by Grignard method almost simultaneously with Kipin. Then he hydrolyzed Ph2SiCl2 _ 2 to PH2Si (OH) _ 2, and then condensed it to give hexaphenyl cyclotrisiloxane (Ph2Si(OH)2 _ 3.
This is the first cyclic siloxane compound, which has played a very good role in promoting the development of polysiloxane. Later generations called this period the growth period of silicone.
In the late 1930s, J.F.Hyed of Corning Glass Company in the United States, W.J.Patnode and E. G.Rochow of General Electric Company in the United States, Dolgov and Andrenov of the former Soviet Union, and Miller of Germany realized the application prospect of silicone polymers and began to explore heat-resistant organic polymers with glass properties. First make silicone resin, and then make dimethyl silicone oil in 1940. 194 1 year, Rochow invented the direct synthesis method of organochlorosilane, and then Miller applied for a patent for the direct synthesis method. 1942, Dow Chemical Company of the United States built a pilot plant for methyl phenyl silicone oil and dimethyl silicone oil. From 65438 to 0943, Dow Chemical and Corning Glass Company jointly established Dow Corning (DC) Company, specializing in the production and research of silicone. 1947, General Electric (GE) established its silicone division (which was later sold to Apollo Private Equity Fund and became silicone, Mai Tu). In 1950s, WACKER (195 1) Bayer (Bayer, 1952, joint venture with GE) and Goldschmidt in Germany; Shinetsu Chemical (1953), Tokyo Shipu Electric (1953 was merged into Toshiba silicone Company, and then joint venture with GE) and Toray silicone Company (1966, and then joint venture with DC, mainly DC); The French company Rhone Planck (later merged into China's Blue Star Company) has established a silicone resin production facility. 、
From 1938 to 1965, due to the increase of monomer output and product variety, the progress of separation and purification technology and the improvement of polymerization process, various silicone oil, silicone rubber and silicone resin products came out one after another. People call this stage the development period of silicone.
After 1965, the development, research, industrial production, popularization and application of silicone, a developed country, entered a new stage of all-round development.
The technological development of silicone in China began at 1952. At that time, Beijing Institute of Chemical Technology (predecessor of shenyang institute of chemical technology) focused on the development of Grignard synthesis of organochlorosilanes, while Shanghai Institute of Organic Chemistry (predecessor of Institute of Chemistry, Chinese Academy of Sciences) focused on the balance and polymerization of siloxanes. 1956 Shenyang research institute of chemical technology builds a pilot plant in silicone, 1958 Shanghai resin factory builds a production device for synthesizing organochlorosilanes by direct method. 1967 Beijing Research Institute of Chemical Technology and Shenyang Research Institute of Chemical Technology silicone merged into Chen Guang Research Institute of Chemical Technology. 1968 Established Spark Chemical Plant (predecessor of Bluestar Silica Gel). During this period, research institutes and manufacturers in silicone developed rapidly. Today, China has become the largest consumer and producer of materials in silicone.