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Polymer History

Designed Monomers and Polymers
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Polymer History
Dorel Feldman
To cite this article: Dorel Feldman (2008) Polymer History, Designed Monomers and Polymers,
11:1, 1-15, DOI: 10.1163/156855508X292383
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Designed Monomers and Polymers 11 (2008) 1–15
Polymer History
Dorel Feldman ∗
Department of Building, Civil and Environmental Engineering, Concordia University,
1455 De Maisonneuve Blvd.W., Montreal, Quebec, Canada H3G 1M8
During the last century and a half, new families of engineering materials known as polymers have been
discovered and produced, that have not only challenged the classical materials but have also made possible
the realization of new products which have contributed to extend the range of activities of mankind. This
paper is a brief review of the history of the most important groups of polymeric materials, such as plastics,
fibers and elastomers. In the growth of polymeric materials during the last century and a half, plastics are
the leader followed by fibers and elastomers.
 Koninklijke Brill NV, Leiden, 2008
Polymers, plastics, fibers, rubber, review
1. Introduction
Polymers are at the basis of important industrial goods. Their rapid growth in
production is caused, beside social factors, by the necessity to replace classical
The word “polymer” was introduced by the Swedish chemist J. J. Berzelius. He
considered, for example, benzene (C6 H6 ) to be a polymer of ethyne (C2 H2 ). Later
this definition underwent a subtle modification [1].
Polymer science is a relatively new discipline which deals with plastics, natural
and synthetic fibers, rubbers, coatings, adhesives, sealants, etc.; all of these materials nowadays have become very common.
The concept of polymers is one of the great ideas of the 20th century. It emerged
in the 1920s amid prolonged controversy and its acceptance is closely associated
with the name of H. Staudinger who received the Nobel Prize in 1953.
Many examples of synthetic polymers can be mentioned; some everyday, like
polyesters or nylons, others less known, like the ones used for medical applications
for organs, degradable sutures, etc.
Tel.: (1-514) 848-2424, ext. 3202; Fax: (1-514) 848-7965; e-mail: feldman@bcee.concordia.ca
 Koninklijke Brill NV, Leiden, 2008
D. Feldman / Designed Monomers and Polymers 11 (2008) 1–15
On the basis of economic and application considerations plastic materials can
be divided in commodity (characterized by high volume and low cost) and engineering plastics (higher cost and low volume). In the first group are considered
polyethylene (PE), polypropylene (PP), poly(vinyl chloride) (PVC) and in the second polycarbonate (PC), poly(etheretherketone) (PEEK), polyimide (PI), etc.
Fibers, natural, artificial (modified natural) and synthetic, are characterized by
high aspect ratio, high strength and modulus and other properties depending on
their applications.
Elastomers exhibit the ability to stretch and retract rapidly.
2. Plastics
The first plastic material was based on nitrocellulose and was obtained by Parkes
in 1862 and Hyatt in 1866. The addition of camphor to nitrocellulose led to the
first thermoplastic (a modified natural polymer) known as celluloid. By 1900 this
material was used for movie film.
In about 1897, galalith (gala = milk, lithos = stone) was produced in Germany
by reacting casein (a milk protein), with formaldehyde [2].
The first synthetic thermoset polymer (a phenol-formaldehyde (PF)), known as
Bakelite, was obtained in 1907 by Baekeland through the polycondensation of
phenol with formaldehyde. Bakelite was commercialized in 1909–1910 [3]. The
commercial development of this PF material is considered to be the beginning of
the truly synthetic plastic era and of the plastic industry, although cellulose nitrate
(semi-synthetic) had been known and in use for some time.
The successful use of PF resin catalyzed the development of other polycondensation products based on formaldehyde (F) with urea (U) and melamine (M), known
as amino resins, aminoplasts or aminoplastics. Such polymers were first described
by Tollens in 1884 and were patented by John in 1918 [4]. Aminoplasts, contrary
to phenoplasts, can be made translucent or in light colors [5]. In 1926 Rossiter produced aminoplasts based on formaldehyde and mixture of urea and thiourea [6].
The production of MF resins began in the mid-1930s [7].
Unsaturated polyesters (uPES) were discovered in 1933 by Ellis and commercialized around 1942. These polycondensation products are known as alkyds, name
which appears to have been derived from alcohol (alk) and acid (yd); they are used
primarily as coatings. From the same family, glycerophthalic (Glyptal) coatings involve glycerol and phthalic anhydride [5].
The existence of vinyl chloride (VC) was reported by Liebeg and Regnault in
1835, but its ability to polymerize was not fully known at that time. The effect of
sunlight on VC was later investigated by Baumann in 1878, when it was observed
that a white substance formed as a result. Very little progress was then made until
1912–1916 when Klatte discovered the basis for VC photo-polymerization [8]. In
1926 Ostramislenski patented flexible film cast from a solution containing PVC and
a plasticizer [4]. Also it was discovered that PVC became a flexible material that re-
D. Feldman / Designed Monomers and Polymers 11 (2008) 1–15
sembled rubber or leather when it was heated in the presence of a high-boiling-point
liquid. This led to the use of phthalate esters as plasticizers for PVC. The industrial
production of PVC using emulsion and suspension technologies had occurred by
the start of WW II. During the war, the acute shortage of rubber accelerated developments in this area, particularly in electrical cable insulation and sheathing [8].
After the war developments were concerned largely with plasticized PVC, handled mainly by extrusion, calendaring and paste techniques (plastisols).
The high-pressure polymerization of ethylene was accidentally discovered in
1933 by Gibson and Fawcett. A small-scale operation in 1937 was followed by
the first commercial production in 1939 [6].
Styrene (S) was obtained by Bonastre in 1831 by distillation of storax balsam; it
was also examined by Simon in 1839, who observed that after storage for several
months the liquid became a solid (which he wrongly supposed to be an oxide). In
1845, by heating S, Blyth and Hofmann obtained, even in the absence of oxygen,
a similar solid which they termed metastyrene. Practical uses of polystyrene (PS)
were considered by Kronstein (1902) and Matthews (1911); the last one described
the thermal and catalytic styrene polymerization to yield a substance able to replace
celluloid, glass and hard rubber [9]. The problem of preventing premature polymerization of S impeded development until Dufraise and Moreau used inhibitors in
1922. Contributions to the study of S polymerization are due to Ostromislenskii
(1911–1925) and Staudinger (1929–1935) [9].
Since the 1930s the monomer has been used in co-polymers with elastomeric
characteristics [6]. Large-scale commercial development dates from 1935 [11, 12].
High impact grades were produced since 1948 and isotactic PS was obtained by
Natta in 1955 [9]. Styrene is used for important co-polymers and terpolymers such
as styrene–acrylonitrile (SAN), styrene–divinyl benzene (S-DVB), styrene–maleic
anhydride, acrylonitrile–butadiene–styrene (ABS) and others [10].
Polymers based on acrylonitrile, butadiene and styrene were first introduced in
the late 1940s. The first patent that claimed a product made of a physical mixture of
B-AN elastomer and AN-S co-polymer was issued in 1948. Improvements in polyblending technology and the development of grafting processes during the 1950s
led to a significant improvement of ABS terpolymer properties [13].
Poly(methyl methacrylate) (PMMA) is produced, first in 1933, for aircraft glazing and for a variety of applications particularly where transparency and/or good
weathering resistance is important [2].
Around 1938 Schlack discovered poly(ε-caprolactam) (polyamide 6, PA-6)
known as nylon 6 which was commercialized in 1939. Carothers started polycondensation studies in 1929 and obtained nylon 66 as a fiber-forming polymer in 1935.
The production of PA as a plastic started in 1941 [5, 14]. Since then many different
polyamides for plastics and fibers were produced. More recently, in 1994, a highperformance PA (Zytel) was commercialized.
The development of fluoro-polymers began with the synthesis of poly(tetrafluoro
ethylene) (PTFE) in 1938: this was a major leap forward in material science.
D. Feldman / Designed Monomers and Polymers 11 (2008) 1–15
Yet the new polymer could not be fabricated by melt processing. The next two
forms of PTFE, fine powder and dispersion, were also not melt-processible. The
pursuit of more easily processible fluoro-polymer led to fluorinated ethylene–
propylene co-polymer (FEP), which could be melted and processed in an extruder.
Poly(perfluoroalkoxy) (PFA), which was introduced in 1973, offers both melt
processing and high thermostability like PTFE. Some other polymers in this family were discovered, such as poly(chloro-trifluoro ethylene) (PCTFE), poly(vinyl
fluoride) (PVF), poly(vinylidene fluoride) and other co-polymers and terpolymers
Saturated polyesters were first studied by Carothers starting 1929; he was able
to obtain a PES of propylene glycol and 1,16-hexadecanoic acid with an average
MW of 12 × 103 . As the aliphatic PES all had boiling points too low, he turned
his attention to polyamides. Later on studies on PES were done by Whinfield and
Dickson (1941–1946). The most important polymer in this group is poly(ethylene
terephthalate) (PET), produced first in 1955 and used as a plastic, film and fiber.
The original discovery leading to the world-wide interest in all classes of
polyurethanes (PU) was made by Bayer and his co-workers in 1937 as a competitive
response to the work done by Carothers on the polyamides. In 1947 Bayer published
an impressive account of the synthesis of PU and polyureas. In the 1950s the basic
technology used polyesters to obtain the flexible foams and polyether polyols were
introduced in 1957 [16]. Later on, PUs were found to be useful for the production of plastics (1961), elastomers, foams, adhesives, fibers and corrosion-resistant
coatings [17, 18]. A new transparent thermoplastic PU was produced recently [19].
In 1909 Prileschajew discovered that olefins would react with peroxy benzoic
acid to form epoxides. Peroxy acid epoxidations play an important role in epoxy
resin production [20]. Epoxy resins (EP) were first synthesized by Schlack (the
inventor of nylon 6), in 1934. Their curing reaction was discovered by Castan and
Greenlee (late in the 1930s) and polymer products were introduced in the market
towards the end of World War II. Although a number of different types are now
commercially available, the major share of the market is still held by systems based
upon the reaction products of epychlorohydrin and bisphenol A [7, 21, 22].
Vinyl ester resins, which may be regarded as hybrids of epoxy and polyester resin
chemistry, were developed in the 1960s. They are made by reacting epoxy resins
with ethylenically unsaturated carboxylic acid in order to give terminal unsaturation
In the early 1950s, Hogan and Bank discovered that ethylene can be polymerized
under moderate conditions (3–4 MPa and 70–100◦ C) with chromium oxide catalysts on silica support. Manufacture of high-density PE (HDPE) produced by this
procedure started in 1956. Currently HDPE is one of the largest commodity plastic
[23]. Shortly after (1953) Ziegler and Natta independently developed a family of
stereospecific transition-metal catalyst that led also beside HDPE to the synthesis
and commercialization in 1957 of polypropylene (PP) as a major commodity plastic
[8, 24–26].
D. Feldman / Designed Monomers and Polymers 11 (2008) 1–15
In 1898 Einhorn reported the formation of polycarbonates (PC) in the reaction
of phosgene with dihydric phenols. In 1902 Bishoff and Hedenstrom confirmed
this work using an ester-exchange reaction. These PCs were intractable, insoluble
materials, and for many years the plastics industry showed no interest in their development, though admittedly Carothers included aliphatic polycarbonates in his
work on polyesters and reported on these in 1930. That same year Carothers and
Natta prepared a number of aliphatic PCs. When bisphenol A was readily available
commercially due to contributions made by Schnell (1956), the time was opportune
for the development of bisphenol A polycarbonates. Such polymers became available for assessment in 1958 and the full-scale production commenced in 1959 in
Germany and 1960 in the USA [11, 27, 28].
In the same period, SAN co-polymer (1954) and polyacetals (1956) were synthesized for the first time.
Ionomers were first prepared in 1964 by co-polymerization of ethylene with a
small amount of an unsaturated carboxylic acid (acrylic or methacrylic acid), using
a high-pressure process. They have the characteristics of thermoplastic and thermosetting polymers. The commercial grades available in 1970s used either zinc or
sodium as the cross-linking ion [11]. An important class of ionomers are perfluoro sulfonate ionomers (PFSI), which are co-polymers of tetrafluoroethylene and a
perfluorinated vinyl ether containing a terminal sulfonil fluoride group (SO2 F) [29].
Polyimide (PI) resins, primarily of the thermosetting type, were developed after 1953 and became commercially available around 1963. The thermoplastic PI
result from the polyaddition of bismaleinimides and HZ-R-ZH compounds, where
HZ may be diamine, disulfide dialdoxim, etc. Although aromatic PI retain usable
properties at 300◦ C for months and withstand exposures of a few minutes well over
500◦ C, their applications have been limited [30]. Polyamide imide was introduced
around 1976 and polyether imide around 1982 [2, 5].
Flory suggested in 1956 that polymers containing long rigid (rod-like) units
could form anisotropic ordered solutions above some minimum concentration depending upon temperature and the length/diameter ratio. Later on in 1974, liquidcrystal behavior for a polymeric system was first observed in a concentrated solution of poly(benzyl L-glutamate) which forms a rod like α-helical conformation in
a variety of organic solvents. Liquid crystal polyesters may have been recognized as
early as 1965; they have highly aromatic structures. Aromatic polyamides (aramid)
form a nematic state, in which there is a parallel but not a lateral order [29].
Polysulfone was introduced around 1965. Polyarylsulfones were commercialized
in the period 1967–1976 and polyethersulfone around 1972. All polysulfones are
transparent, light yellow to amber polymers. Their high heat distortion temperatures
are only surpassed by aramides, polyimides and polyamideimides [2, 5].
In 1976 Kaminsky and Sinn discovered a new family of catalysts (a metallocene
complex) for ethylene polymerization. Kaminsky–Sinn catalysts and a variety of
their modifications afforded the synthesis of ethylene-α olefin co-polymers with a
high degree of compositional uniformity [23].
D. Feldman / Designed Monomers and Polymers 11 (2008) 1–15
PEEK, the most important member of the poly(aryl ether ketone)s (PAEK), has
become commercially available in 1978.
After 1980 continuous growth was recorded with the development of a number
of high performance polymers that could compete with traditional materials such
as polyamide 4-6 (1987), sindiotactic PS (1989) metallocene polyolefins, polyphthalamide (1991), and styrene–ethylene co-polymer and sindiotactic PP in 1992
[31, 32].
3. Fibers
The defining characteristic of a fiber is its thread-like form, without restriction on
chemical composition. Fibers can be metallic, mineral or organic. Nearly all nonmetallic fibers are polymeric materials, either natural, artificial (modified natural)
or synthetic. Natural fibers such as wool and cotton have aspect ratios in the order of 103 or greater. The organic fibers are carbon or heterochain polymers; the
major mineral fibers like glass and asbestos are macromolecular silicates. Organic
synthetic fibers are mostly thermoplastic, some are elastomeric and very few are
thermosets. Their history covers less than 75 years [33–35].
In the beginning, textile fibers came from nature: animal skins, hair, wool, silk
from silkworms, and plants like flax, cotton, hemp, etc.
The utility of flax and hemp twines was recognized even in the Stone Age. Flax
fabrics were used in pre-dynastic Egypt (fine linen cloth being woven in 3800 BC)
and in Neolithic lake dwellings in Switzerland.
References to hemp and ramie (fibers cultivated in temperate latitudes, and unknown to ancient Egyptians and Hebrews or to early Greeks) occur in Chinese
writings dating 2800 BC and in early Sanskrit literature. Jute appears to have been
cultivated in Bengal from the most ancient times.
Traditionally the culture of silk began in 2640 BC in China, where for many
centuries its origin and the art of manipulating it were kept secret (it did not reach
Japan until AD 300). There are Sanskrit records dating from 1000 BC that refer to
the working of silk in ancient India.
Wool sheep appear to have originated as mountain animals in Mesopotamia. It is
well known that their wool was employed for clothing at least 5000 years ago [10].
For centuries, all textiles came from fibers that were harvested from a plant,
animal or insect. Then, at the end of the 19th and beginning of the 20th century,
people discovered that they could create textile fibers of their own. Those early
fibers still originated from a natural source, cellulose from wood pulp, but soon
enough, in the 1930s, 1940s and 1950s, a stream of synthetic fibers came on the
scene that owed their origin in chemical plants instead of plants that could be grown
in the field [36].
The idea for producing artificial fibers seems to have been advanced first by
R. Hooke in his Micrographia, published by the Royal Society in 1665. In 1833
Braconnot described the nitration of various celluloses and Liebeg established the
D. Feldman / Designed Monomers and Polymers 11 (2008) 1–15
tendency of nitrated cellulose to decompose violently when heated. In 1847 Schonbein improved the nitration process by using sulfuric acid as catalyst. The first
fibers based on nitrated cellulose were produced by Swan. In 1890 Count Hilaire
de Chardonnet obtained so-called “artificial silk” based on this modified cellulose
In 1894 Cross and Bevan discovered that cellulose can be converted by alkali
and carbon disulfide to the water-soluble xanthate from which cellulose can be regenerated by various reagents. The new artificial fibers known as “viscose” had two
advantages over nitrated cellulose: they did not require (i) denitration and (ii) the
use of expensive solvents in their manufacture [37, 38].
Mercerized cotton realized by Mercer in 1844 results from physical modification
of cellulose by treatment with a sodium hydroxide aqueous solution [35].
Despaissis patented the cuprammonium process for the production of regenerated cellulose from a solution of cellulose in cuprammonium hydroxide
(Schweitzer’s reagent) in 1890 [10].
The commercial viscose (a process that is still in use) was not developed until
1903. The name rayon was accepted by all producers of regenerated cellulose fibers
in 1924 [39].
It is interesting to remember that, as early as 1926, Lilienfield prepared viscose
rayon filaments with unusually high modulus and high tensile strength. He used
highly xanthated cellulose [40].
The commercial cellulose acetate rayon fiber, process based on acetone solutions
of secondary cellulose acetate was developed and patented by Miles who partially
saponified the triacetate in 1903.
In the 19th century researchers reported unusually high molecular weights in
the case of some natural products. The ensuing confusion between the colloidal
theory and that of macromolecular concepts retarded the progress until Staudinger
championed the true macromolecular theory near about 1930. Thus, the beginning
of the polymer age was delayed until scientists accepted Staudinger’s theory [1].
Carothers is recognized as the inventor of the first synthetic fiber, known as nylon 66. In 1929 he published his theory of polycondensation and compared it with
polyaddition. His initial studies on aliphatic polyesters were done and results were
published before discovering the aliphatic polyamide with higher melting point;
this one could be spun into a useful apparel fiber suitable for many of the same
applications as natural silk. Nylon 66, made from a diamine and diacid, each with
six carbons, was commercialized before 1940 and continues to grow in importance
today [32].
It is mentioned in the literature [41] that in 1899 Gabriel synthesized polyamide
nylon 6. In the 1930s, Schlack repeated this synthesis and produced commercial
nylon 6 in 1940 by the polymerization of ε-caprolactam. Like nylon 66, nylon 6
is produced throughout the world and is used both as a fiber and an engineering
plastic [42].
D. Feldman / Designed Monomers and Polymers 11 (2008) 1–15
The first polyamide that was mechanically spun from a melt was nylon 9, which
had a moderately high melting point of 196◦ C. Considerably work was also done
with nylon 5-10 with a melting point of 200◦ C. Nylon 66 decomposes just above
its relatively high melting point of 265◦ C [43].
The derivation of nylon 11 from castor oil was developed by Zeltner, Genas and
Kastner in 1944, and its production started in 1949 [4]. Nylon 12 first came to the
market in Germany in 1959 [44].
Several polyesters were investigated by Carothers during a DuPont program that
started in 1929. These polyesters were mostly linear aliphatic and they were characterized by low melting points, considerable solubility in organic solvents and
poor resistance to hydrolysis. In 1941 Whinfield and Dickson obtained a aromatic
polyester, PET, and found it to have great promise as a fiber- and film-making polymer. Its large-scale manufacture started in 1953 [10, 27, 45, 46]. Hill, Carothers
co-worker, also contributed to the preparation of fiber-forming polyesters [47].
Acrylonitrile (AN) was prepared by Moreau in 1893. Poly(acrylo nitrile) (PAN)
was developed for fibers in 1940; patents based on the utilization of concentrated
aqueous solutions (in Germany) and organic liquids (USA) were obtained in 1942.
Pilot production of PAN started in USA in 1943, and the first acrylic fiber (Orlon)
was made in 1948 and put into commercial production in 1950. By definition acrylic
fibers contain 85% or more AN. Along with PAN was developed a class of fibers
known as modacrylic. By definition they are based on co-polymers containing less
than 85% but more than 35% AN by weight. Their production started in 1949.
Such kind of fibers often contain as co-monomer a high amount of vinyl chloride,
vinylidene chloride or vinylidene cyanide [10, 48].
Poly(vinyl alcohol) (PVA) was produced in 1924 by the saponification of
poly(vinyl acetate) (PVAc). PVA fibers (Vinylon) were produced in 1951 in Japan
by coagulating the extrudate from an aqueous PVA solution in an aqueous sodium
sulfate solution. Their insolubilization is done by treatment with formaldehyde [49].
Based on the discovery of heterogeneous stereospecific catalysts by Ziegler,
Natta obtained in 1954 crystalline polypropylene (PP). Commercial production of
PP fibers and filaments started in 1957. The excellent wear and resistance to staining associated with low cost led to the use of such fibers for various applications
The first aromatic polyamide (aramid) fiber based on poly(m-phenylene isophthalamid) (MPD), known as HT-1 and later re-named, was commercialized under
the trade name Nomex by DuPont in 1967. It was also produced in Japan and USSR
in 1970. These aromatic polyamides have at least 85% of the amide linkages attached directly to two aromatic rings.
In 1973, DuPont started production of another aromatic polyamide fiber, a
poly(p-phenylene terephthalamide) marketed as Kevlar; this fiber has exceptional
strength competitive with glass, steel and carbon fibers [11, 50].
Aromatic polybenzimidazoles (PBI) were synthesized by Vogel and Marvel in
1961, with anticipation, later justified, that these polymers would have exceptional
D. Feldman / Designed Monomers and Polymers 11 (2008) 1–15
thermal and oxidative stability. In 1983 PBI fiber, spun from solutions of poly(2,2 (m-phenylene)-5,5 -bibenzimidazole) for a wide range of textile applications, was
commercialized [51].
Carbon fibers, first used as light bulb filaments in 1879, trace their modern history back to about 1942. The first commercially produced carbon filament was made
from a cellulosic precursor for its application as incandescent lamp filament. Systematic work regarding carbonization of rayon and PAN yarns and fabrics was initially investigated by Union Carbide during World War II. Two processes for manufacturing high-strength and high-modulus carbon fibers from rayon and PAN were
invented almost simultaneously in 1959 and 1961. Later, in 1963, a high-modulus
fiber made from pitch as precursor was invented. Since 1980, ultra-high-strength
fibers from PAN and ultrahigh-modulus fibers from pitch have been developed and
are used extensively in the aircraft and spacecraft structures [52–55].
Spandex fibers, which by definition consist of at least 85% of segmented
polyurethane, were invented in the 1950s to improve on the process and properties of rubber fibers; they became commercial around 1960 [56].
4. Elastomers (Rubbers)
The first mention of rubber trees is to be found in De Orbe Nuovo by Pietro Martire
d’Anghiera, published in latin in 1516. The outstanding source of natural rubber, the large forest tree Heveea Brasiliensis, occurs in the southern equatorial
region, mainly in Malaysia, Indonesia, Thailand, Ceylon, India, Cambodia, Vietnam, Brazil, Africa and some other countries from Asia and South America. Such
trees were called “Cau-uchu” or “weeping wood” in South-America. The name was
derived from the use of the material as an eraser, “rub off pencil marks”, an application introduced by Priestley in 1770. The original name of caoutchouc is still used
to denote rubber in many languages other than English, where it is reserved for the
rubber hydrocarbon [57, 58].
Until 1823, when Macintosh patented the use of coal tar, the lack of a satisfactory
solvent delayed the progress of rubber utilization and the natural rubber remained
little more than an academic novelty.
In 1839 Goodyear found that heating rubber with sulfur and white lead gave it
far superior properties. Hancock exploited this process, termed vulcanization by
Brockeden, to provide an elastic material insoluble in common solvent, from the
initial thermoplastic one [48]. The so-called cure, namely treatment with sulfur
chloride, which is now obsolete, was discovered by Parkes in 1840 [57].
Page reported the results of his studies on natural rubber in 1847. This endeavor
may well represent the onset of interdisciplinary research activity involving macromolecules [59].
Faraday showed in 1826 that natural rubber was a hydrocarbon of empirical
formulae (C5 H8 ) and Williams gave the name isoprene to the volatile liquid obtained by destructive distillation of natural rubber of composition C5 H8 . A reversing
D. Feldman / Designed Monomers and Polymers 11 (2008) 1–15
process done by Bouchardat in 1879 led to a rubbery material. A similar material
was obtained by Tilden in 1884 using isoprene from terpentine.
The turn of the century led to the development of the automobile and with it the
pneumatic tire. The first inflated tire to be commercially successful was based on the
invention done by Dunlop (1888–1889) and the first successful cord-tire (a bicycle
type tire) was invented by Palmer in 1893. Balloon low pressure tires were first
marketed in 1923 and the tubeless tires date from 1951 [57]. The synthesis of an
isoprene polymer was first reported in 1875 [61].
In the late 19th century it was already known that conjugated diene hydrocarbons
are able to produce elastic items. Indeed in 1881 Hofmann prepared an elastomer
from 1,3-pentadiene and Couturier polymerized 2,3-dimethyl-1,3 butadiene in 1892
[60]. At the beginning of 20th century Matthews, Perkin Jr. and Weismann (1909–
1910) studied the polymerization of isoprene. Similar experiments were done by
Harries (1911), who produced methyl rubber (poly(2,3-dimethyl butadiene)). The
synthesis based on coordination catalysts (Ziegler–Natta type) of an elastomer
equivalent to natural rubber was reported in 1954. One year later a polyisoprene
based on dispersed lithium catalyst was obtained; both these elastomers had more
than 90% cis units [61]. Very active before 1914 in finding new synthetic rubbers were Kondakoff, Butlerov, Ostromislensky and Lebedev, who were making
butadiene as early as 1910 and whose work played an important role in the development of the synthetic rubber industry [57]. During World War I two types of
methyl rubber were obtained and, because of the rise of the price of natural rubber,
the research in view to obtain replacements was intensified. Buna rubber, made by
sodium-catalyzed polymerization of butadiene, became available in the late 1920s
One of the most widely used rubbers is the co-polymer of styrene (S) and butadiene (B), known as SBR. In the 1920s the ability of emulsion polymerization
in the presence of initiators led to polymers with high molecular weight. The first
B-S co-polymer, Buna S was obtained during the next decade based on the research done (1929–1930) by Bock and Tschunker. By 1934 a pilot plant was making
Buna S, which was produced on a large scale during World War II [10, 62]. Major
technical advances (1941–1943) were the introduction of redox initiators making
possible cold polymerization, oil extended co-polymers and of modifiers to regulate the molecular weight [10]. Another interesting development in the field of this
group of rubbers was the production in 1965 of block co-polymers [57]. 75% of all
SBR in North America goes into tires because it provides good traction properties
and abrasion resistance [63].
Buna S discovery and production was followed shortly thereafter (1935) by analogous butadiene-acrylonitrile (B-AN) co-polymer, a highly polar elastomer known
as Buna N [57, 61, 64]. Hydrogenated B-AN co-polymer was commercialized only
in 1984 [65].
In the 1930s metallic sodium (1932) or potassium was used to catalyze butadiene
polymerization. Two types of PB have emerged as important commercial elas-
D. Feldman / Designed Monomers and Polymers 11 (2008) 1–15
tomers: cis-polybutadiene (1956) and medium-cis-polybutadiene (1958). In 1958
Crouch and Kable developed the solution polymerization of butadiene. Although
many chemists new that the structural unit of natural rubber is isoprene, they were
not able to synthesize its polymer until solution polymerization and organo-metallic
catalysts were tried in the 1950s. These studies led to the synthesis of polybutadiene [66].
The first synthetic rubber to achieve true commercial success was polychloroprene (1932) obtained by emulsion polymerization of chloroprene; unlike the natural rubber this one could be vulcanized by zinc oxide, and a more important
advantage is resistance to oil. This elastomer’s use is declining as many applications
are switching to other elastomers, including ethylene-propylene-diene monomer
(EPDM)-based thermoplastic vulcanizates [57, 63, 67].
Butyl rubber has its origin in the studies done by Gorianov and Butlerov (1870)
and Otto (1927); they found that oily (low molecular weight) polyisobutylene could
be obtained in the presence of boron trifluoride. In the 1930s high-molecular-weight
rubber, like polyisobutylene, was produced by Sparks and Thomas and in 1937 they
obtained a vulcanizable polyizobutylene by introducing through co-polymerization
a small amount of a diolefin. This co-polymer known as butyl rubber was first
commercialized in 1942. Halogenated forms of this rubber were commercialized
in 1954 (brominated butyl rubber) and 1961 (chloro butyl rubber) [63, 67–69].
Another oil-resistant rubber, the polysulfide one known as Thiokol, was prepared
in 1934 and was much used during WW II, but was later replaced by other rubbers
because its poor physical properties and odor [45, 57, 70].
Based on Ziegler–Natta catalyst ethylene-propylene co-polymers were produced
around 1955; despite their saturated nature, vulcanisable elastomers can be obtained
by the use of a third co-monomer, a diene one like 1,4-hexadiene [46] EPDM, of
which the commercial production began in 1963 [71].
Ziegler–Natta catalyst proved to be very versatile and could be used to copolymerize ethylene with α-olefins, leading later on to thermoplastic elastomers.
This relatively new class of materials (commercially available since around 1960),
was developed in response to certain disadvantages inherent in the thermoset character of conventional elastomers. In particular, thermoplastic elastomers exhibit
thermal- and solvent-induced reversibility in their network structures. This allows
recycling of off-grade or scrap materials after processing. Thermoplastic elastomers represent an alternative to conventional rubber compounding. They can be
processed like plastics at elevated temperatures but behave like vulcanized rubber
at normal temperature [23, 72, 73].
The possibility of the existence of organo-silicon compounds was first noted by
Berzelius in 1823 and in 1840 by Dumas. In 1863 Friedel and Crafts prepared the
first organosilicon compound, tetraethylsilane. The foundation of silicon chemistry
was really laid by Kipping (1937). The first silicone sealing product was introduced
in 1942–1943 [45, 57].
D. Feldman / Designed Monomers and Polymers 11 (2008) 1–15
From 1957 fluoroelastomers were developed, and in 1959 fluoroelastomer terpolymers were introduced. The 1960s and 1970s saw farther refinement of fluorine
containing elastomers with several new grades developed for specific needs mainly
in the chemical processing. Most of them are co-polymers of vinylidene fluoride
and hexafluoro polypropylene or perfluoro elastomer. These polymers need special
vulcanization agents and in 1970s cross-linking was realized by using bisphenol
AF. In the late 1980s fluoroelastomers with better flow properties and fast curing
were produced, and in 1997 a new member of this family able to withstand strong
bases and ketones, as well as aromatic hydrocarbons, oils, acids and steam [15, 57,
74, 75]. In 1975 ethylene-acrylic elastomers (AEM), best known for their heat and
oil resistance, were introduced [76].
As has been already mentioned the original discovery of PUs was made by
Bayer. In 1937 he used Wurtz’ discovery (1848) of the reaction between hydroxyland amino-compounds and that of Hofman and Hertschel (1884) regarding phosgenation of primary amines to the synthesis of this new class of polymers from
diisocyanates and glycols. After polyurethane plastics and fibers, Bayer developed
elastomers (1950) and flexible foams (1952) [17, 69]. This class of polymers has
been documented in a number of works [17].
5. Conclusion
Polymers initially tended to be viewed as a chemist specialty, but they are now
strongly associated as plastics, fibers and elastomers with engineering as well,
through design, fabrication and testing of products.
The last decades have shown an increasing important requirement in the polymer
industry; it is the rapid development and introduction of new and improved products. In the growth of this family of engineering materials during the last century,
plastics are the leader, followed by fibers and elastomers.
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