Brief History of Organic Silicon Industry

Although organic silicon is widely used, its history is only over one hundred years.

In 1863, French chemists C. Friedel and J.M. Crafts started from SiCl4 and ZnEt2 and reacted in a sealed tube at 160 ℃ to prepare the first organosilicon compound SiEt4 containing Si-C bond

2ZnEt2+SiCl4SiEt4+2ZnCl2

In 1872, A. Ladenburg reacted with Na using ZnEt2, Si (OEt) 3Cl to produce silane with silicon functional group. Two years later, he started from HgPh2 and SiCl4 to produce PhSiCl3 in the sealing pipe. In 1885, A. Polis prepared SiPH4 by sodium condensation (Wurtz reaction). Until 1903, many chemists had made great efforts for the birth of organosilicon chemistry. It is customary to call this stage the origination of organosilicon chemistry.

From 1898 to 1944, British chemist F.S. Kipping conducted extensive and in-depth research on silicone chemistry, and successively published 57 papers. One of his outstanding contributions is to use Grignard reaction to synthesize hydrolyzable silane with different functionality, which will become the foundation of the future silicone industry. This reaction can be illustrated as follows:

solvent

3RMgCl+2SiCl4 =RSiCl3+ R2SiCl2+3MgCl2

During this period, W. Dilthey and Kipping almost simultaneously synthesized organosilicon compounds by Grignard method. Then he hydrolyzed Ph2SiCl2 to Ph2Si (OH) 2, and then condensed to obtain hexaphenyl cyclotrisiloxane (Ph2SiO) 3,

This is the first cyclic siloxane compound, which plays a good role in promoting the development of polysiloxane. Later generations called this period the growth period of organic silicon.

In the late 1930s, J.F. Hyed of Corning Glass Company, W. J. Patnode and E.G. Rochow of General Electric Company, Dolgov and Andrynov of the former Soviet Union and Miller of Germany recognized the application prospect of silicone polymers and began to explore heat-resistant organic polymers with glass properties. First, silicone resin was made, and then dimethyl silicone oil was made in 1940. In 1941, Rochow invented the direct method to synthesize organochlorosilane, and then Miller also applied for the direct method patent. In 1942, Dow Chemical Company of the United States built a pilot test device for methylphenyl silicone resin and dimethyl silicone oil. In 1943, Dow Corning (DC), a joint venture between Dow Chemical and Corning Glass, was established, specializing in the production and research of silicone. In 1947, General Electric (GE) established the Organic Silicon Department (later sold to Apollo Private Equity Fund, becoming the current Maitu Organic Silicon). In the 1950s, Wacker (1951), Bayer (joint venture with GE after 1952) and Goldschmidt in Germany; Shinyue Chemical (1953) of Japan, Toshiba Electric (merged into Toshiba Organic Silicon Company in 1953, and then jointly invested with GE) and Toshiba Organic Silicon Company (1966, later jointly invested with DC, and mainly DC); France's Rhone Poulenc (later incorporated into China's Bluestar) and others have established silicone production plants

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 organic silicon.

After 1965, the development, research, industrial production, promotion and application of organosilicon in developed countries have entered a new stage of comprehensive development.

The development of silicone technology in China started in 1952. At that time, Beijing Institute of Chemical Industry (the predecessor of Shenyang Research Institute of Chemical Industry) focused on the development of Grignard process for the synthesis of organochlorosilane, and Shanghai Institute of Organic Chemistry (the predecessor of Institute of Chemistry of Chinese Academy of Sciences) focused on the balance and polymerization of siloxane. In 1956, Shenyang Research Institute of Chemical Industry built an organic silicon pilot workshop, and in 1958, Shanghai Resin Plant built a direct synthesis organic chlorosilane production plant. In 1967, Beijing Research Institute of Chemical Industry and Shenyang Research Institute of Chemical Industry were merged into Chenguang Research Institute of Chemical Industry. In 1968, Xinghuo Chemical Plant (the predecessor of Bluestar Organic Silicon) was established. During this period, organic silicon research units and manufacturers developed rapidly. Today, China has become the largest consumer and producer of silicone materials.