Products of Chemistry: Rayon
Products of Chemistry: Rayon
Products of Chemistry: Rayon
GEORGE KAUFFMAN
products of chemistry California State Univenihl.Fresno
Fresno, CA 93740
Rayon
The First Semi-synthetic Fiber Product
George B. Kauffman
California State University, Fresno, Fresno, CA 93740
The use of natural fibers (flax,wool, hemp,
cotton, etc.) for textiles (woven materials) Table 1. World Fiber Production in Billions of Pounds (1,3a)
predates recorded history. However, from
the introduction in the late 19th century of Rayon
"Chardonnet silk'-the fust type of rayon to Year Rayon Noncellulosic Total Natural Total %of %oftotal
be marketed, synthetic fibers have chal- manmade Man- manmade
lenged the long-standing monopoly of natu- made
ral fibers for textile and industrial use and
have exerted a large and growing economic 1969 7.87 8.29 16.16 39.12 55.28 48.45 14.1
impact throughout the world. By 1938 U. S. 1978 7.31 21.94 29.25 32.15 61.40 24.99 11.9
rayon consumption was 300 million pounds
and exceeded wool consumption for the first of the Forthe month of December 1990the total U. S. production of rayon was 36.9million pounds or5.42%
total synthetic fiber production of 681 4 milllan pounds (36).
time. However, i t still only amounted to
about 10% of the total cotton consumption.
Between 1950 and 1970 total world fiber production in- dacron (polyester), which the chemist synthesizes from
creased from 35 billion to 55 billion pounds. About one- low-molecular weight compounds by polymerization
third of this increase was due to natural fibers, while two- (chain-building) re-
thirds was due to synthetic fiber production, which actions. Reactions for
increased fourfold during this period-from 13 percent of producing artificial
total fiber production in 1951 to 19 percent in 1969 (1,2). fibers were discov-
Before World War I1 the production of manmade fibers ered during the 19th
consisted almost entirely of rayon, but following the war century, but these ii-
new types of mmpletely synthetic fibers, such as nylon, bers did not become "'.H.~
polyesters, acrylics, and polyolefins, with specificdesirable commercially signifi-
properties have assumed an increasing proportion of both cant until the 20th
the synthetic fiber and total fiber market (3)(Table 1).Yet,
century, when pro- ....
during the early 1970's the annual world production of
rayon was still greater than that of any other fiber except cesses for their man-
cotton, and rayon continues to supplement the use of silk ufacture were ex-
and other natural fibers in a number of textile fields. ploited, along with
those for plastics and
Rayon other polymers to
Rayon i s a generic term for an artificial textile material which they are
composed of reconstituted, regenerated, and purified plant closely related. De-
substance, viz., cellulose or cellulose compounds. Because veloped as a substi-
its long-chain polymer structure is already provided by na- tute for silk, rayon is
ture and is only modified and partially degraded by chem- sometimes called " a r
ical processes, it is called a semi-synthetic fiber in contrast titicid silk" or "wood
to completely synthetic fibers such as nylon (polyamide)or silk," but this i s a
misnomer since its
chemical composi-
tion is completely dif-
ferent from t h a t of
silk. In 1924 this first
semi-synthetic fiber
was given the mined
name rayon, espe-
cially in the United Figure 2. Puckered sheet structure of cel-
S t a t e s and Great lulose chains (the dots denote hydrogen
Figure 1. Chair foml d cellobiose unit in cellulose (Ila), Britain (2,4a, 5). bonding) ($2).
Nitrocellulose Rayon
The first practical progress toward producing a synthetic
fiber was made in Basel, Switzerland by Christian
Friedrich Schonbein (1799-1868) (Fig. 31, who in 1846 ac-
cidentally treated cellulose with a mixture of sulfuric and
nitric acids and produced a cellulose derivative that he
Figure 3. Christian Friedrich Schonbein (1 799-1868). called guncotton (SehiesswoUe) and proposed as an explo-
sesses this solvent power, a n observation made the year fabrication processes were well kept secrets, forcing them
before by Peligot (38,391. to carry out their own research and to solve numerous
Schweizer's last publication on the subject (40) was a let- chemical and mechanical problems (45).Aiter two years of
ter to Otto Lime Erdmann (1804-1869), editor of the Jour- experimenting, Fremery and Urban fded their first patent
nal fur praktische Chemie. He disagreed with Erdmann's under the name of Herman Pauly, director of a technical
view that "cellulose is not really dissolved in Kupferoryd- school a t Munich Gladbach, intended to avoid both compe-
Ammoniak but only strongly swollen" (41) and asserted tition and attracting the attention of other researchers
that the cellulose is actually dissolved. Reihlen later found (47).
that cellulose dissolved in Schweizer's reagent because of I t is sometimes claimed that this first practical patent
the formation of complex compounds between Cu2+and for cuprammonium silk was merely a repetition of
(C6H805)Zions (42). The equilibrium reaction Despeissis' patent of a dozen years earlier. However, unlike
the earlier patent, i t described a technical method for spin-
ning the product and is truly the fundamental basis for the
cuprammonium silk industry. With their additional subse-
is pH dependent: cellul~~se ions are present in appreciable quent patents, as well a s those of the German Emil
concentration only in a rather strongly alkaline solution. If Bronnert, Fremery and Urban began to manufacture a
the hydroxide Ion concentration is lowered, the cellulose is cuprammonium artifical silk called "GlanzstofP' at their
reprecipitated. If it is increased by addition of NaOH solu-
Oberbruch works, beginning in 1898.
tlon. the crllulosc redissolves 1421.The phvsical prooerties
andchemical reactions of Schweizer's reagent have been In 1908 Emil Thiele of J.-P. Bemberg, .. a prominent
. Ger-
investigated extensively (43). man tcxtile firm, perfected the process hy usingas starting
Several investigators recommended t h e u s e of material cotton linters (short fibers that stick to thccotton-
Schweizer's reagent to dissolve cellulose, but i t was not seeds aRer a first ginning), which were more economical
until 1890 that the Frenchman Louis-Henri Despeissis de- and which imparted to the thread more resistance as well
veloped and patented a n industrial process for makingtex- as a softer feel. This so-called "Bemberg silk" was used in
tile fibers of artificial silk using cellulose dissolved in this the hosiery industry for making stockings. The prosperity
solution(4a, 13b, 30,4446). Unfortunately, he diedin 1892 of the cuprammonium process was relatively short-lived. I t
without having utilized his patent on an industrial scale, w a s generally abandoned around 1910, except by
and his process entered the public domain. However, Max Bemberg. However, cuprammonium rayon, prepared by
Fremery, a German chemist from Cologne, and Johan dissolving cellulose in Schweizer's reagent, extruding the
Urban, a n Austrian engineer, who had worked together in resulting solution through spinnerets (nozzles),regenerat-
1885 on the manufacture of carbon fdaments in a n electric ing the cellulose in dilute sulfuric acid, and washing the
light factory in Rotterdam, collaborated in improving fiber in acetic acid (48,49), is still used to produce the most
Despeissis' process. I n 1892 they founded the Rheinische expensive rayon-me most resembling silk. Its extra fme-
Gliihlampen Fabrik, Dr. Max Fremery & Co. to manufac- ness and strength, attractive hand (fabric properties that
ture electric light bulbs. They established a factory in an can be sensed by touching the material, such as resilience,
old paper-making plant at Oberbmch near Aachen. They smoothness, body, etc.), subdued luster, and excellent
obtained a bank credit i n 1895 from t h e Bergische- draping properties justify its added cost. It is used for sat-
Markische Bank, a condition of which was that they con- ins, sheer fabrics (chiffons, nets, and ninons), underwear,
tinue their research to produce textile filaments of artifi- dress fabrics, linings, dresswear, sportswear, curtains,
cial silk. suitings, upholstery fabrics, bedsheets, and other fabrics
Fremery and Urban faced considerable difficulties in (2). Almost all artificial kidney dialysis units now use
complying with this condition. An industry for manufac- membranes prepared from films and hollow fibers of
turing artificial silk from collodion already existed, and its cuprammonium rayon (50,511.
-
Schutzenberger) and Charles Naudin (1315-1899) in 1869
(56).For many years there was considerable confusion wn-
[c,yo2(otl)p,
Na+ln+ n- fCeWz(oH)&+C-s, Na*ln cerning the number of acetyl groups that could be intro-
II duced into the cellulose molecule; however, it is now clear
s that onlv three hvdroxvl e r o u ~ per
s cellulose unit can be
Soda cellulose Cellulose xanthate (wsmse)
esterifiei, and the existenee oihiiher acetates must be at-
The unstable viscose solution is allowed to "ripen" for tributed to degradation or acetolysis of the cellulose, which
yields lower carbohydrates with more hydroxyl groups. In
several days a t carefully controlled temperatures; during
1894 viscose develooers Cross and Bevan patented the
this period i t undergoes repeated filtrations, and it in-
creases in viscosity. It is then extruded through holes in a
first industrial process for the manufacture of cellulose
triacetate, which was soluble in chloroform. In 1903 the
spinneret, and the resulting jet of viscose next enters a co- American chemi~tGeorge Miles (18611-19391 succeeded in
agulating bath of NaHS03, ZnS04, and dilute HzS04, in dissolvina panlallv hydrolyzed cellulose acetate in ace-
which it is reconverted into cellulose, which coagulates to tone. ~ o w e i e rthebricess
, was not used a s the basis for a
form a solid fdament: textile fiber until 1907, when it was so applied by Prince
Guido Henkel von Donnersmark in Germany (13b).
Durine., World War I the British Cellulose & Manufactur-
ing Co. began manufacturing at its large Spondon. Eng-
land plant an acetone-soluble cellulose acetate developed
by the Swiss chemist Henn Dreyfus, one of the company's
heads. The product was used as a dope (fabric coating, for
"---.
32. Kaufhm, 0. B.J Chem. Edue. 1984,61,1095