The main source of chemical fiber is oil, so some people joke that "this is an era of wearing oil", then what is the past life of chemical fiber?

Since ancient times, human life has been closely related to fiber. 50,000 to 100,000 years ago, with the degradation of body hair, humans began to use natural clothing such as hide, bark and grass leaves to cover the body and keep warm. Later, humans mastered the technology of separating and refining plant fibers.

Ten thousand years ago, humans were able to use sheep hair directly. In the early cultures of China, Egypt and South Africa, there are some records of spinning yarn and weaving cloth from natural fibers, dating back to 3000 BC. Flax, for example, was used in Central Europe as early as the Neolithic Age. Cotton has been used in India as long as linen has been used in Europe.

Silk has been found in China since 2640 BC, and the unearthed cultural relics of the Shang Dynasty prove that a variety of silk has been used in the highly developed weaving technology at that time. Wool was also used in Central Asia at the end of the Neolithic Age. Therefore, it can be said that hemp, cotton, silk and wool, which are now widely used as natural fibers, have been applied worldwide since BC.

Compared with the long history of natural fibers, the history of chemical fibers is still very short.

Although Hook had already proposed the idea of chemical fibers in his book Micrographia in 1664, scientists were at a loss to develop chemical fibers because they could not understand the basic structure of fibers, which led to the realization of this wonderful idea more than 200 years later.

Innovation and the initial stage

Cellulose nitrate

In 1846, the German F. chonbein made cellulose nitrate by treating wood cellulose with nitric acid.

In 1855, G.Audemars obtained the first patent in the history of the world's chemical fibers. He proposed to treat the bast fibers of mulberry branches with nitric acid, dissolve them in a mixture of ether and alcohol, and then draw silk through a steel nozzle.

In 1862, the Frenchman M. Ozanam proposed the idea of using spinneret spinning.

In 1883, the British J. W. wan obtained a patent for spinning with acetic acid solution of nitrocellulose, and then carbonizing to produce incandescent filament. He also believed that this silk could be used for weaving, and called it "rayon".

In the same year, the French Chardonnet obtained the most famous patent for the manufacture of chemical fibers from cellulose nitrate, and in 1891 in Besancon produced nitrate ester fibers (cellulose nitrate fibers) on an industrial scale, which marked the beginning of the industrialization of chemical fibers in the world. Subsequently, various forms of artificial cellulose fibers (including copper ammonia fiber, viscose fiber and acetate fiber) have been developed. However, nitrate ester fiber develops slowly because its textile performance is not as good as viscose fiber.

Copper ammonia fibre

In 1857, the German Schweizer invented the method of preparing copper ammonia cellulose.

In 1890, Despassie proposed a method for preparing cellulose fibers from copper ammonia solution. In Germany, Oberbruch, near Aachen, was the first to produce cellulose fibers by the copper ammonia process, and in 1899, the Glanzstoff company, the predecessor of Enka, was established to realize the industrialization of copper ammonia fibers. Bemberg further developed the copper ammonia process. Copper ammonia fiber can not compete with viscose fiber in cost due to the higher price of copper ammonia as a solvent, so it is only used for a few textiles and artificial kidneys.

glue

In 1891, three Englishmen, C.F. ross, E.J. Evans and C.B. Adle, invented a new method of dissolving cellulose into a solution, the viscose method, and obtained patents in Britain and Germany in 1892. The German company H.V. Dennersmarck obtained a license to use the patent in Central Europe and set up a factory in 1901, but production was not normal until 1910. The rights were purchased by the British Courtaulds company, which first industrialised in 1904, becoming the world's first mass-produced chemical fibre variety. Towards the end of the First World War, staple fibers were produced by cutting viscose filaments.

In 1921, the Premnitz factory in Germany produced viscose staple fibers that could be used for textile purposes. During this period, high-strength viscose filaments for industrial use were also developed.

Acetate fibre

At the same time, in 1869, the German P. Schutzenberger successfully studied the use of acetic anhydride for the acetylation of cellulose on a laboratory scale.

In 1904, the Bayer dye Company applied for a patent for spinning acetate fibers based on the invention of the German A.E. ichengrun, but delayed for more than 20 years before the joint venture of IG-Farbenindustrie and Glanzstoff was put into production in 1926. The United States Cellanese company first realized the industrialization of acetate fiber in 1924. The use of acetate fiber in the textile field is limited to lining cloth and so on, so the development is not fast. But it has been devoted to the material of cigarette filters.

Regenerated protein fibre

Since the early 20th century, various regenerated protein fibers have also appeared.

In 1904, pharmacist F.T. Tenhaupt invented the method of extracting casein protein from cow milk and spinning it to produce casein protein fiber.

However, this method was not mature in production until the 1930s by A. etti in the Snia company in Italy.

In the early 1940s, the British company Courtaulds also developed casein protein fibers.

In 1938, the British ICI company prepared peanut protein fiber.

In the 30s and 40s, the American scholar R.A.Boyer successfully developed soybean protein fiber.

In 1938, the Japanese oil company also developed soybean protein fiber.

In 1939, the United States Core Product refining company spun protein from corn to produce corn protein fiber.

In 1948, the American Vaiginia Carolina Chemical Company developed corn gluten fiber.

However, the regenerated protein fibers developed in the early stage did not gain an important position in the market due to poor mechanical properties and technical difficulties. In the United Kingdom, peanut protein fiber was discontinued as early as "AtdilIC" in 1957, and in the United States, corn protein fiber "Vicara" and soybean protein fiber "Soylon" were only produced for a short time. Among them, the casein protein fiber "Chinon" of Japan Toyo Textile Company became one of the top ten inventions of chemical fiber in the world in 1968. However, its main component is grafted copolymer of casein protein and acrylonitrile. Because the cost of raw materials is too high, and its strength is insufficient, heat resistance is not good, so far it has not been used in large quantities.

From the end of the 19th century to the 1930s (before 1938), it can be called the innovation and initial stage of artificial fibers. Artificial fiber is a branch of chemical fiber, so of course, it is also the innovation and initial stage of chemical fiber. It is characterized by a large number of cellulose and protein as raw materials of artificial fiber varieties have come out, especially viscose fiber has begun large-scale production, to make up for the serious shortage of natural silk. Of course, fiberglass also has an ancient history, and it improved in the 1930s and became commercially important. Therefore, it should also have a place in the first generation of man-made fibers.

The development of synthetic fibers

Another branch of the chemical fiber family - synthetic fibers, until the industrialization of artificial fibers half a century later, with the advent of a large number of synthetic polymers and the establishment of the concept of modern polymers, it was on the stage of history.

chlorylon

In 1913, the German F.K latte obtained the first patent for the manufacture of polyvinyl chloride fibers from synthetic raw materials.

In 1931, the German IG chemical company adopted the invention of F.Klatte and realized the industrialization of PVC fiber in 1934, making it the earliest synthetic fiber produced in the world. However, due to its shortcomings such as poor heat resistance, the development is slow.

Polyamide (nylon) fiber

The most famous in the history of synthetic fiber is polyamide (nylon) fiber.

In 1928, Harvard University professor W. H. Carothers published a study on polycondensation into chain molecules and ring molecules. This pioneering work led to the true beginning of the era of synthetic fibers.

In the spring of 1935, he successfully synthesized polyamide 66 with hexamethylenediamine and adipic acid and spun it into silk strips. Du Pont established an intermediate pilot plant in 1938, successfully produced polyamide 66 fiber called "Nylon" in 1939, and was put on the market in 1940, becoming the world's first large-scale production of synthetic fibers for textile.

During this period, P.Schlack of IG Company in Germany successfully synthesized polyamide 6. In 1938, polyamide 6 was first spun into a coarse monofilament, and in 1940, it was spun into a filament, called "Perlon". However, due to the war, large-scale production of the Perlon was not carried out until 1950.

Polyamide fiber is widely used, and its output still ranks second in the chemical fiber family. The advent of polyamide fiber also opened the first melt spinning technology. Because previously all chemical fibers were spun by dry spinning process (such as acetate fiber) or wet spinning process (such as viscose fiber, nitrate fiber, copper ammonia fiber, polyvinyl chloride fiber, the latter of which was also spun by dry spinning process).

polyester

In 1930, W. H. Carothers invented aliphatic polyester, but the low melting point was not conducive to melt spinning.

In 1941, J.R.Hinfield and J.T.Ickson of Calico Printers Association, a dyeing and finishing company in the United Kingdom, successfully studied the polycondensation of terephthalic acid and ethylene glycol, and in 1944, the melt spinning was used to produce silk strips.

In 1947, ICI in the United Kingdom adopted melt spinning technology to realize the industrialization of polyethylene terephthalate fiber. DuPont bought the patent from the United Kingdom and began mass production of polyester fiber Dacron in 1953. Polyester fiber is widely used, and its production has exceeded polyamide since 1972, ranking first in the chemical fiber family.

Acrylic fiber

In 1894, the French chemist C. Melaeu first produced polyacrylonitrile. Since melt spinning could not be carried out, many American and German companies began to search for polyacrylonitrile solvents in the 1940s.

In 1934, H.R. ein of German I.G.Farbenindustrie company used concentrated aqueous solutions of quaternary amine salt and inorganic salts such as NaSCN and ZnCl2 as solvents to carry out the wet spinning test of polyacrylonitrile.

In 1942, H. ein and R.C. Houtz of DuPont Company in the United States respectively identified dimethylformamide as a solvent for polyacrylonitrile. DuPont established a pilot plant in Wagnesboro in 1944, and in 1950 chose the dry spinning route to industrialize the polyacrylonitrile fiber "Orlon".

Vinlon

Polyvinyl alcohol was synthesized in Germany in 1927.

In 1931, W.O.Hermann and W. Heheel began wet spinning experiments for polyvinyl alcohol. However, because this fiber is easily dissolved in water, it has little practical value.

In 1939, Ichiro Sakurada of Japan made a fiber with good heat resistance to water by studying the formalification and heat treatment of polyvinyl alcohol fiber. The fiber was put into industrial production by Japan in 1950. 

polyurethane

The German Bayer company began to develop polyurethane elastic fibers in the 1930s.

In 1941, polyurethane elastomers were synthesized by diisocyanate polymerization. In 1949, polyurethane elastic fiber was prepared by reaction spinning.

In 1959, the United States Du Pont company realized the industrialization of polyurethane elastic fiber "Lycra" through the dry spinning route.

Acrylic fiber

In 1954, Zieglerf used a low pressure polymerization method to make high-density polyethylene that could be spun. G.atta changed the catalyst composition to make isotactic polypropylene.

In 1957, Zieglerf-Natta catalyst was widely used in propylene polymerization. In 1960, the Italian company Montefibre industrialised polypropylene fibre. 

During this period, the artificial fibers developed were three acetate fibers (1954), and the synthetic fibers developed were polyethylene, polystyrene, polyvinylidene chloride, polytetrafluoroethylene, etc., but the output was not large. Large-scale industrial production is mainly polyester, polyamide, polyacrylonitrile and polypropylene fibers. In recent years, polyurethane elastic fiber has developed rapidly, and the global production capacity reached 451,700 tons in 2005.

From the 1940s to the 1950s, it can be called the stage of synthetic fiber innovation and start, and the rapid growth of artificial fibers. It is characterized by the emergence of many synthetic fiber varieties, especially polyamide, polyester and polyacrylonitrile, the three most important synthetic fibers in the 1950s have been put into production. At the same time, man-made fibers (mainly viscose fibers) from the variety development to large-scale change, the rapid surge in production, to 1950 output has reached 1.612 million tons, accounting for 94.4% of the total production of chemical fibers.

From the 1960s to the mid-1970s, it can be called the stage where artificial fibers tend to mature and synthetic fibers grow rapidly. The production of man-made fibers, while still increasing, has leveled off since the mid-1960s (the average annual growth rate declined from 4.93% in 1950-1960 to 2.03% in 1960-1970). Synthetic fibers from the variety development to large-scale change, production soared rapidly, from 702,000 tons in 1960 to 7.436 million tons in 1975, the proportion of total chemical fiber production increased from 20.9% in 1960 to 69.7% in 1975, and in 1968 for the first time more than man-made fibers. Polyester fiber, in particular, has developed very rapidly. At this time, the chemical fiber industry has developed to the stage of high-efficiency production, automation, large-scale production plants continue to put into production to meet the needs of real life, production by leaps and bounds, has become a representative of the high economic value of the industry, it has to marvel at its rapid progress.

From the mid-1970s, the chemical fiber industry in economically developed countries entered a mature stage, and the growth rate began to slow down. However, the developing countries and regions are in the stage of growth. Therefore, since then, the development trend of chemical fibers has two characteristics. On the one hand, the use of chemical fibers continues to expand, especially the proportion of decorative and industrial applications is gradually increasing. As a result, the total production of chemical fibers in the world continued to increase, but the rate of increase slowed significantly, with the average annual growth rate falling from 9.41% in 1960-1970 to 5.36% in 1970-1980, and even a negative growth of man-made fibers. The production of synthetic fibers also experienced a negative growth in 2005 (0.3% lower than in 2004). On the other hand, competition in the chemical fiber market has intensified. In order to expand the use of products and increase the competitiveness of products, fiber manufacturers pay more attention to new product development and strive to seize the initiative in market competition. The development of chemical fibers has entered a stage in which the development focus has shifted from "quantity" to "quality" and from conventional products to new products.

From "quantity" to "quality", from conventional products to new products

A feature of this phase is the flood of new products. Both the modification of the first generation of chemical fibers and the research and development of a new generation of chemical fibers. If divided by performance, the large varieties of chemical fibers that have been industrialized from the 1930s to 50 years can be called first-generation chemical fibers or conventional chemical fibers. These fibers are mainly used in the field of clothing. The new generation of chemical fiber mainly refers to the above mentioned differential fiber, functional fiber and high performance fiber. Since differentiated fibers are new products derived from large varieties of conventional fibers, some of them (such as colored fibers) have become conventional chemical fibers with the expansion of production.

Another characteristic of this phase is its long duration. Its origins can be traced back to the 1960s. For example:

1960 viscose based carbon fiber, imitation silk (triangular shape)

1962 meta aromatic polyamide fiber

1965 para-aromatic polyamide fiber

A hollow fiber artificial kidney from 1967

1970 polyacrylonitrile based carbon fiber, etc.

The high point of development was in the 1980s and 1990s. A large number of differentiated fiber products are transformed from technology into products. Its light Monsanto company launched more than 250 colored fibers in 1987. Japan introduced the "new synthetic fiber" in 1988. The production of high-performance fibers is increasing, and the variety is increasing. Polybenzodioxazole (PBO) fiber is its representative. A number of new functional fibers such as far-infrared, anti-ultraviolet and negative ions have been developed. At the same time, smart fibers, known as the third generation of chemical fibers, began to emerge, such as the United States Gateway company (now renamed Outlast Technology company) began to produce and sell heat storage and temperature control fibers in 1997.

In the process of developing new products of chemical fibers, some new spinning methods have been formed. Among them, there are mainly shaped spinneret spinning, composite spinning, wet and dry spinning, gel spinning, liquid crystal spinning, emulsion spinning, carrier spinning, phase separation spinning, centrifugal spinning, eddy current spinning, flash spinning, high-speed air melt-blowing, electrospinning and film cutting and fibrillating. 

This stage has continued into the 21st century, organic-inorganic hybrid fibers, nanofibers and other research is in the ascends, and will continue. In particular, smart fibers will fully show their charm as the third generation of chemical fibers in the 21st century.

Finally, another important type of fiber should be mentioned - ecological fiber. It is different from the first, second, and third generation chemical fibers, and the difference from other fibers is not its properties, but its relationship with the environment. Due to the large amount of "three wastes" produced in the process of chemical fiber production, especially the production of viscose fiber has caused serious pollution to the environment; Moreover, the existing synthetic fiber is based on non-renewable petroleum resources, and most of its waste is non-degradable, so the research and development of renewable resources, clean production process and degradable waste fibers meet the requirements of sustainable development, and become a hot spot of international research and development.

The development of ecological fibers can be traced back to the 1960s. For example, in 1962, the American Cyanamid company made an excellent absorbable suture with polylactic acid. In 1969, Eastmann Kodak patented a new solvent for cellulose, methyl morpholine oxide (NMMO). Since the 1990s, a number of ecological fibers have been industrialized. The most representative of them are Lyocell fiber and polylactic acid fiber. In addition, although the amount of chitin and chitosan fiber, collagen fiber, alginate fiber is not large in the field of clothing, it has achieved an important position in the medical field. Regenerated protein fibers, such as soybean protein fibers, which had been short-lived in the 1930s and 1940s, also received renewed attention because of their ecological fiber characteristics.