User:Tiraxxis/sandbox

David Spence was one of the pioneering rubber chemists. He helped the war effort during the Second World War by devising new ways of extracting natural rubbers from plants and worked to improve the processing of the rubber. Over the course of his career, he also worked to improve the dyeing processes for rubber products and the vulcanization of rubber, and in developing new accelerants for strengthening lower quality natural rubber. In 1941, he became the first recipient of the Charles Goodyear Medal awarded by the American Chemical Society.

Biography
Spence earned his PhD from the University of Jena in Germany in 1906. Three years later, he accepted a position as research lab director at the Diamond Rubber Company in Akron, Ohio.

He stayed at the Diamond Rubber Company even after it was purchased by B.F. Goodrich Company in 1912. There, he succeeded in synthesizing isoprene for use in synthetic rubber. He left the company in 1914 and jointly started Norwalk Tire & Rubber Company where he was vice president and manager until 1925. He retired in 1931 where he continued to do his own rubber research.

During his career, he also developed accelerators for the vulcanize process, a process to devulcanize rubber, extract natural rubber from guayule, and modify the physical properties of rubber. During World War I, Spence headed the National Research Council's Rubber Division, and he was a consultant to the War Production Board during World War II. In 1941, he became the first recipient of the Charles Goodyear Medal. He died on September 24, 1957 in New York.

Organic accelerators
In the early years of rubber production, high quality natural rubber was obtained from the tree, Hevea braziliensis, from the regions bordering the Amazon river. The high quality rubber exhibited desired properties such as a high tensile strength (>2800psi) and a two hour vulcanization time. Vulcanization is the process by which natural rubber is strengthened by cross-linking the different polymer chains with either elemental sulfur bridges or other molecules known as accelerators. However, high quality natural rubber was expensive with a price exceeding $1.50/lbs. The Diamond Rubber Company experimented with various additives, such as mercury iodide and aniline, in an attempt to improve the properties of lower quality rubber rubber. The addition of only 2.5-6 percent of these additives improved the tensile strength of low quality rubber from 1800 psi to 2800 psi and shortened the vulcanization time to a mere 90 minutes. However, these additives were detrimental to the lifetime of the vulcanized rubber. In 1912 Spence was working with George Onsager at the Diamond Rubber Company to discover novel additives to the vulcanization process to overcome the shortcomings of the previous additives. Working off of Onsager's aniline additives, Spence discovered that p-aminodimethylaniline was a far superior accelerator, requiring only 0.5 weight percent addition to the vulcanization process to vastly improve the tensile strength of the rubber. P-aminodimethylaniline was adopted as the accelerator of choice by the Diamond Rubber Company in 1912.



Development of guayule as a rubber alternative
Throughout World War II, the allied forces suffered from a shortage of latex rubber due to Japan cutting off America's access to the Maylasian rubber plantations. Spence along with other allied scientists scrambled to secure another natural rubber resource. Latex derived from Parthenium argentatum, more commonly called Guayule, was an ideal candidate for a replacement rubber as the properties of the vulcanized rubber produced from Guayule had properties similar to rubber produced from Maylasian rubber plantations. Latex from Guayule was first prepared in 1876 via a solvent extraction of the latex using acetone and this extraction process was used commercially by the Diamond Rubber Company up until the 1930s. However the acetone extraction process was too expensive to meet the large rubber demand brought on by World War II, therefore there was a push to implement more conventional mechanical processing methods to extract the latex. A significant production challenge in the production of latex from Guayule was that both the mass of the latex extracted and the tensile strength of latex fell off due to the long storage time between the harvesting of the Guayule and the processing of the Guayule. Spence was brought on by the Intercontinental Rubber Company to solve this challenge. Spence patented methodologies to both improve the quality and yield of rubber produced from Guayule via conventional mechanical techniques in 1933   Upon investigation, Spence determined that the drying of the Guayule was responsible for the high variability in both the yield and quality of the latex produced from Guayule. Spence's retting processes of handling the Guayule shrub increased both the uniformity of the yield and the quality of rubber extracted from the Guayule plant. The retting process included soaking a crushed Guayule plant in a 1% para-dimethylphenylamine solution in order for natural occurring bacteria and enzymes to decompose unwanted plant material into water soluble by-products that could be washed away during the milling process and to prevent the oxidative loss of the plant's natural rubber. The retting process improved the milling extraction process of Guayule upwards of 6 percent, and improved the tensile strength from 1800-2000psi upwards of 2800psi, a tensile strength comparable to that of the rubber trees.

Synthetic production of isoprene
Unfortunately the rubber from the Guayule plant could not satisfy the American demand for rubber. Even though President Franklin D. Roosevelt at the time stockpiled roughly 1 million tons of rubber, the annual U.S. consumption rate was 600 thousand tons of rubber per year. Therefore additional rubber supplies would need to be secured in order to avert a rubber shortage. This would present a serious vulnerability in the American war machine, as rubber was used to manufacture a wide variety of war materials. In order to quickly produce more rubber to replace the dwindling national supply, President Roosevelt commissioned American rubber and petroleum industries to quickly design and implement synthetic rubber replacements. Thus a rapid expansion of the petroleum and rubber industries ensued to meet this demand for a novel source of synthetic rubber. To solve the rubber shortage, Spence and scientists from Goodyear, Firestone, Goodrich, and New Jersey Standard, joined together under a patent sharing agreement. The goals of the synthetic rubber project were to either synthetically produce the isoprene monomer, or combine multiple monomers to produce a suitable synthetic substitute for rubber. Spence, together with Dr. Alexander Clark, provided a method for producing synthetic isoprene via the dehydration of 2,3 dimethylbut-1-en-3-ol and other alcohols using glacial acetic acid. Due to his involvement in the synthesis of the isoprene monomer, Spence was the first recipient of the Charles Goodyear Medal.

The development of a novel vulcanization and dyeing process for rubber products
While working at the Goodyear rubber company, Spence altered the processes for vulcanization and application of colored dyes to rubber. Traditionally vulcanization is accomplished in air with sulfur and other accelerators. While observing devulcanization, Spence observed that the decomposition products are dependent on the oxygen content in the system, and that without oxygen the rubber failed to devulcanize. Upon these observations Spence developed an oxygen, sulfur, and accelerator free vulcanization process by using organic oxidizers such as quinones or organic peroxides. Spence's vulcanization process required placing the latex mixture in a pH 7 buffered solution and applying an organic oxidizer agent to the mixture under an inert atmosphere of nitrogen. In addition to redeveloping the vulcanization process, Spence developed a method for applying dyes to raw rubber. Prior to Spence's novel method to apply dyes, the dyes were applied during the processing of the rubber. This proved too expensive and was limited by thermal decomposition of the dyes. Submerging the rubber products in an adsorbent bath of amine dye, sodium hydrate, sodium chloride, and sulfuric acid allowed for the dyes to be bound covalently to the rubber matrix. The amines in solution will react with primary amines in the rubber matrix to form azo dyes on the rubber fibers. This methodology of dyeing rubber was found to be applicable to raw, vulcanized, and other manufactured rubber products.