Storax distillation

In 1786 William Nieholson wrote A Dictionary of Practical and Theoretical Chemistry. In this work Nicholson mentions that a chemist named Neuman, on distillation of storax (a balsam derived from the tree Liquambar orientalis), had produced a fragrant empyreumatic oil . In 1839 E. Simon carried out some similar experiments, apparently quite independently, and again obtained this essential oil which he ealled styrol. In 1845 M. Glenard and R. Boudault reported on the production of styrol (now known as styrene) by dry distillation of dragons blood, a resin obtained from the fruit of the Malayan rattan palm. 

The principal constituent of storax is cinnamic acid and for laboratory purposes styrene is still most easily obtained in high purity but dry distillation of cinnamic acid and its salts under atmospheric pressure (Figure 16.1). 

Ethyl dnnamate occurs in small amounts in storax.1 It has been prepared by the action of ethyl alcohol on cinnamic acid in the presence of dry hydrochloric or sulfuric acid 2 by the distillation of the copper salt of the monoethyl ester of benzylidene oxalacetic acid3 and by the condensation of ethyl acetate and benzaldehyde in the presence of sodium.4 The method described in the procedure is a slight modification of the one originally described by Claisen.5... 

In 1839, Eduard Simon, an apothecary in Berlin, distilled storax resin obtained from the Tree of Turkey , (liquid ambar orientalis) with a sodium carbonate solution and obtained an oil which he analysed and named styrol (what we now call styrene) [1]. He recorded the following observation that with old oil the residue which cannot be vaporised without decomposition is greater than with fresh oil, undoubtedly due to a steady conversion of the oil by air, light and heat to a rubberlike substance . Simon believed he had oxidised the material and called the product styrol oxide. Later, when he realised that it contained no oxygen, the product became known as metastyrol. This puzzled the early chemists as there was no change in empirical formula despite the very pronounced alteration in chemical and physical properties. Unknowingly, this was the first recorded instance of polymerization. 

Styrol. Mix 20 part.s of storax with 7 of carbonate of sodii, and put them into a retort with water, and apply heat. A limpid Ouid distills, which becomes, when heated to a certain point, a transparent solid. 

Simon in 1839 named the distillate of Storax officinalis a styrol. By 1845, the thermal polymerization of styrene as well as the thermal depolymerization of PS were known. In 1915 I. G. Farbenindustrie started commercial production of PS, Trolitul . Until the 1950 s, PS was produced in small quantities — the resin was brittle, thermally unstable, with poor solvent and scratch resistance. The main use of styrene was in the manufacture of styrenics, viz. Buna-S, SBR, or ABS. 

Styrene, CeHs.CH = CH2, phenylethylene, or styrole, derives its name from its occurrence in storax. It can be prepared by methods which are indicated by its structure. The hydrocarbon bears the same relation to cinnamic acid, C6H5CH = CHC00H, that benzene bears to benzoic acid. It can be prepared by heating sodium cinnamate with sodium hydroxide, or by simply distilling the free acid —... 

Storax, a liquid resin of the Liquidamhar orientalis tree, was known at a very early date and exported by the Arabs to India and China. J. F. Bonastre, who was an expert on essential oils, obtained from it styracin, which is cinnamyl cinnamate CQHg-CgHyOg, the earliest aromatic ester known and by distilling storax he obtained a volatile oil, which E. Simon concluded was a hydro-... 

Neuman obtained styrene monomer by the distillation of storax (liquid amber) in the early 1800 s. Subsequently, in 1839, Simon repeated this experiment and obtained an elemental analysis of the distillate which he called "styrol". Bl3rth and Hoffman heated styrol and produced a solid which they called metastyrol. 

Styrene and its polymers deserve a special place in polymer science history. The polymerization of a liquid obtained by Simon by the pyrolysis of storax in 1839 was the first recoiled polymerization of a vinyl monomer (1). Since he confused the polymer with an oxidation product, he called it styrene oxide. Blythe and Hofmann (2) suggested the name meta-styrol and Kopp (3) showed that this product and cinnanol, obtained by the distillation of cinnamic acid to be identical. Erlenmeyer (4) described this product as vinyl benzene. 

Andrew lire s Dictionary of Chemistry and Minerology of 1831 lists Storax as the resinous exudate of the Sweetgum (Liquidambar) tree [19]. The sweet fragrance is due to cinnamic acid. When pure cinnamic acid is heated in a steam distillation it readily decarboxylates to yield styrene. 

An earlier citation in William Nicholson s A Dictionary of Practical and Theoretical Chemistry of 1808 describes experiments by Neuman where he subjected Storax resin to steam distillation and obtained an empyreumatic oil [20]. The first person to name the oil was E. Simon in 1839 he called it styrol [21]. Careful elemental analysis of this substance by G. Gerhardt and A. Cahours in 1841 yielded the empirical formula CH [22]. Vapor density measurements, a standard in the land of Regnault and Dumas, yielded the correct molecular formula CgHg. Extensive physical measurements on styrol by E. Kopp in 1845 yielded its boiling point(144 C), and its specific gravity (0.928). Chemical analysis with bromine revealed a single aliphatic double bond [23]. 

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