The first commercial production of MSA, developed in the 1940s by Standard Oil of Indiana, was based on oxidation of dimethylsulfidebyO 2 from air. Although inexpensive, this process suffered from a poor product quality and explosion hazards.
In 1967, the Pennwalt Corporation (USA) developed a different process for dimethylsulfide (as a water-based emulsion) oxidation using chlorine, followed by extraction-purification. In 2022 this chlorine-oxidation process was used only by Arkema (France) for making high-purity MSA. This process is not popular on a large scale, because it co-produces large quantities of hydrochloric acid.
Between years 1970 and 2000 MSA was used only on a relatively small-scale in niche markets (for example, in the microelectronic and electroplating industries since the 1980s), which was mainly due to its rather high price and limited availability. However, this situation changed around 2003, when BASF launched commercial production of MSA in Ludwigshafen based on a modified version of the aforementioned air oxidation process, oxidising dimethyldisulfide with nitric acid which is then restored using atmospheric oxygen. The former is produced in one step from methanol from syngas, hydrogen and sulfur.[4]
An even better (lower-cost and environmentally friendlier) process of making methanesulfonic acid was developed in 2016 by Grillo-Werke AG (Germany). It is based on a direct reaction between methane and oleum at around 50 °C and 100 bar in the presence of a potassium persulfate initiator. [5] This technology was acquired and commercialized by BASF in 2019.[6]
Methanesulfonic acid can be used in the generation of borane (BH3) by reacting methanesulfonic acid with NaBH4 in an aprotic solvent such as THForDMSO, the complex of BH3 and the solvent is formed.[7]
Solutions of methanesulfonic acid are used for the electroplating of tin and tin-lead solders. It is displacing the use of fluoroboric acid, which releases corrosive and volatile hydrogen fluoride.[8]
Methanesulfonic acid is also a primary ingredient in rust and scale removers.[9] It is used to clean off surface rust from ceramic, tiles and porcelain which are usually susceptible to acid attack.
^Towler, Christopher S.; Li, Tonglei; Wikström, Håkan; Remick, David M.; Sanchez-Felix, Manuel V.; Taylor, Lynne S. (December 2008). "An Investigation into the Influence of Counterion on the Properties of Some Amorphous Organic Salts". Molecular Pharmaceutics. 5 (6): 946–955. doi:10.1021/mp8000342. PMID19434850.
^Gernon, M. D.; Wu, M.; Buszta, T.; Janney, P. (1999). "Environmental benefits of methanesulfonic acid: comparative properties and advantages". Green Chemistry. 1 (3): 127–140. doi:10.1039/a900157c.
^US patent 6531629B1, Matthias Eiermann, Christian Tragut, Klaus Ebel, "Method of producing alkanesulfonic acid", issued 2003-03-11, assigned to BASF SE
^Lobree, Lisa J.; Bell, Alexis T. (2001). "K2S2O8-Initiated Sulfonation of Methane to Methanesulfonic Acid". Ind. Eng. Chem. Res. 40 (3): 736–742. doi:10.1021/ie000725b.
^Lobben, Paul C.; Leung, Simon Shun-Wang; Tummala, Srinivas (2004). "Integrated Approach to the Development and Understanding of the Borane Reduction of a Carboxylic Acid". Org. Process Res. Dev.8 (6): 1072–1075. doi:10.1021/op049910h.
^Balaji, R.; Pushpavanam, Malathy (2003). "Methanesulphonic acid in electroplating related metal finishing industries". Transactions of the Imf. 81 (5): 154–158. doi:10.1080/00202967.2003.11871526. S2CID91584456.
