History of PNS in North America
Polynaphthalene sulfonates (PNS)
or as they are also called, naphthalene sulfonate condensates, were developed in the 1930’s by IG Farben(Interessen-Gemeinschaft Farbenindustrie AG) in Germany. IG Farben consisted of the following major companies and several smaller ones:
- BASF (Badische Anilin und Soda Fabrik)
Originally the product was used in leather and textile chemicals and later in the development of synthetic rubber. PNS was used in addition to rosin emulsifiers to maintain synthetic rubber in solution until the polymers had grown to a sufficient molecular weight. PNS was a secondary emulsifier allowing the rubber to stay in an emulsified state after the polymer chain reaction was halted. As a secondary emulsifier, PNS has been used since the development of synthetic rubber. It continues to be an important part of certain synthetic rubber processes today.
The original PNS from IG Farben was called Tamol®. Rohm and Haas developed in cooperation with IG Farben and began selling Tamol® in the US. Rohm and Haas began producing the product in Philadelphia by the late 1930’s. Rohm and Haas was a critical player in the development of synthetic rubber during the war years.
In the 1920’s, before World War II, Jacques Wolf Company in Carlstadt, NJ expropriated the German PNS technology. Wolf began manufacturing PNS to compete with Rohm and Haas in 1946. This PNS product was originally called Ramol, but the word was too close to Rohm and Haas’s product, Tamol®. In a twist, illustrating the competitiveness of the market, Wolf reversed the letters and called the product Lomar®.
A long line of owners would then pass Wolf on as a business.
- Jacques Wolf Company – 1920’s
- NOPCO Corporation- 1952
- Diamond Shamrock – 1960’s
- Henkel- 1988
- GEO Specialty Chemical- 1997
Dewey and Almy, another chemical manufacturer, also obtained the PNS technology from Germany. Along with Rohm and Haas, Dewey and Almy developed a synthetic rubber to replace natural rubber for the war effort in 1941. Polynaphthalene sulfonates were an important part of this development. After seeing the product-naming skirmish between Rohm and Haas and Jacques Wolf, Bradley Dewey decided that he wanted a unique name, Daxad®. He did not want anyone reversing his product name. Dewey and Almy followed a similar fate of the Jacques Wolf Company and followed a list of owners until the merger today into GEO Specialty Chemicals.
- Dewey and Almy (1919)
- W. R. Grace (1954)
- Hampshire Chemical (1994)
- Dow Chemical (1998)
- GEO Specialty Chemical (2005)
Rohm and Haas, Dewey and Almy and Nopco manufactured PNS during World War II for the US government owned synthetic rubber plants.
Rohm and Haas manufactured the product in Philadelphia, Jacques Wolf in New Jersey, and Dewey and Almy Chemical Company manufactured in Cambridge Massachusetts.
In the meantime, PNS manufacturers proliferated in Europe, all with the original German IG Farben technology. These products were low molecular weight products used in rubber, textile and leather applications. Expanding the uses for PNS did not seem possible because the molecular weight was not high enough. The science of the time believed that the molecule could not be made larger without forming a gel. Therefore PNS applications were limited.
In the early 1950’s a chemical technician, Alex Jacavino, was working on PNS formulations at Wolf. He developed a method to make a higher molecular weight product that would not gel. The original application was for refractory crucible manufacturing, but by the mid 1950’s a company in Texas, Fritz Chemical, found an application in oil field cementing. This was the beginning of a very large market for high molecular weight PNS oil field. Halliburton and Dowell Schlumberger were two of many companies who used this product extensively.
Nopco (Formerly Wolf) was successful in promoting its PNS worldwide. The Lomar® trade name was well recognized. San Nopco, a joint venture between Nopco and Sanwa in Japan, tried to expand Lomar®’s sales into Asia, but were only marginally successful. A Japanese soap company, Kao, investigated the PNS technology. At Kao, Dr. Kenichi Hattori developed a product to reduce the water required in regular concrete. This product was called Mighty 150. In the early 1960’s Kao was the first company to use PNS in ready-mix concrete.
By 1965 Mighty 150 was a major product in the Japanese concrete industry. Kao brought the product to the US through a joint venture with ICI in 1970. ICI manufactured the product in the mid 70’s but never achieved the large volumes that they expected. ICI stopped production and had the product toll manufactured by Boremco in Massachusetts. This put a fourth company into production of PNS in North America.
Also in the 1970’s a retired technician from Nopco worked with Handy Chemical to develop PNS in Canada. Handy was a floor cleaning and detergent company, but under the direction of Nehlu Spiratos, took to the PNS business rapidly and quickly became the fifth manufacturer of PNS in North America. Several changes have occurred at Handy. In the early 2000’s Ruetgers purchased Handy Chemicals and changed their name except in the U.S. Nehlu Spiratos was pushed out of the company and more cosmetic changes occured as Ruetgers was bought out by Rain CII of India, a coal tar company.
Today the methods for manufacturing PNS are relatively standard. Specific nuances in temperature and ingredient ratios will vary from one manufacturer to the other, but the base product is relatively the same. Outside the US, BASF and Kao remain the major manufacturers of PNS. Clariant and Huntsman have purchased PNS plants through their acquisitions, but they divested most of their PNS operations by 2010. There are various manufacturers in Eastern Europe and India. The largest manufacturers and, by far, the largest markets for PNS are now in China. PNS is a major product for concrete construction in China.
A significant increase in naphthalene pricing outside of China, aggressive pricing among competitors and a new replacement product in the concrete segment, has reduced the number of competitors significantly. Clariant closed their manufacturing plant in England. Kao’s production in Japan has declined significantly due to product changes away from naphthalene sulfonates.
In North America, Rohm and Haas shut down their production in 1990. Boremco closed their plant in Fall River, MA in 2002. GEO Specialty Chemicals purchased the Dow plant leaving only two competitors, GEO and Handy in North America. The future of naphthalene sulfonates is not rosy, but new applications continue to be discovered. The product will continue to be used in the foreseeable future.
Update: GEO Specialty Chemicals has shut down naphthalene sulfonate production in the Deer Park, Texas plant. Now only 2 producers remain in North America. This has made North America the highest priced market in the world for naphthalene sulfonates.