Historical Development of Cellulose Material

Sheets of papyrus made by pressing the pitch tissue of a sedge, Cyperus papyrus, were used for writing as early as 3000 B.C. in Egypt. In China strips of bamboo or wood were used for drawing and writing until the discovery of paper, which is attributed to Ts'ai Lun in A.D. 105. The original paper was made in China from rags, bark fiber, and bamboo. Pieces of bamboo were soaked for more than 100 days and boiled in milk of lime for approximately 8 days and nights to release the fibers. The art of papermaking  finally reached to Persia by A.D. 751 and from there spread to the Mediterranean countries from whence the Moors took the industry to Europe in the twelfth century.

Acceptance of paper and the spread of the paper industry in Europe created a chronic shortage of rags for use a raw material. The shortage of paper eventually was relieved by production of pulp from wood. The credit for starting this immense industry is obviously shared by many scientists and inventors, but it is interesting to note that seeds for the idea of extracting the cellulosic fiber from woody tissues not only can be found in the Chinese practice of boiling bamboo in milk of lime, but also in a treatise submitted to the French Royal Academy by Rene Antoine Ferchault de Reaumurin 1719. In this treatise Reaumur a noted physicist and naturalist, observed that: The American wasps from very fine paper, like ours. They extract the fibers of common wood of the countries where they live; they teach us that paper can be made from the fibers of plants without the use of rags and linen, and seem to invite us to try whether we cannot make fine and good paper from the use of certain woods.

Another 120 years elapsed before the French chemist, Anselme Payen, demonstrated that a fibrous substance, which he called cellulose (in 1839), could be isolated by treatment of wood by nitric acid. Isolation of this substance opened the door for production of wood pulp by commercial method of delignification including soda process patented by Watt and Burgers (1853), the sulfite process invented by Tilghman (1866), the kraft process developed by Eaton (1870) and Dahl (1879), and various bleaching methods. Numerous refinements of these processes in the twentieth century have led to the rapid growth and adaptation of paper not only for writing and printing, but also for wrapping, packaging, and a variety of disposable products.

Isolation of cellulose from plant tissues bu laboratory and industrial processes naturally focused scientific interest on defining the structure, composition, properties, and the biogenesis of this material. It is interesting to note that after more than a century of scientific investigation, numerous findings, controversies, and debates the term cellulose (in pure from) still means different things to different groups. To organic chemist, it means β-D-(1,4)-linked glucopyran. To the technologist, it means an asymptotic entity, often called α-cellulose, which represents the alkali insoluble portion of wood pulp. To the biologist, it means the fine microfibrils of plant cell walls that rich a high degree of purity and perfection in a group of green algae, including Valonia, Cladophora, and Chaetomorpha. These groups have been concerned not only with the chemical structure of cellulose and its reactions, but also with its interrelated physical, morphological, and biological properties. Through various types of inquiries, they have tried to find out: how cellulose is crystallized and packed in the fibrils to give it various and other physical properties; what the fibrils and microfibrils are and how they are organized within the layer and lamella of the cell wall; and whether the microfibrils are produced and organized by in animate physical forces or by biological influence of the living cell.

The isolation and chemical investigation of cellulose led to the production of derivatives, including cellulose nitrate, cellulose acetate, rayon, and cellophane, which were the forerunner of the modern plastic and polymer industry. Cellulose nitrate is the oldest known derivative of cellulose. The efforts of John Wesley Hyatt to produce synthetic ivory for billiard balls led to the development of the first synthetic plastic known as celluloid. In 1870 this material was produced from a mixture of partially nitrate cellulose (called pyroxylin) with camphor. Pyroxylin was also used in the manufacture of lacquers, films, and adhesives. Highly nitrated cellulose has been developed as a modern explosive and propellant. Because of the high flammability of cellulose nitrate, cellulose acetate was developed as a safer substitute, first for coating wing fibrics of World War I airplanes and subsequently for photographic and motion-picture films. Cellulose acetate was one of the first materials to be used for manufacturing plastic objects by the injection molding process. In 1892 Charles Frederick Cross and E.J. Bevan discovered cellulose xanthete. This form a viscous solution from which cellulose can be regenerated as a continuous fiber (rayon) or film (cellophane). Development of industrial processes for production of rayon for textiles and cellophane film for packaging led to the development of the dissolving pulp industry in 1911. Until then, the pulp industry was concerned only with the manufacture of fibers for the paper industry; chemical derivatives of cellulose were produce from purified rags or cotton linters. Development of dissolving pulp from wood made available a relatively cheap and pure source of cellulose as a raw material for the expanding chemical industry.

The above industrial developments involve the isolation, modification, and application of cellulose in the form of a fibrous or structural polymer. However the fact of cellulosic material can be converted ti its sugar component and used a source of food, alcohol, and industrial chemical has created another kind of industrial opportunity. This has been repeatedly explored, but practiced only within the controlled economy of the USSR and Japan during the two World Wars. The increasing demand for food, chemical, and fuel as well as the limited supply of petroleum has made the conservation and efficient utilization of cellulosic materials a more urgent problem. The investigation of the conversion of cellulosic material to a wide variety of chemical is gaining momentum. The efforts are directed toward the development of pyrolytic or enzymatic methods as a substitute for the simple acid hydrolysis that has been practiced in the past. Since only a fraction of the annual harvest of cellulosic material produce by forests and agricultural lands is being utilized, conversion of this material to food and chemical may someday provide a fundamental solution to the problem of supply for these products.


Source: James P. Cassey, PULP AND PAPER - Chemistry and Chemical Technology