Abstract
Polymers of natural origin (gums, fibers, skins) have been used by man since prehistoric times. The technology of improving the useful qualities of such materials was developed empirically without benefit of the unifying conceptual framework of chemistry. The early chemical efforts which lead to the modification of rubber via isomerization with acid (1781)2 or Vulcanization with sulfur (1839)3 were also largely serendipitous discoveries. By the mid-19th century investigators like Bracconnot (1833)4 and Schönbein (1845)5 had begun systematic efforts to apply the emerging science of organic chemistry to the task of modifying the end-use properties of natural materials, or imparting wholly new properties to them. The careful study of the reaction of cellulose with nitric acid ultimately led to Parkes’ production of the first semisynthetic commercial plastic, “Parkesine” (1864)6. The chemistry of polyisoprene isolated from a variety of natural sources was also a subject of intense chemical investigation. It had been chlorinated in 18597, and was later hydrochlorinated in 18818. Weber (1894)9 recognized similarities between the Vulcanization process and the insolubilization of rubber by S2Cl2. The production of rayon by treatment of alkali-cellulose with CS2 was patented in 189210.
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References
Excluded from this discussion are those processes which degrade the macromolecule to small molecules and lead to the loss of properties associated with high molecular weight. The simple processes of the various growth mechanisms of polymerization are also not considered polymer reactions in this context.
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Catalysis
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Peptides
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Polymeric Reagents
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Polymeric Supports
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N. K. Mathur and R. E. Williams, J. Macromol. Sci., Rev. Macromol. Chem. C15, 117–142 (1976), “Organic Syntheses Using Polymeric Supports, Polymeric Reagents and Polymeric Catalysts”.
C. C. Leznoff, Acc. Chem. Res. 11, 327–333 (1978), “The Use of Insoluble Polymer Supports in General Organic Synthesis”.
P. Hodge, Chem. Brit. 14, 237–243 (1978), “Polymer Supports in Organic Synthesis”.
J. M. J. Frechet, Tetrahedron 3, 663–683 (1981), “Synthesis and Applications of Organic Polymers as Supports and Protecting Groups”.
Modifications of Polymers
R. C. Schulz, Angew. Makromol. Chem. 4/5, 1–25 (1968), “Reactions on Polymers” (in German).
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Miscellaneous
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Progress in Macrocyclic Chemistry, Vol 2, R. M. Izatt and J. J. Christensen, eds., Wiley, NY, 1981, J. Smid, “Solute Binding to Polymers with Macroheterocyclic Ligands, p. 91–172.
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Moore, J.A., Carraher, C.E. (1983). Modification of Polymers. In: Carraher, C.E., Moore, J.A. (eds) Modification of Polymers. Polymer Science and Technology, vol 21. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-3748-5_1
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