2 Brief History of Thermoplastic Elastomers

The development of thermoplastic materials

having more or fewer elastic properties started in the
early 1930s with the invention of plasticization of
polyvinyl chloride (PVC) at the B.F. Goodrich
Company [1]. This invention led to further interest in
exible plastics and eventually to the development of
blends of PVC and butadiene-acrylonitrile rubber
(NBR) [2,3]. When properly formulated, the PVC/
NBR blends have a rubber-like look and feel and
bridge the gap between liquid plasticized PVC and
conventional cured elastomers. Thus, they can be
considered precursors of thermoplastic elastomers, as
we know them today.
A major breakthrough occurred in 1937 [4] with
the discovery of the basic diisocyanate polyaddition
reaction, which was rst applied to produce polyurethane bers and then to the development of some
elastomeric polyurethanes at DuPont and ICI [5e7].
The work at DuPont focused on elastic bers and
eventually led to the invention of elastic linear
copolyesters, prepared by melt-ester interchange
between two melt-copolymerized polymers [8]. This
synthetic elastomer had higher strength than vulcanized natural rubber and exhibited a rapid elastic
recovery. It was used to make bers by extrusion or
spinning from solutions, and can be considered to be
the rst thermoplastic elastomer. The DuPont patent
dated 1954 [9] describes it as segmented polyurethane ber with excellent elastic properties.
Further development of thermoplastic polyurethanes continued through the 1950s and 1960s. In
1962, a group from the B.F. Goodrich Co. presented
a paper on virtually cross-linked polymer, Polyurethane VC, which was soluble, had high tensile
strength, good elasticity, high abrasion resistance,
and could be processed as a thermoplastic [10,11].
Commercial polyurethane thermoplastic elastomers
were introduced in the 1960s by B.F. Goodrich,
Mobay, and Upjohn in the United States, and by
Bayer A.G. and Elastogran in Europe.
Styrene-diene block copolymers were rst
developed by Shell utilizing anionic block

copolymerization of styrene with butadiene

(SeBeS) and styrene with isoprene (SeIeS) and
introduced commercially in 1966 as Kraton.
Phillips Petroleum Co. entered this eld in 1968
with radial styrenic block copolymers. In 1972,
Shell added the SeEBeS copolymer, where EB is
ethylene-butylene copolymer segment. SeEBeS
copolymer is prepared by hydrogenation of the
polybutadiene center block thus eliminating the
double bonds and improving resistance of the
product to oxidative scission and ozone attack [12].
The product was introduced as Kraton G.
Copolyetherester thermoplastic elastomers were
developed during the 1960s and commercialized by
Du Pont in 1972 as Hytrel. The randomly
segmented copolymer contains poly(tetramethylene
oxide) terephthalate soft segments and multiple tetramethylene terephthalate hard segments. The attributes of this material were high strength, high
elasticity, excellent dynamic properties, and creep
resistance. Similar products were commercialized by
GAF Corporation in late 1970 (Pelprene), by
Eastman Chemical Co. in 1983 (Ecdel), and by
General Electric Corporation in 1985 (Lomod).
Thermoplastic polyolen blends (TPOs) were
developed throughout the 1960s. The rst patent on
record is that of Hercules Inc. covering blends of
crystalline polypropylene and ethylene-propylene
copolymers (EPM), in which the propylene content
was more than 50% [13]. Dynamically vulcanized
blends of polypropylene and chlorinated butyl rubber
were patented in 1962 [14]. Partially dynamically
cured blends of EPM or EPDM (ethylene propylene
diene monomer rubber) with polypropylene using
peroxide curing were the subject of two Uniroyal
patents issued in 1974 [15,16]. Uniroyal Inc. introduced TPR thermoplastic rubber materials consisting
of blends of partially dynamically cured EPDM with
polypropylene in 1972.
Thermoplastic vulcanizates (TPVs) are materials
based on extensive research done at Monsanto
Company during the 1970s and 1980s. These are

Handbook of Thermoplastic Elastomers. http://dx.doi.org/10.1016/B978-0-323-22136-8.00002-8

Copyright 2014 Elsevier Inc. All rights reserved.

13

14

mechanically mixed blends of an elastomer with

a thermoplastic [17e30]. The rst commercial product
was Santoprene, based on a blend (or alloy) of EPDM
and polypropylene introduced in 1981. A similar
product based on the blend of butadiene-acrylonitrile
rubber (ASTM designation NBR) with polypropylene,
Geolast, was introduced in 1985 [31].
Polyamide thermoplastic elastomers were introduced in 1982 by ATO Chemie followed by
Grilamid and Grilon produced by Emser Industries and by Dow Chemical Companys Estamid
[32e34]. The properties of polyamide TPEs depend
upon the chemical composition of the hard (polyamide) block and the soft (polyether, polyester, or
polyetherester) block.
Single-phase melt processable rubber (MPR) is
based on work done at Du Pont in the early 1980s and
led to the commercialization of proprietary products
under the name Alcryn in 1985.
During the 1990s and 2000s, many new developments took place, such as functionalized styrenic
TPEs [35,36], new and improved TPVs, softer
MPRs and MPRs with improved physical properties, TPEs based on blends of natural rubber and
polypropylene [37], thermoplastic uoroelastomers
[38,39], etc. Many more companies have developed
new products and their applications. The above
subjects will be discussed in chapters dealing with
individual TPEs and their applications as well as in
a chapter summarizing the newest developments
and trends.

References
[1] Semon WL. U.S. Patent 1,929,453 (1933, to B.F.
Goodrich Co.).
[2] Henderson DE. U.S. Patent 2,330,353 (1943, to
B.F. Goodrich Co.).
[3] Wolfe Jr JR. In: Legge NR, Holden G,
Schroeder
HE,
editors.
Thermoplastic
elastomersda comprehensive review. Munich:
Hanser Publishers; 1987 [chapter 6].
[4] Bayer O, Siefken W, Rinke H, Orthner R, Schild
H. German Patent 738,981 (1937, to I.G. Farben,
A.G.).
[5] Christ AE, Hanford WE. U.S. Patent 2,333,639
(1940, to Du Pont).
[6] British Patents 580,524 (1941) and 574,134
(1942) (both to ICI Ltd.).
[7] Hanford WE, Holmes DF. U.S. Patent 2,284,896
(1942, to Du Pont).

H ANDBOOK

OF

T HERMOPLASTIC E LASTOMERS

[8] Snyder MD. U.S. Patent 2,632,031 (1952, to Du

Pont).
[9] U.S. Patent 2,629,873 (1954, to Du Pont).
[10] Schollenberger CS, Scott H, Moore GR. Paper at
the Rubber Division Meeting; September 13,
1957; Rubber Chem Technol 1962;35:742.
[11] Schollenberger CS. U.S. Patent 2,871,218 (1959,
to B.F. Goodrich Co.).
[12] Gergen WP. In: Legge NR, Holden G,
Schroeder HE, editors. Thermoplastic
elastomersda comprehensive review. Munich:
Hanser Publishers; 1987. p. 507 [chapter 14].
[13] Holzer R, Taunus O, Mehnert K. U.S. Patent
3,262,992 (1966, to Hercules Inc.).
[14] Gessler AM, Haslett WH. U.S. Patent 3,307,954
(1962, to Esso).
[15] Fisher WK. U.S. Patent 3,806,558 (1974, to
Uniroyal).
[16] Fisher WK. U.S. Patent 3,835,201 (1972, to
Uniroyal).
[17] Coran AY, Patel RP. U.S. Patent 4,104,210
(1978, to Monsanto).
[18] Coran AY, Patel RP. Paper presented at the
international rubber conference, Kiev, USSR;
October 1978.
[19] Coran AY, Patel RP. U.S. Patent 4,130,534
(1978, to Monsanto).
[20] Coran AY, Patel RP. U.S. Patent 4,130,535
(1978, to Monsanto).
[21] Coran AY, Patel RP. Rubber Chem Technol
1980;53:141.
[22] Coran AY, Patel RP. Rubber Chem Technol
1980;53:781.
[23] Coran AY, Patel RP. Rubber Chem Technol
1981;54:91.
[24] Coran AY, Patel RP. Rubber Chem Technol
1981;54:892.
[25] Coran AY, Patel RP. Rubber Chem Technol
1982;55:116.
[26] Coran AY, Patel RP. Rubber Chem Technol
1982;55:1063.
[27] Coran AY, Patel RP. Rubber Chem Technol
1983;56:210.
[28] Coran AY, Patel RP. Rubber Chem Technol
1983;56:1045.
[29] Coran AY, Patel RP, Williams-Headd D. Rubber
Chem Technol 1985;58:1014.
[30] Coran AY. In: Legge NR, Holden G,
Schroeder HE, editors. Thermoplastic
elastomersda comprehensive review. Munich:
Hanser Publishers; 1987. p. 132 [chapter 14].

2: B RIEF H ISTORY

T HERMOPLASTIC E LASTOMERS

15

[31] Rader CP. In: Walker BM, Rader CP,

editors.
Handbook
of
thermoplastic
elastomers. 2nd ed. New York: Van Nostrand, Reinhold Company; 1988. p. 85
[chapter 7].
[32] Nelb II RG, Chen AT, Farrissey Jr WJ,
Onder KB. Paper at the SPE 39th annual technical conference (ANTEC), Proceedings
Boston; May 4e7, 1981. p. 421.
[33] Deleens G. In: Legge NR, Holden G,
Schroeder
HE,
editors.
Thermoplastic
elastomersda comprehensive review. Munich:
Hanser Publishers; 1987. p. 215 [chapter 9B].
[34] Farrisey WJ, Shah TM. In: Legge NR,
Holden G, Schroeder HE, editors. Thermoplastic elastomersda comprehensive review.

Munich: Hanser Publishers; 1987. p. 258

[chapter 8].
Modication of thermoplastics with Kraton
polymers, Shell Chemical Publ 5C:165e187,
11/87.
Kirkpatrick JP, Preston DT. Elastomerics
1988;120(10):30.
Tinker AJ, Icenogle RD, Whittle I. Paper no. 48,
presented at the Rubber Division of ACS
Meeting, Cincinnati, OH; October 1988.
Daikin America, Inc., DAI-EL Thermoplastic,
www.daikin.com.
Park EH. Dynamic vulcanization of elastomers
with in situ polymerization. U.S. Patent
7,351,769 (December 19, 2006, to FreudenbergNOK General Partnership).

OF

[35]

[36]
[37]

[38]
[39]