The Development Process of Rubber Chemicals in the World

Introduction to Rubber Chemicals

Rubber chemicals, collectively known as "rubber auxiliaries," are a series of refined chemical products added during the processing of natural rubber and synthetic rubber, collectively referred to as "raw rubber." These additives serve the purpose of enhancing the performance, extending the service life, and improving the processing characteristics of rubber products. They play a crucial role in structural adjustments, new product development, process improvements, and the overall enhancement of performance and quality in the rubber industry, making them indispensable raw materials.

Natural rubber was discovered in 1493 when Columbus found the new continent. However, it wasn't until 1839 that sulfur was found to act as a vulcanizing agent, giving rubber usability and marking the birth of the global rubber industry.

Rubber chemicals can be categorized into three generations based on their development history, as detailed below.

First Generation Rubber Chemicals: 1839-1904

During this era, rubber chemicals products were represented by inorganic vulcanization accelerators. The rubber industry entered the era of inorganic vulcanization accelerators, although issues such as low promotion efficiency and poor vulcanization performance existed.

1839: Discovery of the role of sulfur in rubber vulcanization. 

1844: Discovery of inorganic vulcanization accelerators. 

1846: Discovery that sulfur monochloride can induce "cold vulcanization" of rubber, using urea as a foaming agent. 

1904: Discovery of the vulcanization activator zinc oxide and the reinforcing effect of carbon black on rubber.

Second Generation Rubber Chemicals: 1905-1980

This era saw the dominance of organic vulcanization accelerators. The early organic rubber vulcanization accelerator, aniline, was accidentally discovered in 1906 by German chemist Oenslaber, who was working in the United States at the time.

1906: Invention of organic vulcanization accelerators, thiazole-type accelerators. 

1912: Invention of thiuram-type accelerators and the discovery of aminobenzothiazole.

1914: Invention of amine-type accelerators and β-naphthylamine, and discovery of diphenylamine and para-phenylenediamine as antioxidants. 

1915: Invention of organic peroxides and aromatic nitro compounds, zinc mercaptobenzothiazole accelerators. 

1920: Invention of thiazole-type vulcanization accelerators. 

1922: Invention of guanidine-type vulcanization accelerators. 

1924: Invention of antioxidant AH. 

1928: Invention of antioxidant A. 

1929: Invention of thiram-type vulcanization accelerators. 

1931: Invention of non-staining antioxidants. 

1932: Invention of dithiocarbamate-type vulcanization accelerators (DIBS, CBS, NOBS).

1933: Invention of antioxidant D. 

1937: Invention of antioxidants 4010, 4010NA, 4020, etc. 

1939: Invention of diazotization compounds for rubber vulcanization. 

1940: Invention of silane coupling agents. 

1943: Invention of isocyanate adhesives. 

1960: Invention of processing rubber chemicals. 

1966: Invention of Cohedur adhesives. 

1969: Invention of anti-scorching agent CTP. 

1970: Invention of triazine-type accelerators. 

1980: Invention of Manobond cobalt salt adhesion enhancer.

Third Generation Rubber Chemicals: 1980-Present

After over 100 years of research, by the 1980s, the variety of rubber chemicals began to increase, and the system became more mature. This stage of rubber chemical products is characterized by their environmentally friendly and multifunctional nature.

1980-1981: Development of NS accelerators in China, which had already appeared overseas in 1957. 

1985: Introduction of MTT accelerators. 

From 1991 to the present, the continuous development and application of environmentally friendly, nitrosamine-free or nitrosamine-safe additives, such as thiazoles, dithiocarbamates, zinc salt accelerators, vulcanizing agents, anti-scorching agents, plasticizers, etc. Products such as ZBPD, TBSI, CBBS, TBzTD, TIBTD, TIBTM, ZDIBC, OTTOS, ZBEC, AS100, E/C, DBD, etc., have been successively invented.