Article No : o23_o02

Rubber, 5. Solution Rubbers

HEINZ-DIETER BRANDT, Bayer AG, Dormagen, Germany
WOLFGANG NENTWIG, Bayer AG, Dormagen, Germany
NICOLA ROONEY, Bayer Inc, Sarnia, Ontario, Canada
RONALD T. LAFLAIR, Bayer Inc, Sarnia, Ontario, Canada
UTE U. WOLF, Bayer AG, Dormagen, Germany
JOHN DUFFY, Bayer Inc, Sarnia, Ontario, Canada
JUDIT E. PUSKAS, University of Western Ontario, Department of Chemical and
Biochemical Engineering, London, Ontario, Canada
GABOR KASZAS, Bayer Inc, Sarnia, Ontario, Canada
MARK DREWITT, Bayer Inc, Sarnia, Ontario, Canada
STEPHAN GLANDER, Bayer Inc, Sarnia, Ontario, Canada

1. Synthesis by Anionic Polymerization . . . . . . 649 2.2.1. Properties, Grades, and Applications. . . . . . . 665
1.1. Solution 1,3-Butadiene – Styrene Rubber 2.2.2. Basic Chemistry and Production Processes . . 667
(S-SBR) and Styrene – Isoprene – 2.2.3. Producers and Production Capacities . . . . . . 670
Butadiene Rubber (S-SIBR). . . . . . . . . . . . 649 3. Synthesis of Butyl Rubber by Cationic
1.1.1. Properties, Grades, and Applications. . . . . . . 649 Polymerization . . . . . . . . . . . . . . . . . . . . . 671
1.1.2. Basic Chemistry and Production Processes . . 652 3.1. Properties, Grades, and Applications. . . . . 671
1.1.3. Producers and Production Capacities . . . . . . 653 3.1.1. Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 671
1.2. Lithium – Butadiene (Li-BR) and 3.1.2. Grades . . . . . . . . . . . . . . . . . . . . . . . . . . . . 672
Lithium – Isoprene (Li-IR) Rubber . . . . . . 653 3.1.3. Specialty Rubbers . . . . . . . . . . . . . . . . . . . . 672
1.2.1. Properties, Grades, and Applications. . . . . . . 653 3.1.4. Applications . . . . . . . . . . . . . . . . . . . . . . . . 672
1.2.2. Basic Chemistry and Production Processes . 655 3.2. Basic Chemistry and Production Processes 673
1.2.3. Producers and Production Capacities . . . . . . 657 3.2.1. Basic Chemistry . . . . . . . . . . . . . . . . . . . . . 673
2. Synthesis by Ziegler – Natta Polymerization 658 3.2.2. Industrial Production . . . . . . . . . . . . . . . . . . 674
2.1. Polybutadiene and Polyisoprene Rubber . . 658 3.3. Producers and Production Capacities . . . . 676
2.1.1. Properties, Grades, and Applications. . . . . . . 658 3.4. Storage and Transportation. . . . . . . . . . . . 676
2.1.2. Basic Chemistry and Production Processes . . 660 3.5. Legal Aspects. . . . . . . . . . . . . . . . . . . . . . . 676
2.1.3. Producers and Production Capacities . . . . . . 664 3.6. Toxicology and Occupational Health . . . . . 676
2.2. Ethylene – Propene Elastomers (EPM, References . . . . . . . . . . . . . . . . . . . . . . . . . 677
EPDM) . . . . . . . . . . . . . . . . . . . . . . . . . . . 665

1. Synthesis by Anionic Polymerization Copolymerization can be performed either in a

free radical emulsion process (E-SBR; see !
1.1. Solution 1,3-Butadiene – Styrene Rubber, 4. Emulsion Rubbers, Chap. 1) or in a
Rubber (S-SBR) and Styrene – solution process by anionic initiation (S-SBR).
The emulsion process yields pure random copo-
Isoprene – Butadiene Rubber (S-SIBR)
lymers with a fixed microstructure of the incor-
1.1.1. Properties, Grades, and Applications porated butadiene moieties. The solution process
is more versatile: the microstructure of the buta-
Copolymers of styrene and 1,3-butadiene (SBR) diene moieties and the styrene sequence distri-
are elastomers of great technical importance that bution (pure random to true block copolymers)
are used predominantly in automobile tires [3]. can be adjusted [4, 5]. In addition, a great variety

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.o23_o02
650 Rubber, 5. Solution Rubbers Vol. 31

of endgroups can be incorporated by using the the trade-off relationship between rolling and wet
solution process [5]. skid resistance.
S-SBR with a random styrene sequence dis- Many investigations to optimize the balance
tribution is predominantly used for standard between high wet grip and low rolling resistance
rubber applications, whereas styrene – butadi- in combination with high wear performance are
ene block copolymers are used in plastics appli- based on S-SBR. Typical polymer and vulcani-
cations such as high impact polystyrene (HIPS) zate properties of E-SBR and S-SBR are com-
and acrylonitrile – butadiene styrene terpolymer pared in Table 1. Because of its broad molar
(ABS) (see also ! Polystyrene and Styrene mass distribution and its high degree of branch-
Copolymers). ing E-SBR can be processed more easily than S-
SBR. S-SBR cures faster than E-SBR. However,
Random Styrene – Butadiene Copolymers E-SBR has a higher tensile and tear strength than
(S-SBR). The main application area of S-SBR S-SBR. S-SBR shows lower hysteresis and pro-
is in passenger car tire treads, although E-SBR is vides a higher modulus. Moreover, the green
still predominantly used in this field. However, strength of S-SBR is significantly improved in
with investigations focusing on improvements in comparison to E-SBR.
wet grip (higher safety) as well as rolling resis- E-SBR and S-SBR also differ in hydrocarbon
tance (lower fuel consumption) and abrasion content. E-SBR contains only ca. 90 % hydro-
resistance, the consumption of S-SBR has been carbon due to the high level of soap residue (see
increasing [3]. The proportion of energy loss ! Rubber, 4. Emulsion Rubbers, Section 1.2),
ratio via the tire tread accounts for 40 % of the while the hydrocarbon content of S-SBR is close
energy losses brought about by the whole tire [6, to 100 %. These soap residues are responsible for
1]. Therefore, the reduction of the energy loss due the high hysteresis of E-SBR [10]. However,
to tire tread is the most effective way to lower the
rolling resistance. However, any improvement in
Table 1. Polymer and vulcanizate properties of E-SBR and S-SBR
rolling resistance is normally combined with a
deterioration of wet grip performance (wet skid Property S-SBR E-SBR
resistance). Elastomers with a low Tg show very SL 705 EM 1500
low rolling resistance but poor wet grip perfor- Polymer
mance, while elastomers with a high Tg have a Styrene content, % 25 23.5
good wet grip performance in combination with Vinyl (1,2) content, % 10 19
cis-1,4-content, % 33 14
high rolling resistance [2, 7, 8]. Figure 1 shows trans-1,4-content, % 57 67
Mooney viscosity ML1þ4 (100
C) 48.0 51.5
Tg (by DSC),
C  65  50
Mn*/1000 200 145
Mw*/1000 420 651
Mw/Mn 2.1 4.5
Compound (ASTM)
ML1 þ 4 (100
C) 88.0 86.0
Rheometer tests (160
C)
ts1, min 4.7 5.8
tc90, min 14.9 19.4
Tensile strength, MPa 18.0 19.0
Elongation at tear, % 565 635
300 % modulus, MPa 8.9 7.8
Ring tear strength (23
C), N 240 265
Ring tear strength (70
C), N 235 255
Rebound resilience (23
C), % 49 45
Rebound resilience (70
C), % 49 49
Abrasion DIN S 40, mm3 135 148
Abrasion DIN S 60, mm3 78 65
tan d, 0
C 0.190 0.216
tan d, 60
C 0.172 0.183
Tg (torsional pendulum),
C  50  39

Figure 1. Trade-off relationship between rolling resistance

*
Mw ¼ mass-average molar mass; Mn ¼ number-average molar
and wet skid resistance for tire tread rubbers [9] mass.
Vol. 31 Rubber, 5. Solution Rubbers 651

Figure 2. ‘‘Integral rubber’’ – wide modal tan d concept [19]

these residues also improve the processibility and Styrene – Isoprene – Butadiene Terpoly-
increase tear strength. mer (S-SIBR). The development of S-SIBR is
Due to the difference in microstructure [dif- based on the ‘‘wide modal tan d concept’’ [19]. S-
ferent content of 1,2-(vinyl)-configurations], SIBR rubber is often referred to as integral rub-
standard S-SBR has a lower Tg than E-SBR at ber. It has a tailor-made chain consisting of
the same level of bound styrene (Table 1). Also different segments exhibiting different Tgs. The
the difference in macrostructure is obvious. S- maxima of the damping peaks of the separate
SBR has a narrower molar mass distribution and segments result in a tan d curve of the polymer
a more linear backbone. In tire tread applications with a wider peak profile. The principle is shown
S-SBR therefore provides lower rolling resis- in Figure 2. The absolute values for tan d given
tance, improved dry slide traction, and superior for the three temperature ranges in Figure 2 indi-
wear resistance, while E-SBR provides the better cate the generally accepted relationship between
wet slide traction [11, 12]. tan d and tire characteristics regarding rolling
In 1991 the ‘‘green tire’’ concept was launched resistance (50 to 80
C), wet grip ( 20 to 20
C),
with Michelin’s patent application [180]. In this and wear resistance ( 50 to  100
C). This
concept, the subsitution of silica for carbon black concept has been known for several years [20–22,
gives rise to lower rolling resistance, improved 25]. Commercial production of S-SIBR began in
wet grip, and good wear properties. In terms of the United States in 1991 [3].
rubber, this concept is based on S-SBR or blends Improvements in the manufacture process
of S-SBR with BR or NR: An strong increase in were reported in the 1990s [26, 27]. The concept
the demand for ‘‘green tires’’ is anticipated [26]. of chain-end coupling can be applied also with S-
SIBR [28]. Tire tread compounds containing S-
Vinyl-S-SBR (VS-SBR). Traditional S- SIBR and silica as filler are claimed to have
SBR types with 10 % vinyl content are of minor improved properties [29].
interest for use in modern high performance tires
[3]. S-SBR grades with a vinyl content up to 70 % Styrene – Butadiene Block Copolymers.
and with a styrene content up to 40 % are tailor- These block copolymers exhibit two separate
made for this application and are commercially ranges of Tgs:  80 to  90
C for the polybu-
available. They meet the demand for lower roll- tadiene block and 70 to 80
C for the polystyrene
ing resistance and higher wet grip. By additional block [30]. These polymers are not suitable for
variation of the macrostructure (bimodal molar standard rubber applications such as tires [8].
mass distribution), the aforementioned effects
are enhanced and, furthermore, the processibility Butadiene – Styrene Diblock Copolymers
is improved [16–18]. (SB). SB diblock copolymers are used for the
652 Rubber, 5. Solution Rubbers Vol. 31

production of HIPS and mass polymerized ABS, leads to the formation of tapered diblock copo-
either alone or in blends with polybutadiene. By lymers in which the almost pure polybutadiene
using diblock copolymers, HIPS properties such block is connected to a polystyrene block through
as gloss and transparency which are often unsat- a transitionally random polymer segment con-
isfactory can be improved [31, 32]. SB diblock sisting of increasing proportions of styrene.
copolymers can also be used to increase impact About 75 % of the total bound styrene content
strength of polystyrene and polyolefins by me- is incorporated as a polystyrene block [4, 41].
chanical blending.
SB diblock copolymers with different styrene SBS Triblock Copolymers (SBS). Differ-
content are available: 40 % bound styrene (for ent strategies exist for the synthesis of triblock
HIPS), 30 % bound styrene (for ABS, HIPS), styrene – butadiene copolymers:
25 % bound styrene (for carpet pads and bitumen Due to the ‘‘living character’’ of the anionic
modification), and 10 % bound styrene (for ABS). polymerization, SBS can be produced by poly-
merization of styrene to form living polystyrene
Styrene – Butadiene Triblock Copolymers chains, followed by chain extension with buta-
(SBS). Linear [33] and radial SBS types [34, diene to form a diblock (SB) which then can be
35] are commercially available. They are typical (1) extended with a second polystyrene end-
thermoplastic elastomers (see ! Thermoplastic block [33] or (2) coupled with di- or polyfunc-
Elastomers). tional coupling agents (e.g., mono- or diesters,
metal halides) to produce linear, 3-, 4- or multi-
branched copolymers [35].
1.1.2. Basic Chemistry and Production
Processes

The versatility of anionic solution polymeriza-

tion allows the formation of tailor-made diene –
styrene copolymers. The unique features of copo-
lymerization initiated by butyllithium in nonpo-
lar hydrocarbon solvents are:

1. Absence of spontaneous chain terminations Triblock copolymers can also be produced by

(living chains polymerization, ! Plastics, dilithium compound-initiated polymerization of
General Survey, Section 3.3.3), which allows butadiene to form living polybutadiene chains
the sequential addition of monomers and the followed by building the styrene blocks on both
use of chain-coupling techniques ends of the polybutadiene chain by adding sty-
2. Absence of chain-transfer reactions to give rene [42, 43].
essentially linear and gel-free polymers
3. A wide choice of chain microstructures [5, 36, S-SBR. Completely random copolymers
40] can be obtained in nonpolar solvents either by
a continuous polymerization process [44] or a
The use of butyllithium in nonpolar, hydrocarbon semibatch process with programmed addition of
solvents leads to polybutadienes in which the butadiene to the reaction mixture [45]. S-SBR
diene units are present mainly in the 1,4-config- made by these routes is characterized by a vinyl
uration (ca. 90 %), the remainder being in the content of ca. 10 % in the diene fraction.
1,2-configuration (vinyl structure). Another route utilizes randomizers, in batch or
continuous operation. These randomizers or modi-
SB Diblock Copolymers. SB copolymers fiers are polar compounds such as ethers or amines
are usually produced in a batch polymerization. which decrease the difference between the reactiv-
Because of the different reaction rates of the two ities of butadiene and styrene to such an extent that
monomers in hydrocarbon solvents (reaction rate both monomers are consumed at virtually equal
of butadiene is higher), the diene dominates the rates [46, 47]. The randomizing action of these
initial copolymerization reaction. This inevitably polar compounds results from an effect they have
Vol. 31 Rubber, 5. Solution Rubbers 653

small hysteresis loss at high temperature and a

large loss at lower temperature [64].

Process Description. S-SBR, VS-SBR, and

S-SIBR are commercially produced by batch and
continuous anionic solution processes. Typically,
these processes consist of four operating stages:
polymerization, monomer and solvent recycling,
product recovery, and product finishing. The po-
lymerization is carried out at 50 – 100
C and 1 –
5 bar in a batch reactor or in a reactor train of two
to four stirred-tank reactors. Conversion is com-
Figure 3. Relationship of Tg to bound styrene and vinyl plete after a residence time of ca. 1 – 4 h depend-
content [2] ing on the temperature, monomer concentration,
catalyst, and modifier levels. Immediately down-
on the initiator and coincides with an increased stream of the reactor, the polymerization is termi-
amount of 1,2-addition in butadiene polymeriza- nated with alcohol or other polar liquids. After the
tion. The vinyl content in the polybutadiene de- addition of stabilizers and, depending on the poly-
pends on the modifier type, modifier – catalyst mer type, extender oils, the polymer solution is
ratio and concentration (modifier and catalyst), coagulated and stripped with steam and hot water
and the polymerization temperature [7]. The vinyl to remove unreacted monomers and solvents. The
content of the diene fraction can be up to 90 %. rubber crumb is then passed over a screen to
This process flexibility is an important and remove free water and subsequently dried. Either
attractive possibility – in addition to changing extrusion or hot air drying may be used. S-SBR,
the bound styrene level – to control the Tg of the VS-SBR, and SB are sold in the form of bales.
derived polymers. The relationship between the
vinyl and styrene contents and Tg is illustrated in
Figure 3 for a series of random S-SBR. The high 1.1.3. Producers and Production
linearity together with a narrow molar mass Capacities
distribution of the S-SBR results in a relatively
poor processing performance during mixing and The commercial production of S-SBR started
molding operations. This can be improved by the around 1965. The consumption increased from
coupling of polymer chains through the ‘‘living’’ 400 000 t in 1980 (16 % of total SBR market) to
chain ends. Various coupling agents (dihalides, 440 000 t in 1991 (15 % of total SBR market).
tetrahalides, divinylbenzene, etc.) are available The production capacity was ca. 610 000 t in
[16–18, 48]. Tin tetrachloride shows not only 1996. The S-SBR plant capacity is, in almost all
good coupling efficiency but also an improved cases, part of a multipurpose anionic solution
interaction (e.g., better rolling resistance) with polymerization facility. Thus, if the demand for
the filler carbon black. A similar effect can be S-SBR increases in the future, parts of the multi-
obtained by a chain end modification by termi- purpose plants can be used for S-SBR production.
nating the ‘‘living’’ chain end with a modifier Table 2 gives an overview of the S-SBR produ-
such as N-methyl-2-pyrrolidone [49], N-substi- cers, their S-SBR capacities in 1992, and the
tuted aziridines [50], aminobenzophenone com- capacities of their multipurpose facilities [52].
pounds [23, 24], and substituted imines [51].
The concept of introducing polymer-bound
functionalities can be extended by using functio- 1.2. Lithium – Butadiene (Li-BR) and
nalized initiators such as lithium cycloalkyla- Lithium – Isoprene (Li-IR) Rubber
mides [37–39], lithium compounds containing
imine groups [59, 60], and LiSn alkyls [62, 63]. 1.2.1. Properties, Grades, and Applications
Novel S-SBR types formed by selective hy-
drogenation of 1,2-vinyl units have been pre- Polybutadiene produced with lithium initi-
sented. They are characterized by an extremely ators is often described as a low- or medium-
654 Rubber, 5. Solution Rubbers Vol. 31

Table 2. Producers of S-SBR, plant locations, and production capacities (1996)

Company Location Capacity*, t Multipurpose plant

Capacity, t Products

Western Europe
Bayer Lillebonne 20 000 75 000 BR, SB
Enichem Ravenna, 15 000 85 000 SBS, SIS
Grangemouth 10 000 80 000 BR
Michelin Bassens 70 000 100 000 BR
Petrochim Antwerp 20 000 80 000 BR, SBS
Repsol Santander 40 000 75 000 BR, SBS
Shell Pernis 5000 30 000 IR
North America
American Synthetic Rubber Louisville, KY 60 000 160 000 BR
Firestone Lake Charles 90 000 150 000 BR. SBS
Orange 50 000 110 000 BR, SB
Goodyear Beaumont, TX 20 000 290 000 BR, SIBR, IR
Latin America
Coperbo Muncipo d. Cabo (1976) 35 000 110 000 BR, SB, SBS
Negromex Altamira 45 000 94 000 BR, SBS
Far East
Asahi Chemical Ind. Kawasaki 20 000 130 000 BR, SB, SBS
Japan Elastomers Tsurusaki (Oita) 10 000 48 000 BR, SBS
Japan Synthetic Rub. Yokkaichi 15 000 25 000 BR
Nippon Zeon Tokuyama 20 000 78 000 BR, SBS
Sumitomo Chem. Chiba 10 000
Hyundai Petrochem. Daesan 10 000 40 000 BR
Kumho Petrochem. Yeochon 25 000 150 000 BR, SBS
Taiwan Synthetic Kaohsiung 16 000 100 000 BR. SBS
Africa
Carbochem Newcastle 10 000 36 000 BR, IR
*
Estimated.

cis-1,4-polymer. When produced in an aliphatic, mity and high purity. It competes in this applica-
cycloaliphatic, or aromatic solvent, a polymer of tion with cobalt polybutadiene produced by
ca. 36 – 38 % cis-1,4-, 52 % trans-1,4-, and 10 % Ziegler – Natta catalysis (see Section 2.1). The
1,2-content is produced. The 1,2-content of the viscosity of the rubber solution in styrene is
polymer can be varied over the range from 10 to important to the HIPS producer. The solution
90 % by the addition of polar additives. The viscosity of the rubber in styrene is a function of
higher the 1,2-content, the higher is the Tg of the molar mass, molar mass distribution, and
the polymer. Standard lithium polybutadiene of branching of the polymer. Various proceses can
10 % vinyl (i.e., 1,2-)content has a Tg of  93
C, be used to branch lithium polymers. Small
whereas the Tg of a 90 % vinyl polymer can be amounts of divinylbenzene (DVB) may be added
expected to be ca.  20
C [53, 54]. or the branching process may be carried out
A considerable amount of lithium-initiated thermally. Branching also helps in handling the
polybutadiene is used to produce high-impact rubber because linear polymers are very prone to
polystyrene (HIPS) (! Polystyrene and Styrene cold flow. Levels of gel in the polymer must be
Copolymers, Chap. 1) [55]. BR is the rubber of  200 ppm. A higher 1,2-content of the lithium
choice because it dissolves readily in styrene and polymer (10 %) causes faster grafting than that
gives rubber domains of the appropriate size that observed with cobalt polymers with a 1,2-content
inhibit crack propagation. BR is the most effi- of only 2 %. Because of this the HIPS process
cient impact modifier for polystyrene on the basis must be adjusted to the polymer in use.
of impact improvement relative to rubber level Some lithium polybutadiene grades have been
used. Lithium polybutadiene is used in this ap- used in tires, but the production volume of these
plication because it can be produced with unifor- grades is relatively small. The standard lithium
Vol. 31 Rubber, 5. Solution Rubbers 655

polymer exhibits poor processing behavior and chemistry, see [65]. Polymerization of dienes
does not give the excellent tread wear that is such as butadiene and isoprene can be initiated
typical of the high-cis-polybutadienes made by by alkali metals or organoalkali compounds. The
Ziegler – Natta polymerization [56]. More re- use of organolithium initiators is advantageous
cent work to produce lithium polybutadienes for because of their solubility in polar and nonpolar
improving tire performance, however, has been solvents. In the case of organolithium initiators
relatively successful. Lithium chemistry allows (e.g., butyllithium), the initiation step can be
the production of polymers with very specific regarded as a nucleophilic attack of the initiator
molecular architecture (branching, end groups, on the monomer, generating an allylic organo-
microstructure, copolymerization control, etc.). lithium compound, which is able to add the next
Specific lithium polybutadiene polymers and monomer molecule. Further addition of mono-
solution SBR polymers are now being made to mer leads to polybutadiene or polyisoprene
meet the increasing demands of tire manufac- chains, which still possess an organolithium unit
turers [57]. Lithium polymers with high vinyl at the end. Depending on the nature of the solvent
content are used in winter tires and tires with and other reaction conditions, the carbon – lithi-
lower rolling resistance. um bond has a more or less ionic character. In
Specific polar end groups are sometimes sufficiently pure systems at moderate tempera-
added to improve the bonding of the polymer to ture, transfer and termination reactions do not
carbon black. Branched and coupled polymers occur to a significant extent. Therefore, the active
are made to improve processing and to alter the species retain their reactivity, and the polymeri-
dynamic properties of the tire. Star-branched zation is often described as living (! Plastics,
lithium polymers are used in very highly carbon General Survey, Section 3.3.3). In pure systems
black-loaded compounds, such as bead or chafer the polymerizations go to completion. The molar
compounds, because they can easily be com- mass of the product can be calculated from the
pounded with large amounts of carbon black. number of moles of monomer divided by the
Copolymers with styrene and, in some cases, number of moles of butyl lithium. The product
isoprene further extend the range of special has a narrow Poisson distribution, if the initiation
products available to tire designers. To date, the is rapid and side reactions are avoided. In the
market volume of such materials is not large (see ideal case, the polymer chains are linear. The
Section 1.1), but growth of these materials is narrow molar mass distribution and high linearity
expected. Functional lithium initiators with an usually yield polybutadienes that are difficult to
end group that can bond to carbon black are now process. Thus, introduction of branches or broad-
being studied to further improve rolling ening the molar mass distribution can be useful.
resistance. Copolymerization of butadiene with small
amounts of a branching comonomer such as
Lithium Polyisoprene is produced on a divinylbenzene yields products that are easier to
small scale for use as a processing aid for natural process and have a reduced cold flow. Partial or
rubber and in other applications where its high quantitative coupling of polymer chain ends [72]
purity is an asset. A tread specialty polyisoprene can also be used. Common coupling agents are
with a high 3,4-content is also produced, as well metal halides, such as SnCl4 and SiCl4, or die-
as a liquid IR. sters. Moreover, anionic polymerization offers
the possibility of using multifunctional initiators
and introducing functional groups at the chain
1.2.2. Basic Chemistry and Production end during termination [71, 73]. Of the many
Processes [58, 71] functional end groups which can be used to
terminate the polymer, two main types have been
Lithium Polybutadiene. Anionic polymer- used to improve tire properties. The use of tin
ization offers many possibilities for synthesizing compounds in any form (R3SnCl, R2SnCl2,
tailor-made polymers. Only the most important RSnCl3, or SnCl4) leads to a tin-containing group
aspects of lithium chemistry are covered here. in the molecule which improves the bonding
For a broader understanding of the many com- of the rubber to carbon black [66, 67]. Depending
plex products which can be made using lithium on the number of chlorine atoms in the tin
656 Rubber, 5. Solution Rubbers Vol. 31

compound, these materials can also introduce concentration. Temperature does not strongly
branching of the polymer and alter processing affect microstructure in nonpolar media. Con-
characteristics Another class of compounds ventional Li-BR has about 33 – 38 % cis content
used commercially to introduce end groups are [74] and is therefore called low-cis-BR [53]. The
benzophenone derivatives such as bis(4,4’- content of 1,2-units in the polybutadiene chain is
diethylamino) benzophenone [68]. Many other increased by the addition of polar modifiers; the
end groups have been described in the patent level is influenced by the amount and type of
literature to be useful for reduction of rolling polar modifier used and by the polymerization
resistance. temperature [72]. Considerable attention is need-
The success at improving rolling resistance by ed for the selection of a suitable polar modifier.
terminal functional groups has prompted consid- Some modifiers give rise to side reactions which
erable research to incorporated similar groups at may prohibit coupling or addition of functional
the initiation end of the molecule [69]. end groups. Amount and cost of the polar modfier
In batch polymerization with a rapid initiator may be important, especially if the polymeriiza-
such as sec-butyllithium, narrow molar mass tion temperature or the desired vinyl level is high.
distributions can be obtained. In some tire appli- Both conditions necessitate addition of higher
cations bimodel molar mass distributions are levels of modifier. Being polar molecules, mod-
desirable. This can be achieved by coupling some iifiers are of concern as regards hygiene and
of the polymer with, e.g., SnCl4 or SiCl4. To this pollution and may pose problems in solvent
end, a substoichiometric amount of coupling reprocessing systems.
agents is added, so that some of the polymer is
left uncoupled. Lithium-Polyisoprene. The basic chemis-
In many applications, Li-Br with a narrow try in anionic polymerization of isoprene via
molar mass distribution is not needed. Products alkyllithium initiation does not differ much from
for these markets are thus often made in a simple that of butadiene. Since isoprene can be regarded
continuous process with high polymerization as a butadiene that is methyl substituted in the 2-
temperature and hexane as the solvent, which position, the 1,2- and 3,4-addition products are
results in a broader molar mass distribution. not identical. Consequently, four different units
The kinetics of the initiation as well as of the can exist in the polymer chain. In nonpolar media
propagation reactions show a first-order rate or with no solvent, very high cis-1,4-content is
dependence on monomer concentration that is attainable by alkyllithium initiation (e.g., 96 %
independent of the solvent used [58], whereas cis-1,4- and 4 % 3,4-units with no solvent and
various reaction orders are found with respect to with low concentrations of sec-butyllithium).
the initiator concentration, depending on solvent The presence of solvent or an increased initiator
type and other parameters. This is a consequence concentration can decrease the cis and increase
of the different nature of the initiator, the propa- the trans content [75]. By the addition of polar
gating chain end, and the mechanism under solvents, polyisoprene with mainly 3,4-units and
different reaction conditions. In nonpolar sol- possibly some 1,2-units can be synthesized [58].
vents, the growing polydienyllithium molecules Commercial ‘‘low-cis’’ polyisoprene has a cis
associate in pairs, whereas the addition of polar content of ca. 92 % [53] in contrast to the Zieg-
solvents such as tetrahydrofuran results in partial ler – Natta IR types with higher cis content.
dissociation of the pairs, and stabilization of the
ionic bond by solvation of the lithium ion, lead- Process Description. (see Fig. 4). A typical
ing to charge separation. In addition to the effect process for the production of lithium polybutadi-
of kinetics, the microstructure is strongly affect- ene is shown in Figure 4. The polymerization can
ed by the nature of the propagating chain end, by be carried out in a broad range of aliphatic, cyclo-
solvation and association, and by the polarity of aliphatic, or aromatic solvents. The solvent system
the alkyl – metal bond; therefore changing the is chosen to have a solubility parameter appropriate
alkali metal in the initiator drastically changes to the polymer. Especially when styrene copoly-
the microstructure. In nonpolar media, Li-BR mers are to be made in the same plant, the solubility
with ca. 90 % 1,4-units is obtained and the cis : parameter of the solvent must be sufficiently high
trans ratio increases with decreasing initiator to keep the polymer in solution. Simple Li-Br is
Vol. 31 Rubber, 5. Solution Rubbers 657

Figure 4. Schematic of a polybutadiene plant

a) Purification towers; b) Polymerization reactors; c) Stripping vessels; d) Dewatering extruder; e) Drying oven; f) Packaging

usually made in mixed hexane isomers, however, excessive shear or temperature increase. Effec-
in plants where SBR or block copolymers are also tive processes for shortstopping and for extrac-
produced, it may be necessary to improve the tion of lithium residues are also required, because
solubility parameters by adding other better sol- residues left in the rubber will lead to gel and
vents such as cyclohexane. Because of the sensi- color formation.
tivity of the system to polar impurities, the mono- Removal of the solvent and any residual
mer and solvent streams must be very pure. The monomer is carried out by contacting the dis-
feed is typically dried by azeotropic distillations (a) solved rubber with steam and water (c). The
to lower the water content to a few parts per hydrocarbon is stripped off, and small rubber
million. The polymerization (b) itself is quite particles remain suspended in the water. Further
straightforward. The butyllithium initiator is added contact with steam reduces the content of hydro-
to the reaction mixture, and polymerization occurs carbon in the rubber. Improvement of the strip-
usually going to completion. Different reactor ping process has been necessary because of the
configurations can be used to produce either nar- need to reduce the pollution of air and water; this
row or broad molar mass distributions as desired, has been accomplished with better contactors and
and DVB may be added to increase branching of additional stripping vessels. The slurry of rubber
the polymer. is then dewatered (d), usually with an extruder
One of the advantages of lithium chemistry is that squeezes out most of the water. A final drying
the ability to polymerize at relatively high tem- stage in a fluidized bed or tunnel dryer (e)
perature where water cooling is adequate and completes the process, and the rubber is baled
reactions are rapid. and packaged (f).
For HIPS application a colorless polymer with Earlier processes for removing solvent direct-
a good stability, and a gel level < 200 ppm is ly with drum dryers have now largely been
required. This means that the polymer must be abandoned. A thin layer of polymer cement was
well protected during the production process. dried on a large heated drum but this process is no
Tradionally, a combination of a hindered phenol longer used extensively because of the inherently
as a free radical scavenger and a phosphite as high solvent losses.
hydroperoxide decomposer has been used as
antioxidant. Concerns about the deleterious ef-
fects of nonylphenol produced by hydrolysis of 1.2.3. Producers and Production
trinonylphenyl phosphite has led to the search for Capacities [74, 76]
new antioxidant systems.
The need for a low gel content requires that the Polybutadiene Rubber is the second larg-
drying and finishing steps be carried out without est synthetic rubber product after SBR: In 1995,
658 Rubber, 5. Solution Rubbers Vol. 31

Table 3. Producers of polybutadiene rubber 2. Synthesis by Ziegler – Natta

Company Country Trade name Polymerization
Asahi Chemical Japan Asadene
Bayer France Buna
2.1. Polybutadiene and Polyisoprene
Bayer United States Taktene 550 Rubber
Coperbo Brazil Coperflex BR
Enichem Italy Intene, Intolene
Firestone United States Diene
2.1.1. Properties, Grades, and
Japan Elastomer Japan Asaprene Applications
Karbochem South Africa Afdene
Kumho Korea High-cis-Polybutadiene. High-cis-polybu-
Negromex Mexico Solprene
Petrochim Belgium Finaprene
tadiene is the second largest volume synthetic
Repsol Spain Calpene elastomer, second only to emulsion SBR: It is
used primarily in the manufacture of tires. Mod-
erate amounts are also used in high-impact poly-
styrene and ABS. In these markets it competes
1 402 000 t was produced, exclusive of Eastern with lithium polybutadiene (see Section 1.2).
Europe and the socialist countries of Asia. Small amounts of high-cis-polybutadiene (2 –
Worldwide annual BR capacities were about 3 %) are used in other applications, such as golf
2 3280 000 t at the end of 1996, as estimated balls, hose roll covers, and conveyor belts.
by the International Institute of Synthetic Rubber The principal characteristic of this polymer is
Producers. This figure is, however, difficult to the high content of cis-1,4-microstructures,
interpret, because most of the capacity can be which is generally 92 – 98 % (Table 4). The
used to produce BR, SBR, and block copolymers. cis-1,4-polymer chain has a very low Tg ( 10
Special BR types – e.g., polymers with special

C). This leads to high resilience, good low-
end groups, liquid polymers, high-vinyl poly- temperature properties, and low heat buildup on
mers – are produced only in small amounts. repeated deformation [79–81]. These character-
The technology for the preparation of Li-BR istics are needed in tire treads, carcass stocks, and
was developed by Firestone Tire & Rubber Co. [54, sidewalls [82]. High cis-BR provides the ex-
77] in the 1950s; Firestone is still proucing Li-BR tremely rapid chain motions needed for abrasion
with the trade name Diene. Among the other resistance and resilience of tires. In the tread
producers of low- and medium-cis-BR, and in some portion of the tire, cis-BR is blended with rubbers
cases of high-vinyl types as well, are the following with a higher Tg, such as SBR, to improve
producers listed in Table 3 (with trade names). traction.
The differences in microstructure shown in
Isoprene Rubber. According to IISRP sta- Table 4 do not decisively affect product perfor-
tistics, 116 000 t of synthetic isoprene were pro- mance. The vinyl group has a higher Tg
duced in 1995 outside the Eastern bloc countries. (  106
C), but since the vinyl content is only
Most of this is high-cis material produced by 0 – 4 %, it has only a small effect on the overall
Ziegler – Natta catalysts. Shell Nederland Che- glass transition temperature. The higher level of
mie produces Li-IR under the trade name Cari- cis-1,4-microstructure seen when neodymium is
flex [78]. A 3,4-polyisoprene previously pro- used as catalyst seems to improve fatigue prop-
duced by H€ uls (Vestogrip) is now made by erties in some applications. The higher linearity
Karbochem under the trade name Isogrip. Kur- of Nd-Br polymers may also contribute to this
arary produces a small amount of liquid IR. result.

Table 4. Dependence of microstructure of Ziegler – Natta polybutadiene on catalyst used

Cis content, % Trans content, % Vinyl content, % Molar mass distribution Tg,
C

Cobalt 97 1 2 moderate  106

Titanium 93 3 4 moderate  103
Nickel 97 2 1 broad  107
Neodymium 98 1 1 very broad  109
Vol. 31 Rubber, 5. Solution Rubbers 659

High cis-BR polymers show significant vari- due to stress relaxation, which is too fast. Slower
ation in processing characterstics because of relaxations as a result of branching or molar mass
differences in molar mass, molar mass distribu- jumping improves processing on mills. Proces-
tion, and degree of branching. These factors vary sing problems with high cis-polymer are dimin-
even within polymers produced by the same ished in compounds of higher cis-BR where
catalyst system, so overall conclusions about either SBR or natural rubber is also present.
preferred catalyst systems are somewhat difficult As with all polymers, mechanical properties
to reach. On balance, the nickel-catalyzed poly- are a function of molar mass. Tensile strength,
mers, with their broad molar mass distribution abrasion resistance, and fatigue resistance all
and slightly higher degree of branching are some- improve as the molar mass of the polymer in-
what easier to process (better mill compound creases. Balanced against this, of course, is the
behavior and extrudability), but their tensile greater difficulty of mixing and processing high-
properties and fatigue resistance are inferior. er molar mass polymers.
Titanium-catalyzed polymers, with their lower
branching and moderate molar mass distribution, Oil Extension with naphthenic or aromatic
are more difficult to process but better in tensile oil is used to make higher molar mass products
strength and fatigue resistance. Polymers synthe- processible. One producer of high-cis-BR also
sized with cobalt catalyst systems can be pro- makes a polybutadiene black masterbatch. In this
duced with a varying degree of branching. The case, both carbon black and oil are added to the
branched grades are easy to process, whereas the polymer while it is still in solution. This facil-
more linear polymers have better dynamic me- itates subsequent processing and allows high
chanical properties. Polymers made with neo- molar mass polymers to be handled with relative
dymium systems are highly linear and have a ease.
broad molar mass distribution. This gives them As mentioned previously, the degree of
a desirable balance of properties with the excep- branching of these polymers can vary. Relatively
tion of poor extrudability and high cold flow. little is known about the nature of this branching
The processing properties of some neodymium- or about its cause. However, the branching dif-
catalyzed polymers are improved by ‘‘molar ferences in the products can be observed fairly
mass jumping’’ as described below. easily in dynamic mechanical or stress relaxation
Most high-cis-BRs do not have the high tack tests.
and green strength of natural rubber. When the Another important characteristic of some
products were developed, extensive work was grades of polybutadiene is the gel content. In
carried out to determine the reasons for this and to tire applications this is not generally a concern.
improve the product, but a commercially attrac- However, BR used in high-impact polystyrene
tive route does not seem to have been found. must have very low gel levels. It is primarily the
Polymers produced with neodymium systems are cobalt-catalyzed BR that is used to produce HIPS
somewhat improved in this regard, but still not to (the other product used is lithium-catalyzed BR;
the level of natural rubber. see Section 1.2). The neodymium catalyst sys-
High-cis-BR is also prone to cold flow (i.e., tem may be capable of producing HIPS-quality
the tendency of unvulcanized rubber to flow BR, but unsatisfactory control of solution viscos-
during storage). In extreme cases, the bales of ity has so far kept it out of this application.
high-cis-butadiene rubber are completely dis- In addition to the low gel content, HIPS-BR
torted to the point that the film wrap splits. Cold must also contain low residues of catalyst, have
flow is most serious for low molar mass or highly little color, and contain a suitable type and level
linear materials. Long-chain branching is intro- of antioxidant so that the HIPS polymerization is
duced into some products to reduce cold flow. not retarded. The most common antioxidant sys-
This can be carried out by postpolymerization tem is a combination of a hindered phenol and a
reactions, sometimes termed ‘‘molar mass jump- phosphite. Concern about the adverse health
ing’’, that involve reacting the polymer in solu- effect of free nonylphenol formed by hydrolysis
tion with disulfur dichloride. of trinonylphenyl phosphite has led to the evalu-
As noted above, high-cis-BR has relatively ation of new stabilizers that do not contain tri-
poor processing properties. In many cases, this is nonylphenyl phosphite.
660 Rubber, 5. Solution Rubbers Vol. 31

Although the content of 1,2-units is only 0 – Other Commercial Ziegler –

4 %, it can still influence the HIPS process by Natta-Catalyzed Polydienes.
affecting the rate of grafting of the polystyrene Trans-1,4-Polyisoprene. A Ziegler – Natta
on the rubber. The solution viscosity of the system is used by Kuraray (Japan) to produce
rubber in the styrene monomer is also of con- trans-1,4-polyisoprene that is similar in molecu-
siderable importance because it determines lar structure and properties to the natural product
how, and when, the rubber phase breaks up to balata. Because of its low melting point the
yield rubber particles. The size and nature of the crystalline product can be used for splinting or
rubber particles are very important in determin- prosthetic applications. Sheets of the product are
ing the impact properties of HIPS (see also softened in an oven or with hot water and then
! Polystyrene and Styrene Copolymers, Sec- molded to the body and allowed to cool. Trans-
tion 1.1). 1,4-polyisoprene is also used for golf ball covers,
where it competes with ionomers. The process
High-cis-Polyisoprene. Polyisoprene pro- used to make the trans polymer gives a lower
duced with a Ziegler – Natta catalyst attracted yield of product, and the relatively high price of
considerable interest when it was developed and the product limits it to low-volume specialty
commercialized in the 1960s. The polymer has a applications.
microstructure very similar to that of natural
rubber, but it has inferior green strength and tack Syndiotactic 1,2-Polybutadiene. Another
[82, 83]. Considerable research has been carried low volume polymer produced by Ziegler –
out to determine why high-cis polyisoprene Natta catalysis is syndiotactic 1,2-polybutadiene
does not duplicate all the properties of natural (JSR BR). This partly crystalline product is a
rubber. Although natural rubber contains almost thermoplastic elastomer with high purity. It is
100 % cis-1,4-structures, the microstructure is produced with only 15 – 30 % crystallinity to
not the only important difference between the make it flexible and processible, and is used as
synthetic and the natural products. Functional a high-permeability film in food packaging. It is
groups on the natural product and nonrubber also used as a dispersible film wrap for rubber and
components are also important in influencing rubber chemicals, but in this application it faces
green strength, tack, and tensile properties. Un- stiff competition from much less expensive films,
fortunately, the availability and cost of isoprene such as polyethylene and ethylene – vinyl ace-
have remained a problem. Isoprene synthesis is tate copolymer films.
more difficult than that of butadiene, and its Research on tires is devoted to reduction of
purification is also more complicated (! Iso- rolling resistance without detracting from
prene, Chap. 3). Isoprene containing C5 streams wear or traction properties. This has resulted
from cracking operations are used to the extent in a trend toward S-SBR instead of E-SBR (see
available. As a result, both the monomer and the ! Rubber, 4. Emulsion Rubbers, Chap. 1).
polymer are relatively expensive. The availabil- Tread compounds are also increasingly rein-
ity of natural rubber at reasonable cost has made forced with silica instead of carbon black. In
the synthetic polymers unattractive, and a num- the endeavor to improve rolling resistance the
ber of plants in the Western World have been levels of high-cis-BR in tread compounds
closed. Some high-cis-polyisoprene is still pro- were also increased. Some research on novel
duced by Goodyear JSR and Nippon Zeon. It is Ziegler – Natta polymers such as butadiene –
used where its high purity is an advantage and isoprene copolymers has been carried out.
also as a processing aid for natural rubber. Shell Thes products have had little commercial
also produces a polyisoprene in the Netherlands success.
using a lithium catalyst.
Substantial volumes of Ziegler – Natta poly-
isoprene were produced in Eastern Europe. How- 2.1.2. Basic Chemistry and Production
ever, most of the production capacity cannot be Processes
operated economically and has been shut down.
The operation of such facilities depends on natu- High-cis-Polybutadiene. Ziegler – Natta
ral rubber pricing. polybutadiene was first produced by Phillips
Vol. 31 Rubber, 5. Solution Rubbers 661

Petroleum in 1956 using titanium catalysts [84]. terminate the reaction. Antioxidants are added,
This was followed very rapidly by development and steam and water are brought into contact with
of cobalt and nickel systems [85–87]. The ability the polymer solution to strip off the solvent and
of these catalysts to produce high-cis polymers any residual monomer. This coagulation and
with properties similar to those of natural rubber stripping operation leaves the rubber in the form
led to rapid commercialization of both high-cis- of small particles floating in water. The water is
polybutadiene and high-cis-polyisoprene. The drained off through a screen, and the material is
latter business dwindled due to the lack of ac- dewatered, usually in an extruder. The final
ceptably priced monomer and to competition drying is carried out in a fluidized-bed dryer,
from relatively low-cost natural rubber. In con- tunnel dryer, or twin-screw drying extruder.
trast, the production of polybutadiene has Good operation of the solvent removal step is
benefited from a ready supply of cheap monomer. important to minimize air and water pollution.
Technical developments in the field have been Solvent loss of 1 or 2 wt %, based on the weight
fairly modest since the 1980s, but more recent of polymer, occurred in older processes. Im-
work on rare-earth catalyst systems has revived proved stripping conditions, additional stripping
interest in product and process improvement. vessels, and other changes have been implemen-
Very good early studies have been carried out ted to reduce losses of solvent to  0.3 wt %.
by GIPPIN [88, 89]. Reviews of the technology Work has been carried out to improve engineer-
have been published [90–92]. ing practices throughout the plants in order to
Ziegler – Natta polybutadienes are produced reduce losses at valves, flanges, and pumps. In
by solution processes using a variety of solvents. some cases, air from these sources is ducted and
Some, such as the titanium process, are best used as boiler combustion air to prevent losses to
carried out in aromatic solvents, whereas others, the environment. There has also been some con-
such as the neodymium-catalyzed process, can cern regarding exposure to butadiene monomer,
be carried out only in aliphatic or cycloaliphatic and the improved stripping mentioned above is
solvents. As indicated below, each catalyst sys- important in minimizing this exposure.
tem has its own unique features. However, the
various Ziegler – Natta systems share common Co-BR. Polymerization to form high-cis-
elements. All are sensitive to impurities, thus BR, based on cobalt catalysts, was disclosed in
monomer and recycle solvent streams must be early patents to B. F. Goodrich [86], and this
well purified. Carbonyl and acetylenic impurities technology was later licensed to other compa-
in the monomer must be at the level of a few parts nies. Various cobalt compounds can be used.
per million, and the polymerization inhibitor (tert Because CoCl2 is insoluble in the aromatic sol-
butylcatechol) is usually removed from the vent used, work was carried out to use soluble
monomer prior to reaction. cobalt salts such as the acetylacetonate, the octo-
The feed streams of monomer and solvent are ate, or the versatate. These materials are readily
usually dried by azeotropic distillation and fed to available and are easy to handle in solution.
a series of polymerization reactors. Ziegler – The other catalyst components are an alkyla-
Natta catalysts are, commonly, three-component luminum compound and small amounts of water.
systems, and both the order of addition and the Various alkylaluminum compounds can be used.
mixing conditions can be important. The catalyst The most common material is diethylaluminum
components may be added directly into the first chloride [(C2H5)2AlCl], but aluminum com-
reactor or some components may be added into a pounds containing more chlorine, such as the
premix vessel ahead of the reactor or into the feed sesquichloride [(C2H5)3Al2Cl3], can also be em-
line. Various methods are used to control the ployed. Catalysts with lower chlorine content
molar mass of the products. Molar mass modi- have reduced activity.
fiers specific to the catalyst system are used The amount of water used in the system is very
where necessary. The final conversion of ca. important. With diethylaluminum chloride, very
70 – 99 % is achieved in a polymerization time little polymerization occurs in the absence of
of 2 – 3 h. water. As the water content is increased, the
After polymerization a short stop is added. reaction becomes more rapid, then passes
Water, fatty acids, or alcohols, can be used to through a maximum, and again declines to zero
662 Rubber, 5. Solution Rubbers Vol. 31

at higher concentration. As the water level is As mentioned above, the rate of polymeriza-
increased, so does the solution viscosity of the tion is a complex function of the amount of water
polymer at a given Mooney viscosity. This in- present. The water concentration also influences
creased solution viscosity results in improved molar mass, branching, and to a small degree, the
dynamic properties and is commonly interpreted microstructure of the resulting polymer. The
as a lower degree of branching. degree of branching decreases with increasing
Polymerizations carried out with alkylalu- water level. Gel levels in the product also in-
minum compounds containing more chlorine in crease with the amount of water charged. It does
the molecule than diethylaluminum chloride not appear, therefore, that gel forms because
can be used without adding water, but in prac- branching has increased to the point at which a
tice, this method generally does not offer any network can form.
advantages. Cobalt-catalyzed polymerization is usually
Polymerization is usually carried out at 5 – carried out with very low levels of cobalt. Many
35
C, depending on the solvent and the heat chains are formed by each cobalt atom. In con-
removal capability of the reactor. Early work was trast, the alkylaluminum is present in large ex-
based mostly on benzene as the solvent. Howev- cess. Water levels in the range of 0.1 – 0.5 mol
er, with increased concern about loss of solvent to per mole of alkylaluminum compound are gen-
air or water, work has been carried out to find erally used.
other suitable solvents. Cyclohexane can be used The mechanism of polymerization is only
in place of benzene, although side reactions partially understood [93]. The functional groups
leading to gel formation or to fouling of the attached to the aluminum and cobalt appear to be
reactor may be more pronounced. Aromatic sol- exchanged, and cobalt is reduced from Co2þ to
vents with methyl substituents can be added in Coþ. Coordination of butadiene to the catalyst
small amounts. These substituted aromatics sta- complex is involved in the stereoregulating
bilize the catalyst complex but also reduce the mechanism. When aromatic solvents are present,
reaction rate. they can form strong complexes with the catalyst
The molar mass of the polymer produced can and displace the monomer as a ligand. With
be controlled by monomer concentration or by substituted aromatics, the catalyst complex can
the addition of modifiers, such as hydrogen, 1,2- become so stable that little polymerization
butadiene, propadiene, or cyclooctadiene. a- occurs.
Olefins, such as ethylene, propene, 1-butene, or
1-hexene can also be used to reduce the molar Titanium-Catalyzed Polybutadiene. The
mass of the polymer. Ziegler – Natta polybutadiene process devel-
Cobalt polybutadiene is often used in high- oped by Phillips Petroleum uses a catalyst of
impact polystyrene. HIPS used for extrusion titanium tetraiodide and triisobutylaluminum
applications must contain less than 200 – [94]. The low solubility of the titanium tetraio-
300 ppm of gel to prevent visible defects in the dide in the hydrocarbon solvent led to production
HIPS. To meet such stringent conditions, a cata- difficulties, and numerous other systems were
lyst system must be selected that does not favor developed to improve handling and product uni-
side reactions, and the feed must be very pure. formity. The common element in the various
Extra care is required to keep the product free of systems is the presence of iodine with the even-
gel particles. The polymer solutions are filtered tual formation of a titanium – iodine bond
after polymerization, and wash steps are incor- [95–98]. Catalysts that contain other halogens
porated to remove catalyst residues. Extra care do not yield the desired high content of cis
imust be taken to ensure that the product is not microstructure in the polymer and are prone to
degraded. other difficulties such as the formation of gel and
The reaction rates of cobalt-catalyzed poly- low molar mass oligomers.
merization are generally proportional to the con- A precipitate forms during these polymeriza-
centrations of both cobalt and monomer. With tions, which further complicates the process.
increasing cobalt concentration the molar mass Extra care must be taken to bring the catalyst
of the polymer decreases and the polymer be- species together in a desirable and reproducible
comes more branched. way.
Vol. 31 Rubber, 5. Solution Rubbers 663

Polymerization is usually carried out in ben- of the chloride: neodymium ratio. The chain-
zene or toluene. However, mixed aromatic – transfer agents used in other Ziegler – Natta
aliphatic solvents or even totally aliphatic sys- catalyst systems (olefins, hydrogen, allene, etc.)
tems can be used with some difficulty. Polymeri- are inactive in this system [109]. In the neodymi-
zation can occur over the range 5 – 50
C. um system the molar mass is varied by using a
The efficiency of titanium catalyst systems is hydride such as diethylaluminum hydride or
influenced by the aluminum – titanium ratio. diisobutylaluminum hydride.
The cis content, molar mass, molar mass distri- The neodymium polybutadiene system gives
bution of the product, and catalyst activity are all rapid polymerization to achieve very high con-
influenced by this ratio. The optimum ratio de- versions. Monomer concentrations of 10 –
pends on the system in use. 20 wt % are generally used. The upper concen-
tration limit depends on the ability of the equip-
Nickel-Catalyzed Polybutadiene. Many ment to handle the highly viscous solution and on
Ziegler – Natta catalyst systems, based on nic- the efficiency of heat removal. The polymers
kel, have been disclosed in the literature. Those obtained have a very broad molar mass distribu-
containing fluorine generally give a high content tion and thus a high solution viscosity.
of cis-1,4-microstructure in the polybutadiene. The neodymium catalyst system does not
These catalysts were developed by Bridgestone tolerate aromatic solvents. Polymerization can
[87, 99, 100] and studied in other laboratories be carried out in a variety of aliphatic and cyclo-
[101, 102]. The most common catalyst system aliphatic solvents, generally at 50 – 90
C. The
consists of a nickel carboxylate with an alkyla- molar mass of the product is inversely propor-
luminum and BF3 etherate or HF. These systems tional to the reaction temperature, and the cis
can give cis-1,4-contents of up to 98 % in the content of the polymer declines slightly with
polymer, along with good reactivity at low levels increasing temperature. The system is not sensi-
of nickel and relative freedom from gel. As in tive to water at part-per-million levels as are
most of the Ziegler – Natta catalyst systems used some other Ziegler – Natta systems.
for production of polybutadienes, the molar mass High-cis-BR has been improved incremental-
of the resulting polymer is inversely proportional ly, but the basic product has not been altered
to catalyst concentration. Allenes, acetylenes, significantly for many years. Most of the research
and vinylcyclohexane all retard polymerization has been concerned with process improvement to
and reduce molar mass. The molar mass de- increase yield and reduce cost and environmental
creases with increasing polymerization tempera- hazards. Research is directed toward solvent-
ture. Most polymerizations described in the lit- free, so-called ‘‘gas phase’’ processes, whereby
erature are carried out in either benzene or mixed polymer particles fluidized in monomer vapors
aromatic – aliphatic solvents. are formed. This technology is used for produc-
tion of polyethylene and polyproplyene (!
Neodymium-Catalyzed Polybutadiene. Polyolefins, Section 1.5.3, ! Polyolefins, Sec-
High-cis-polybutadiene can be prepared using tion 2.5.6). Its application to production of high-
some of the lanthanide elements as catalysts cis-BR has been studied in a number of
[103]. A basic patent was filed by Union Carbide laboratories.
in 1963 [104]. Considerable research work on the
system has been carried out by Russian and Syndiotactic 1,2-Polybutadiene. Syndio-
Chinese scientists [105]. The preferred system tactic 1,2-polybutadiene is produced only by
seems to be based on neodymium. Commercial Japan Synthetic Rubber in small amounts [110,
products are now made by Bayer and Enichem. 111]. This partly crystalline material is produced
Rare-earth systems are also in use in South Africa by using a Ziegler – Natta polymerization pro-
and China. The catalyst system consists of rare- cess. Although a 99.7 % 1,2-content can be
earth carboxylates with alkylaluminum and a achieved, the product is deliberately produced
source of chloride, such as diethylaluminum with only ca. 90 % 1,2-content to reduce the
chloride [106–108]. Bulky carboxylates are pre- crystallinity to 15 – 30 %.
ferred to improve catalyst solubility. The reac- The polymer is produced with a cobalt catalyst
tivity is a function of the carboxylate chosen and and an alkylaluminum compound. Triphenyl-
664 Rubber, 5. Solution Rubbers Vol. 31

phosphine is added to give the syndiotactic 1,2- 2.1.3. Producers and Production
microstructure [112]. Capacities

High-cis-Polyisoprene. Titanium catalysts High-cis-Polybutadiene. Production data

are often used to make high-cis-polyisoprene on BR including high-cis-polybutadiene are giv-
[83]. Titanium tetrachloride together with en in Section 1.2.
trialkylaluminum was used in early work, and Of the high-cis-BR technologies, the cobalt
the catalysts currently in use appear to be very process is most widely employed. B. F. Good-
similar [85, 113–115]. This catalyst is not rich technology was licensed during the 1960s
suitable for the production of high-cis-polybu- and 1970s in Canada, the United States, the
tadiene, but it can produce a cis-1,4-polyiso- Federal Republic of Germany, Japan, and Aus-
prene with a cis content as high as 97 % [116]. tralia. Other plants were later built in Turkey,
Isoprene is more easily polymerized than India, the People’s Republic of China, and
butadiene to form polymers with high cis France. This technology has since been refined
content. Even lithium-catalyzed polymers to produce cis-BR with low gel grades for pro-
have ca. 93 % cis-1,4-microstructure (see ductions of HIPS and to control branching. The
Section 1.2). more linear titanium-catalyzed polymers were
The conditions under which the Ziegler – first developed by Phillips. These are now pro-
Natta catalyst components are brought together duced in France, Germany, Japan, and the United
are quite important. In the preferred process, States. Nickel-catalyzed polymers are produced
AIR3 is slowly added to TiCl4 in an aliphatic in the United States, the People’s Republic of
solvent at low temperature. Ethers and amines China, and Japan. A more recently developed
may be used to reduce gel and oligomer forma- process is based on neodymium. High-cis-poly-
tion. The optimum molar ratio of titanium to butadiene is now produced in the United King-
aluminum is about one. This gives a good reac- dom and Germany by this method.
tion rate and minimizes problems of oligomer Producers and trade names are listed in
formation. Molar mass can be influenced by Table 5.
controlling monomer concentration and
temperature. High-cis-Polyisoprene. Worldwide pro-
High-cis-polyisoprene and butadiene – iso- duction of polyisoprene is presently difficult to
prene copolymers can also be produced with estimate and subject to rapid changes. Most of the
neodymium catalysts. This may prove to be of
Table 5. High -cis-polybutadiene producers
interest because of its potential to produce im-
proved polybutadiene products with low levels Company Country Trade name
of the higher-cost isoprene monomer.
American Synthetic United States Cisdene
Rubber Co.
High-trans-1,4-Polyisoprene. Highly crys- Australian Synthetic Australia Austrapol CB
talline trans-1,4-polyisoprene can be produced Bayer United States/ Buna CB, Taktene
by using various vanadium, titanium, or mixed Canada/ Germany
Bridgestone/ Firestone United States Duradene
vanadium – titanium catalysts [116, 117]. The Enichem UK/ Italy Europrene Neocis
VCl3 system has been used commercially [118] Goodyear United States Budene
because it produces less material with low molar Japan Synthetic Rubber Japan JSR BR
mass and gives a higher overall trans-1,4-con- Hyundai Petrochemical Korea
Indian Petrochemicals CL India Cisamer
tent. The process is usually performed at 20 – Karbochem South Africa Neodene
90
C. The addition of ethers or Ti(OR)4 is Kumho Petrochemical Korea Kosyn
claimed to increase the polymerization rate, Michelin France
which is otherwise slow [117, 119]. High solu- Nippon Zeon Japan NIPOL
Petkim Turkey Petcis
tion viscosity necessitates operation at lower Petrochim Romania
solids levels and this limits the productivity of Taiwan Synthetic Rubber Taiwan Taipol
the system. Aliphatic solvents are preferred Ube Industries Japan Ubepol
because the solution viscosity is reduced in this Voronezh SR Russian Republic SKD
Yefremor Russian Republic SKD
case.
Vol. 31 Rubber, 5. Solution Rubbers 665

Table 6. High -cis-polyisoprene producers Properties. The saturated carbon backbone

Company Country Trade name
structure accounts for the following features:
Goodyear United States Natsyn 1. Outstanding ozone resistance
Japan Synthetic Rubber Japan JSR
Nippon Zeon Japan NIPOL IR
2. Excellent weathering stability
Petkin Turkey Petcis 3. Excellent heat resistance (< 175
C)
Petrochim Romania 4. Good insulating properties
Shell Nederland Netherlands (Li polymer) 5. Low-temperature flexibility (glass transition
temperature: ca.  55
C)
Voronezh SR V/O Russian Republic SKI
Raznoimport
Yefrenov V/O Raznoimport Russian Republic SKI 6. Good chemical resistance (toward polar or-
Shanghai GAO DIAO People’s Rep. China ganic and inorganic compounds)
7. Good moisture and steam resistance

capacity is in Eastern European but the econom- EPM and EPDM have the lowest density
ics of these plants are marginal now and much of (0.86 kg/L) of any commercial elastomer. In
the capacity is shut down. The other major addition, during compounding, EP(D)M can be
economic factor is the price of natural rubber heavily loaded with oil and fillers resulting in low
which can fluctuate widely. Current producers compound costs.
and trade names are given in Table 6. The structure of the polymer can generally be
described by three features:
Syndiotactic 1,2-Polybutadiene is pro-
duced by Japan Synthetic (trade name JSR RB). 1. Ethylene: propene ratio and monomer se-
quence distribution
2. Molar mass and molar mass distribution
2.2. Ethylene – Propene Elastomers 3. Content and type of diene incorporated
(EPM, EPDM) [120–122]
These structural features are directly related to
2.2.1. Properties, Grades, and the polymerization conditions. By varying the
Applications conditions, polymers with different properties
can be obtained and a large selection can be
Ethylene – propene elastomers are a family of provided, suitable for various applications.
random elastomeric copolymers with a As ethylene content increases:
completely saturated polymer backbone. These
elastomers are therefore designated with an ‘‘M’’ Stress – strain properties improve
according to the ASTM standard DIN/ISO 1629. Green strength improves
There are two basic types of ethylene – pro- Compression set deteriorates
pene elastomers: Low temperature flexibility deteriorates
Hardness increases
1. Ethylene – propene copolymers (EPM)
2. Ethylene – propene – diene terpolymers As molar mass increases:
(EPDM)
Stress – strain properties improve
The copolymers are generally amorphous elasto- Green strength improves
meric polymers without unsaturated bonds, thus Extendability improves
necessitating the use of peroxide cure systems for Compression set improves
vulcanization. The terpolymers contain small
quantities (< 12 wt %) of a nonconjugated di- As diene content increases:
ene. Only one of the double bonds of each diene
molecule takes part in polymerization, resulting Stress – strain properties improve
in a saturated polymer backbone with a pendant Compression set improves
double bond that facilitates the use of conven- Cure rate increases
tional sulfur curing. Heat aging resistance declines
666 Rubber, 5. Solution Rubbers Vol. 31

The diene type (see Section 2.2.2) influences Table 7. Applications of EPM and EPDM (1991)
compound properties as follows: Ethylidenenor- Market Market Typical applications
bornene (ENB) gives the fastest cure rate; dicy- segment breakdown
clopentadiene (DCPD) the best processability;
Automotive 32 % radiator/heater hoses, weatherstrips,
and 1,4-hexadiene (HD) the best heat resistance. window channels,
The EP(D)M grades (ca. 250 available world- sponge seals, mounts, car mats
wide) are constantly optimized to fit specialty Plastics 15 % impact-modified polypropylene,
applications. Although many manufacturers pro- modification thermoplastic olefins
Construction 14 % roofing membrane, window seals
duce particular grades which are reasonable sub- Industrial 11 % steam and garden hoses, gaskets
stitutes for one another, EP(D)M elastomers are O-rings, mounts
not standardized as are general-purpose rubbers. Oil 10 % oil viscosity improver
Listings of grades are summarized in [123]. Electrical 6% cable jacketing, insulation, cable filler,
connectors
Tire 4% sidewall construction, inner tubes, tire
Specifications. The amount of information valves
provided by manufacturers in their specifications Miscellaneous 8% footwear, carpet underlay
differs. Mooney viscosity – the basic qualitative
index of molar mass and processability – is always
specified. Mooney viscosity is usually expressed at
100
C, 125
C, or 150
C. Higher temperatures Uses in Tires. In the 1960s, EPDM was
are used for accurate Mooney measurements of expected to become the new tire elastomer. But
higher molar mass grades with a Mooney viscosity until recently, its utilization for tire applications
> 80 – 100 at 100
C. There are no absolute has been limited to some inner tubes and to
measurements of molar mass. Each manufacturer blends for white side-walls. The main deficiency
quotes his own set of numbers. The conditions of EPDM is inability to develop adhesion and to
under which the number is measured must be covulcanize with unsaturated polymers such as
clearly specified in all cases. Oil content, if any, natural rubber, or polybutadiene.
is given in phr. Some manufacturers specify ethyl- The physical properties of blends with highly
ene content (40 – 80 wt %), diene content (0 – unsaturated rubbers are poor, due to a lack of co-
12 wt %), iodine number, and maximum residues cure between the polymers. The conventional
(e.g., 50 ppm transition metal, 0.3 % ash, 0.5 % explanation is that the unsaturated polymer is
water or volatiles content). Performance of a stan- overcured before the EPDM phase in the blend
dard compound is usually given, including cure can achieve a high state of cure. This is due to the
characteristics (delta torque, cure times), tensile very different cure rates of the two polymers.
strength (4 – 22 MPa). Elongation at break EPDM is generally much slower than highly un-
(150 – 800 %), and compression set (5 – 20 % saturated rubbers [124]. The physical properties of
after 22 h at 70
C). Density varies according to blends can be improved by modifying the EPDM
diene content and crystallinity, but is in the range with, for example, maleic anhydride [125], but this
0.86 – 0.90 kg/L. approach is too costly for tire applications.
In blends with NR, excellent physical proper-
Storage and Transportation. The rubber is ties and adhesion can be achieved when the
generally shipped in boxes containing bales of 25 EPDM has high molar mass and high (> 8 %)
to 34 kg, multiunits of bales, or bags of pellets for ethylidenenorbornene content [126, 127]. This
certain semicrystalline grades. Rubber proces- concept is commercially being used in veneers
sors prefer loosely packed bales, whereas plastic for radial passenger tires. The veneer is resistant
blenders prefer pellets. to weathering, since the EPDM phase is immune
to ozone attack, and the NR phase domains are so
Uses. As a result of their versatility, EP(D)M small that cracks cannot easily grow. No chemi-
polymers find use in a number of market seg- cal antidegradants are required in the formula-
ments, both in the traditional thermoset areas, tion, so discoloration from staining antioxidants
and increasingly in thermoplastic blends and is avoided [128]. Development of this technology
alloys. Typical applications for EP(D)M are for tire sidewalls and other tire components is
given in Table 7. underway in tire companies worldwide.
Vol. 31 Rubber, 5. Solution Rubbers 667

2.2.2. Basic Chemistry and Production polymerization and gives high quality, fast cur-
Processes ing elastomers. ENB polymers cure faster than
polymers containing other termonomers. This is
Monomers. The monomers ethylene and essential for high productivity in continuous
propene are normally used as polymerization curing extruded applications.
grade (purity > 99 %) and must be free of impu-
rities such as carbon monoxide, oxygen, water, Dicyclopentadiene is used as a termonomer
acetylene, methanol, or methylacetylene (con- due to its low cost and its high reactivity in the
tent < 10 ppm). These impurities are potent polymerization. The main deficiency of DCPD
poisons of Ziegler – Natta catalysts, which are terpolymers is their slow cure rate relative to
exclusively used for EP(D)M polymerization terpolymers containing ENB. Another disadvan-
[122, 129]. tage is that DCPD can be easily cracked to
cyclopentadiene (CPD) during stripping and
Termonomers. The ideal termonomer has monomer recovery operations. Catalyst efficien-
to meet several important criteria. It should have cy is severely reduced, if CPD levels build-up in
two double bonds of widely different reactivity. the process streams.
One double bond should react rapidly in the There are some similarities between DCP
terpolymerization, while the second one should and ENB. Both molecules contain a seven-
be relatively inert. However, this second double membered dicyclic norbornene ring in which
bond must be reactive toward the vulcanizing one double bond is a member of a highly
agent. The monomer should also be volatile, so strained five-membered carbon ring. This dou-
that the residual unreacted monomer can be ble bond enters rapidly into the polymerization.
easily removed from the polymer after polymer- The exocyclic ethylenic double bond in ENB is
ization. Finally, the termonomer should be read- sterically hindered so it does not react during
ily available and inexpensive. However, no ter- polymerization. In DCPD, the second double
monomer meets all criteria. Many compounds bond is not ‘‘protected’’ by steric hinderance. It
have been investigated as possible termonomers can, therefore, take part in the polymerization
[120]. Most research has been restricted to non- leading to branching, cross-linking, and possi-
conjugated dienes as termonomers since they bly gel formation. The processability of DCPD
have minimal influence on copolymerization, terpolymers is improved in comparison with
yield normal molar mass distributions, and only ENB polymers because of the broadening
introduce unsaturation in side chains. The differ- of molar mass distribution as a result of
ent termonomers commercially used for EPDM branching.
are shown in Figure 5.
1,4-Hexadiene (HD) is exclusively used by
Ethylenenorbornene is the most commonly Du Pont. It is a linear nonconjugated diene.
used termonomer because it reacts rapidly in the Polymerization favorably occurs via the 1,2
position because of the steric hindrance of the
4,5 double bond. In contrast to ENB and DCPD
rings, HD is less reactive in polymerization due
to the lack of bond strain. 1,4-Hexadiene has a
low boiling point (66
C) and is not separated
from the solvent during the solvent recycle.
The cure rate of EPDM using HD as the ter-
monomer is slower than with EPDM using
ENB and is comparable with DCPD as termo-
nomer. Due to the relative absence of side
reactions, compounds based on HD polymers
show the best heat resistance of all EPDM
vulcanizates. HD polymers are most suitable
for post modification, e.g., reaction with maleic
Figure 5. Termonomers used for production of EPDM anhydride.
668 Rubber, 5. Solution Rubbers Vol. 31

Catalysts. Commercial EP(D)M polymeri- molar mass. As in homopolymerization, transfer

zation processes employ vanadium or titanium agents such as hydrogen and diethyl zinc are
catalysts. Metallocene catalysts, although com- widely used for the primary control of molar
mercially used for polyolefin polymerization (! mass of the polymer during copolymerization.
Polyolefins, Section 1.3.2) are currently in the
pilot plant stage for EP(D)M polymerization Production Processes. At present, com-
[130–132]. mercial EPM and EPDM polymers are produced
by solution or suspension processes. Most man-
Vanadium Compounds are used more widely ufacturers use a solution process. The reaction is
than titanium compounds as catalysts. Vanadium homogeneous; the process is flexible and capable
compounds are soluble in hydrocarbons and form of producing many different grades of products.
an essentially homogeneous system, in addition Enichem and Miles (Bayer) use a suspension
the elastomeric polymers produced by these process [122]. Both solution and suspension are
catalysts contain no or a minimal amount of continuous processes which typically consist of
crystalline, homopolymer fractions. However, four operating sections, i.e., polymerization, mo-
vanadium catalysts are less active than titanium momer and solvent recycling, product recovery,
or metallocene catalysts. and production finishing.
The most widely used commercial vanadium
compounds are vanadium oxytrichloride, vana- Solution Process. The schematic of a typical
dium tetrachloride, and vanadium trisacetyla- solution process is shown in Figure 6. Typcially,
cetonate. polymerization is carried out at 10 – 50
C and
There are also many different aluminum al- 1 – 20 bar in a single continuous stirred-tank
kyls which can be used as cocatalysts for EP(D) reactor (CSTR) (a). The polymerization is exo-
M polymerization. The most widely used com- thermic (DH   2.4 MJ per kilogram of poly-
mercial compounds are diethylaluminum chlo- mer). The heat of reaction is removed by pre-
ride and ethylaluminum sesquichloride. cooling the reactor feeds and/or evaporative
cooling of the reaction mixture. The residence
Reactivators. Catalyst efficiency (typically times in the reactor range from 15 – 60 min,
800 – 8000 g polymer per gram vanadium) can depending on the catalyst employed, tempera-
be improved by using reactivators. The active ture, etc. Ethylene conversion is nearly complete
oxidation state of vanadium is þ 3; vanadium is in a single pass through the reactor. Unreacted
reduced from oxidation state þ 4 (VCl4) or þ 5 propene is recovered and recycled to the poly-
(VOCl3) during alkylation [133]. Vanadium in merization. Solvent (usually hexane) and un-
the inactive oxidation state of þ 2 can be reacti- reacted diene are also recovered for reuse after
vated by treatment with compounds containing purification. Immediately downstream of the
active halogen atoms which can oxidize the de- reactor, the polymerization is shortstopped with
activated vanadium species back to the þ 3 va- water, alcohol, or other polar liquids (b). The
lence state [134, 135]. Ethyl trichloroacetate and polymer solution is then mixed with water, aque-
n-butyl perchlorocrotonate are commercially ous sodium hydroxide, or dilute acid under vig-
used. DSM has promoted the EP(D)M reactivator orous agitation to remove catalyst residues (c).
ethyl dichlorophenylacetate. It is claimed that this After addition of chemicals such as extender oils
compound combines an excellent reactivation and stabilizers (d), the polymer solution is coag-
effect with lower residual vanadium and chlorine ulated and stripped with steam and hot water to
levels in the finished polymer [136, 137]. remove unreacted monomers and solvents (e).
Antiagglomerants and antifoaming agents may
Molar Mass Control. In most Ziegler – be added to control crumb agglomeration and
Natta systems, the molar mass of the polymer is facilitate the separation of gas and liquid. The
influenced by the type of solvent, the concentra- rubber crumb is then passed over a screen (f) to
tion of monomers, catalyst and reactivator, the remove free water and subsequently dried. Either
temperature, the aluminum : vanadium ratio and extrusion drying or hot air drying may be used.
the ethylene : propene ratio [129]. Trace levels of EP(D)M is sold in the form of crumb, bales, or
impurities can also have a significant effect on pellets.
Vol. 31 Rubber, 5. Solution Rubbers 669

Figure 6. Solution process for production of EPM/EPDM [138, 139]

a) Reactor; b) Shortstopping section; c) Separation of catalyst; d) Addition of chemicals; e) Steam stripping section;
f ) Screen; g) Expeller; h) Expander

Suspension Process. Suspension polymeri- polymers [122], due to multiple active sites with
zation is carried out in an excess of liquid titanium compared with essentially single sites
propene. The polymer precipitates out of the with vanadium.
reaction medium as soon as it is formed. Conse-
quently, the viscosity increase in the polymeri- Gas-Phase Polymerization. Gas-phase po-
zation medium is negligible, compared with that lymerization is now commonplace for polyole-
of solution polymerization. The solids content in fins [142, 143] (! Polyolefins, Section 1.5.3)
the reaction medium can therefore be higher than and some types of modified polypropylenes (re-
in the solution process, e.g., 20 – 30 wt % in- actor-modified thermoplastic olefins) [144]. Ex-
stead of 5 – 10 wt %. Monomer recovery, strip- tension of this technology to the full range of
ping, and finishing are carried out as described elastomeric co- and terpolymers is in the ad-
for the solution process except that the coagula- vanced pilot plant stage [145–147]. A schematic
tion step is not required since the polymer already of the overall Union Carbide gas-phase process is
exists as particles. The slurry process is well shown in Figure 7.
suited to the production of grades with high Monomers and catalysts are fed to the reactor
Mooney viscosity, which can be oil extended for (c) and the product is removed intermittently.
easier processing. Heat of reaction is removed by circulating the
Dutral (now Enichem) is running a simplified fluidizing gas through heat exchangers outside
suspension process for the production of EPM, the reactor. The process uses no solvents and
using a highly active catalyst based on titanium. does not require a catalyst residue removal step.
The product is recovered directly from the sus- Solvent stripping and recovery operations are
pension in an extruder-based system, without avoided, although unreacted monomers must be
the prior catalyst residue removal. The un- purged before discharging the product. In prin-
reacted monomers are recycled to the reactor ciple this technology offers the advantages of
without treatment or distillation [140, 141]. This reduced capital and operating costs when com-
new slurry process offers the advantages of pared to the conventional processes. It has yet to
reduced capital and operating costs. However, be proven, however, that the fluidized-bed pro-
presently this process is limited to the produc- cess can produce as wide a range of products,
tion of EPM. Unfortunately, polymers produced having the same or comparable properties (e.g.,
with titanium catalysts tend to have a less ran- high ENB or low Mooney) as those produced by
dom monomer sequence distribution compared existing processes and that the product grade
with existing vanadium-based commercial co- changeover time is not prohibitive.
670 Rubber, 5. Solution Rubbers Vol. 31

Figure 7. Gas phase EPM/EPDM process of Union Carbide [148]

a) Monomer purification; b) Cycle cooler; c) Cycle compressor; d) Fluidized-bed reactor; e) Product discharge; f ) Monomer
separation; g) Balers/baggers

2.2.3. Producers and Production 4 % per year, the EP(D)M consumption is pre-
Capacities dicted to increase to 726 000 t by 1996. In 1992,
the production capacity of the 12 EP(D)M manu-
The commercial production of EPM and EPDM facturers that operate 15 plants was ca. 854 000 t.
started in the early 1960s. Today EP(D)M has the Table 8 gives an overview of the EPM/EPDM
largest market volume of all special elastomers: producers, their plant locations, their production
601 000 t in 1992 [149]. With a growth rate of ca. capacities (1992), and their trade names.

Table 8. EPM/EPDM producers, locations, production capacities (1992), and trade names [149]

Country, company Plant location Start-up Capacity, t Trade name

Western Europe
France
Socabu/Exxon Gravenchon 1972 80 000 Vistalon
Germany
H€uls Marl 1972 41 000 Buna AP
Italy
Enichem Ferrara 1963 85 000 Dutral
Netherlands
DSM Beek 1965 60 000 Keltan
North America
United States
Copolymer/DSM Addis, LA 1968 73 000 Epsyn
Du Pont Beaumont, TX 1963 77 000 Nordel
Exxon Chemical Baton Rouge, LA 1962 85 000 Vistalon
Miles (Bayer) Orange, TX 1967 52 000 Polysar EPDM
Uniroyal Chem. Geismar, LA 1963 91 000 Royalene
South America
Brazil
Nitriflex Triunfo 1988 10 000
Asia
Japan
DSM-IDEMITSU Chiba 1991 40 000
JSR Yokkaichi 1970 45 000 JSR-EP
Mitsui Chiba 1970 60 000 Mitsui-EPT
Sumitomo Chem. Chiba 1969 35 000 Esprene
Korea
Kumho E P. Yochon 1988 20 000
Vol. 31 Rubber, 5. Solution Rubbers 671

3. Synthesis of Butyl Rubber by For applications, butyl rubber is compounded

Cationic Polymerization [150, 151] with fillers, plasticizers, and curing agents (see
Section 3.1.4)
Butyl rubber is a copolymer of isobutene (2- The highly saturated IIR chain is resistant to
methylpropene) and a small amount of isoprene chemical attack. Thus IIR compounds exhibit
(2-methylbuta-1,3-diene, 1 – 3 mol %). It is ab- better heat and ozone resistance than highly
breviated IIR in the ISO nomenclature unsaturated elastomers such as BR, NR, and
(ISO 1629, 1987) (butyl rubber see ! Rubber, SBR. IIR also has excellent resistance to acids,
3. Synthetic Rubbers, Introduction and Over- bases, and other chemicals. As are all hydrocar-
view, Section 1.2). The isoprene units introduce bon polymers, IIR is highly swollen by gasoline
unsaturated sites into the polymer chain to enable and other hydrocarbons. Butyl rubber has good
vulcanization. Historically, butyl rubber was the electrical insulating properties and is biocom-
first saturated polymer into which limited olefinic patible [153]. As a viscoeleastic material,
functionality was deliberately introduced [152]; uncured IIR creeps (cold flows) at ambient
EPDM (see Section 2.2) is a more recent exam- temperature. This deformation is prevented by
ple of the same principle. vulcanization (i.e., cross-linking via the iso-
The principal structure of the polymer chain is prene units).
as follows: Typical properties of the uncured polymer are
as follows [154]:

Density 917 kg/m3

Glass transition temperature  70
C
Heat capacity 1.95 kJ kg1 K1
Thermal conductivity 0.130 W m1 K1
Refractive index 1.51
Dielectric constant (at 1 kHz) 2.38
3.1. Properties, Grades, and Dissipation factor (at 1 kHz) 0.003
Applications

3.1.1. Properties The proton NMR spectrum of IIR has singlets

at 1.1 and 2.3 ppm from tetramethylsilane
The most significant property of butyl rubber (TMS) due to the methyl and methylene groups
that differentiates it from the other hydrocarbon of the polyisobutene, a triplet at 5.1 ppm that
elastomers, is low permeability to gases; most stems from the single hydrogen attached to the
significantly, in practice, to air and water vapor. double bond [155], as well as a peak around 4.9
Due to its low resilience, butyl rubber is also ppm that has been identified as a branching point
used when vibration damping is important. [156]. The isoprene content listed in Table 9 is

Table 9. Selected grades and properties of IIR

Producer Butyl grade

Bayer 100 101–3 301 402

Exxon 065 007 268 365
Mooney viscositya, MU 333 515 515 334
Isoprene contentb, mol % 0.90.2 1.750.2 1.850.2 2.250.2
Cure characteristics c
Maximum torque, dN  m 646.0 – 826.0 876.0
Minimum torque, dN  m 114.5 – 16.04.5 11.54.5
Antioxidant contentb, min wt % 0.03 min none 0.03 0.03
Ash contentd, wt % 0.3 0.3 0.3 0.3
Volatiles content, max % 0.3 1.0 0.3 0.3
a
Bayer grade according to ASTM D 1646, ML/1þ8 (125
C).
b
Bayer standard method.
c
ExxonMobil grade according to ASTM D-2084, modified (rheometer ODR 2000).
d
According to ASTM D 5667.
672 Rubber, 5. Solution Rubbers Vol. 31

Table 10. Producers and production capabilities of butyl and halobutyl rubber

Producer Location Plant Nameplate, 103 t/a

North America Bayer Inc. Sarnia, Canada Butyl I þ II 140

Exxon Mobil Chemical Baytown, USA 121
Exxon Mobil Chemical Baton Rouge, USA 132
Western Europe Bayer Antwerp, (B) B.R.N.V. 115
Exxon Chemical N. Dame de Gravenchon (F) Socabu 56
Exxon Chemical Fawley (UK) 93
Cental Europe and CIS Nizhnekamskneftekhim 60
Nizhnekamsk, Tartarstan
Sintezkauchuk Togliatti, Russia 35
Pitesti Romania 5
Asia Japan Butyl Kawasaki 80
Company Kashima 35
Yan Shan Petrochemical Yan Shan (Beijing), China 30
Reliance Industries Hazira, China 25
World total 972

the sum of the regular and the branched 3.1.4. Applications

structures.
The majority of the IIR produced is used
captively by manufacturers as base polymer
3.1.2. Grades for halobutyl rubber production, discussed in
Section ! Rubber, 8. Synthesis by Polymer
Each producer listed in Table 10 makes several Modification, Chapter 1. A significant portion
grades of IIR, which differ primarily in the of the remainder is used in tire-related appli-
amount of isoprene and the Mooney viscosity cations: inner tubes, tire-curing bladders, or as
(i.e., molar mass and molar mass distribution). blends with BIIR – inner liners. A small
Equivalent grades of the two main producers are amount of this is used in other applications,
listed in Table 9 together with illustrative values principally sealant tapes and caulks, pharma-
of specified or important properties. The actual ceutical closures, membranes for roofing and
specification ranges differ slightly for different water retention, and various mechanical seals
producers, the comparison in Table 9 being based and mounts.
on Mooney Viscosity. For most applications, IIR is vulcanized via
the isoprene units to cross-link the individual
polymer chains into a network. Vulcanization or
3.1.3. Specialty Rubbers curing is carried out commercially by three
methods, using sulfur, phenolic resins, or qui-
Specialty rubbers include Bayer’s XL 10000, a none dioximes as curing agent. Of these methods,
cross-linked grade containing DVB [154], and accelerated sulfur cures are used for most appli-
Exxon’s Star-branched butyl rubber, containing cations, phenolic resin cures are used for making
5–20 % of a very high molar mass branched tire-curing bladders, and quinone dioxime cures
fraction [157, 158]. The latter was introduced are used infrequently.
by Exxon Chemical Co. in 1989. A broad, bi- The measured properties of the vulcanizate
modal molar mass distribution was achieved are affected by the method and extent of cross-
using branching agents in the polymerization. linking and by the quantity and type of fillers and
One mode consists of normal linear chains, as plasticizers used.
previously described. The second mode consists IIR is also used as a component of food and in
of branches of normal chains connected through the manufacture and storage of foods. IIR is an
an SBS polymeric branching agent added to the allowed component of chewing gum in most
polymerization. The concept was labeled ‘‘Star- countries [159]. Bayer’s XL 10000 may be used
branched butyls’’, and exhibits higher green in sealing cements, and is also commonly used in
strength and faster stress relaxation. condenser caps [156].
Vol. 31 Rubber, 5. Solution Rubbers 673

3.2. Basic Chemistry and Production Alternative mechanisms have been proposed
Processes [163].
The incorporation of isoprene is governed by
3.2.1. Basic Chemistry the ratios of homo- and cross propagation rate
constants, r1B ¼ k11/k12 and r1P ¼ k22/k21,
Butyl rubber is composed of linear polyisobutene where isobutene and isoprene are referred to as
chains with isoprene units distributed randomly monomer 1 and 2, respectively. It was shown
along them [160]. The isobutene moieties are that the composition of butyl rubber can be
linked exclusively head to tail; the isoprene units described by r1B alone [156]. The rate constant
have mainly the trans-1,4-configuration, with for isobutene homopolymerization is k11 ¼
about 10 % of the branched structure [156]. (6  2  108) L mol1 s1 but this number has
always been a source of heated debate [164].
Industrially the copolymerization is carried
out at low temperature (ca.  90
C) in order to
obtain high molar masses. The strong depen-
The copolymerization of isobutene and vari- dence of molar mass on temperature is due to
ous monomers such as isoprene or isoprene and the high activation energy of chain transfer rela-
DVB (divinylbenzene) is a carbocationic process. tive to that of the polymerization. In the produc-
This is initiated by a species resulting from an tion process of butyl rubber, isoprene is both the
activated Lewis acid such as AlXnR3-n (X ¼ Cl, dominating poison and chain transfer agent. In
n ¼ 1  3, R ¼ Et) in the slurry or solution process general, most unsaturated and substituted hydro-
[161, 162]. The Lewis acid is activated by pro- carbons and some alkyl halides affect the poly-
togenic compounds such as water, hydrochloric merization. The compounds classified as ‘‘poi-
acid, or hydrogen sulfide. Specialty rubbers such sons’’ reduce the degree of conversion, while
as XL10000 (Bayer) or Star-branched butyl (Ex- those classified as ‘‘chain transfer agents’’ reduce
xonMobil Chemical) can be formed by the addi- the molar mass (Mooney viscosity) [165]. The
tion of a third monomer during the polymerization slurry process uses chloromethane as a diluent,
(see Section 3.1.3). The mechanism of the copo- while the solution process uses a hydrocarbon
lymerization is still not fully understood; the such as isopentane as solvent. Both solvents
generally accepted scheme is given below:
674 Rubber, 5. Solution Rubbers Vol. 31

are inert in terms of polymerization chemistry. Raw Materials. The monomers used for
Although isobutene is believed to polymerize by both production processes of butyl rubber, iso-
a carbocationic mechanism only [153], alterna- butene, and isoprene are extracted from internal
tive mechanisms such as a radical – cationic petroleum refinery streams (! Butenes, Chap. 5;
[166] or a cationic – coordination [167] mecha- ! Isoprene, Section 3.3 (more details in [171])
nism have been suggested. The claim of the
cationic-coordination mechanism has yet to be Slurry Polymerization Process. In the tra-
substantiated but continues to be an area of ditional method of manufacture, practiced since
considerable research due to the cost saving that 1943, an aluminum trichloride catalyst is used
could be realized by not having to polymerize at with a small quantity of water as cocatalyst in
ca. 90
C. Considerable research effort is be- chloromethane as diluent. The terms catalyst and
ing directed towards a system that would allow cocatalyst reflect established industrial usage;
copolymerization at higher temperature [168]. the correct terms are initiator and coinitiator,
respectively [153]. The catalyst solution
(0.2 wt % AlCl3 in chloromethane with a small
3.2.2. Industrial Production amount of water) is prepared by passing pure and
dry chloromethane through a bed of solid AlCl3
Historical Development. During the late (Fig. 8, a). Water is added to this concentrated
1920s M. OTTO working at the IG Farben labora- solution, which is further diluted with chloro-
tories in Germany, investigated synthetic oils methane and chilled to the reaction temperature.
made by polymerizing olefins with strong acids. The catalyst is quite active; the polymer to cata-
He made the important discovery that the poly- lyst mass ratio is normally on the order of several
merization temperature regulated molar mass. thousands. The catalyst activity is proportional to
By chilling isobutene with dry ice before addition the water content of the catalyst solution in the
of boron trifluoride catalyst, OTTO succeeded in low concentration range. Excessive amount of
making rubberlike products instead of oils. water destroys the catalyst. The catalyst solution
Around 1930 F. A. HOWARD, the President of is then fed into the reactor together with the
Standard Oil Development Company, visited monomer feed. The nominal isobutene cocentra-
Germany and learnt of OTTO’s discovery. In tion in the feed is ca. 30 wt %. The reaction is
1932 OTTO, invited by HOWARD, came to the USA carried out continuously in an intensely agitated
and worked with R. M. THOMAS to exploit the vessel (Fig. 8, b) at ca.  90
C. The polymer is
polymers of isobutene. The process for formed instantaneously, and since it is insoluble
manufacturing butyl rubber was further devel- in the diluent, precipitates as a fine slurry (parti-
oped by R. M. THOMAS and O. C. SLOTTERBECK at cle size 10 – 30 mm). Agglomeration is not a
Standard Oil Development Company (Esso, now problem because the rubber is below its glass
Exxon) (Linden, New Jersey, United States). transition temperature of  70
C. The slurry
They firstly used butadiene and then isoprene to circulates through concentric rows of heat-
introduce sites for vulcanization. During World exchanger tubes surrounding a central draft tube.
War II, most of the world was cut off from The circulation : feed ratio is very high (> 100),
natural rubber supplies in the Far East and, in but kinetic analysis showed that the reactor flow
a remarkably brief time, large-scale manufactur- regime is closer to that of a plug flow reactor than
ing of various synthetic rubbers was implemen- that of a continuous stirred tank reactor because
ted in North America [169, 170]. of the extremely high reaction rate [172]. The
The first commercial-scale production unit heat of reaction ( 0.8 MJ/kg) is removed by
came into operation in 1943 in Baton Rouge, boiling subatmospheric ethylene in the reactor
Louisiana. Units in Baytown, Texas, and Sarnia, jacket.
Ontario, Canada, followed in 1944.
Today, butyl rubber is produced by two dif- Reactor Control. Reactors are controlled to
ferent processes, the slurry and the solution produce the desired molar mass of polymer,
processes. The vast majority of butyl rubber is measured as Mooney viscosity, with the catalyst
produced by the slurry process, so this will be flow as the principal control variable. An increase
discussed in more detail. in catalyst flow decreases the Mooney viscosity.
Vol. 31 Rubber, 5. Solution Rubbers 675

Figure 8. Flow diagram for production of butyl rubber

a) Dissolver; b) Catalyst tower; c) Recycle tower; d) Recycle gas dryer; e) Reactor; f ) Flash drum; g) Vacuum stripper;
h) Finishing extruders

The isoprene content of the polymer, the second chloromethane and the unreacted monomers are
most important control parameter, is determined flashed off and the water is separated from the
by the composition of the feed together with the vapors by condensation and subsequent adsorp-
degree of conversion. The reactors are run typi- tion on activated alumina (d). This step some-
cally at incomplete conversion for better control. times is proceeded by absorption in glycol. The
Due to the poisoning effect of isoprene, conver- dried stream is separated by distillation (b, c) into
sion decreases with increasing isoprene content a chloromethane – isobutene stream for feed
in the feed. The catalyst flow also has an effect on make-up, a pure chloromethane stream for cata-
conversion; thus controlling this process is not lyst make-up, and streams which must be purged
easy. The reactors are operated intermittently from the recycle loop to prevent build-up of
because of fouling of the heat exchanger sur- unwanted impurities. The polymer is recovered
faces. When the control of the reactor cannot be in the form of a wet crumb (6 – 10 wt % rubber
maintained due to temperature increase, the op- in water). To control agglomeration, salts of fatty
erations are stopped and the reactors washed. To acids are added in the flash drum. Antioxidants
reduce or prevent fouling, the use of slurry are also added at this stage and sodium hydroxide
stabilizing agents [173] or addition of 3 – is added to neutralize catalyst residues. The
13 % solvent such as hexane to the feed has been rubber is converted into the final commercial
patented [174]. bale form by further drying. Most of the water
is separated by draining, followed by drying
Product Recovery and Finishing. The reac- extruders and finished by a final drying step in
tor discharge stream is treated with steam and hot a fluidized bed. The dry rubber is cooled, baled,
water in a flash drum (Fig. 8, f). Most of the and packed into boxes or crates for shipment.
676 Rubber, 5. Solution Rubbers Vol. 31

When the polymer from the reactor is to be used in different regions reflect the relative num-
processed further, such as by halogenation (see ber of tubed and tubeless tires.
! Rubber, 8. Synthesis by Polymer Modifica-
tion, Chapter 1), the product may be recovered
directly as a solution by discharging the reactor 3.4. Storage and Transportation
content into a hot solvent such as hexane. A
further stripping stage is followed by adjusting IIR is packaged in 34 kg bales wrapped in
the rubber concentration to the desired level for synthetic polymer films, and shipped in crates
further processing, typically 20 – 25 wt % [175]. or skids depending on customer needs.
It is important to remove unsaturated residues IIR is considered a nonhazardous material for
before halogenation, otherwise these unsaturated shipping and storage [178]. Stabilized grades
substances would be halogenated, producing un- should be used within five years of their date of
desirable compounds. manufacture, after which the molar mass may
decrease significantly. The molar mass of grades
Solution Polymerization Process. A pro- without antioxidant can decrease after six months
cess developed in the Soviet Union operates at of storage.
 60 to  90
C using a hydrocarbon solvent,
such as isopentane and an aluminum alkyl halide
catalyst [162]. This eliminates chloromethane 3.5. Legal Aspects
and makes the water slurry step superfluous when
the polymer is to be treated further in solution. The allowable uses and restraints of IIR in foods
However, the polymer concentration in the solu- and storage of foods are covered by regulation of
tion is necessarily lower than that possible in a individual countries. These usually follow the
slurry because the effect of concentration on United States FDA CFR, although local differ-
effective viscosity is greater in solution, which ences may occur.
reduces heat-transfer efficiency. Despite the de- The grades of IIR used in chewing gums,
creased demand for refrigeration, the presence of Bayer Butyl 101–3 and Exxon Butyl 007, con-
the additional diluent leads to energy costs higher tain no added antioxidant and are made with
than those for the slurry process. food-grade fatty acid. The use of IIR in food
manufacture and storage is usually restricted to
nonfat or low-fat foods [14]. In these applica-
3.3. Producers and Production tions, constraints are placed on the types and
Capacities levels of antioxidants used. If the IIR is vulca-
nized, the curatives and other additives in the
Worldwide, several companies produce butyl compound are also subject to restrictions.
elastomers in many different countries. How-
ever, the most prominent producers are Bayer
AG and ExxonMobil Chemical with collectively 3.6. Toxicology and Occupational
two-thirds of the world production capacity. Health
Worldwide production facilities for butyl and
halobutyl rubber are listed in Table 10 [176, IIR is a nonhazardous material, and no special
177]. The capacities given refer to polymeriza- precautions are required in its handling [15]. It
tion, with the exception of Japan Butyl’s Kashi- is generally used in cured compounds, and
ma plant, which is a halogenation facility only. In precautions for handling curatives and other
general, many of the production facilities are compounding ingredients are frequently more
multifunctional, able to produce butyl or halo- significant.
butyl rubber on demand. The global nameplate Butyl rubbers contain only small amounts of
capacity was 972  103 t in 2001. the residual monomers isobutene and isoprene,
Since the 1970s the relative amount of IIR typically < 100 mg/kg in each case. To date, no
used has been decreasing and the amount of threshold limit value has been established for
halobutyl rubber increasing. Differences in the either monomer, since they both exhibit very low
relative amounts of IIR and halobutyl rubber acute toxicity. The 2 h LC50 in mice is 415 g/m3
Vol. 31 Rubber, 5. Solution Rubbers 677

and 157 g/m3 for isobutene and isoprene, respec- 18 Bridgestone Tire, EP 254 766, 1981 (M. Ogawa, M.
tively [179]. Ikegami).
A modified Ames test of isobutene showed 19 K. H. Nordsiek, K. M. Kiepert, Kautsch. Gummi Kunstst.
38 (1985) 178 – 185.
that it is not mutagenic. Only traces of chloro-
20 H€uls AG, EP 256 261, 1986 (C. Herrmann et al.).
methane (< 1 mg/kg) are found in butyl rubbers. 21 The Goodyear Tire & Rubber Co., EP 263 054, 1986 (A.
Thus, the maximum airborne concentration re- F. Halasa, B. B. Gross, T. L. Cox, G. F. Balogh).
leased during processing should be well below 22 H€uls AG, EP 362 514, 1988 (W. Hellermann et al.).
the 50 mL/m3 (8 h weighted average) occupa- 23 Yokohama Rubber, Nippon Zeon, DE 3 635 366, 1986
tional exposure limit set by the ACGIH. (Y. Kikuchi et al.).
Butyl rubber will not burn unless its surface 24 Nippon Zeon DE 3 315 525, 1982 (S. Akita et al.).
temperature reaches 300 – 500
C and an igni- 25 H€uls AG, EP 362 515, 1988 (W. Hellermann et al.).
26 H. H. Grever, G. Marwede, Tyre Tech, Italy, Oct. 1995.
tion source is available. Burning butyl rubber
27 Goodyear, EP 483 046, 1991 (A. F. Halasa et al.).
gives off dense black smoke and toxic gases such 28 Goodyear, EP 698 624, 1995 (A. F. Halasa et al.).
as carbon monoxide and hydrocarbons, resulting 29 Goodyear, EP 645 423, 1994 (J. Berg et al.).
from incomplete combustion. 30 M. Hoffmann, G. Pampus, G. Marwede, Kautsch. Gum-
mi Kunstst. 22 (1969) 691.
31 A. Echte, Angew. Makromol. Chem. 58/59 (1977) 175 –
198.
References 32 BASF, DE 3 345 377, 1983 (A. Echte, H. H€onl, W.
Grohn).
1 Y. Saito, Kautsch. Gummi Kunstst. 39 (1986) 30 –32. 33 Shell, US 3 265 765, 1962 (G. Holden, R. Milkovich).
2 K. H. Nordsiek, Kautsch. Gummi Kunstst. 39 (1986) 34 G. Holden, N. R. Legge: Thermoplastic Elastomers
599 – 611. Based on Polystyrene-Polydiene Block Copolymers,
3 G. W. Marwede, B. Stollfuß, A. J. M. Sumner, Kautsch. Thermoplastic Elastomers, Hanser, M€unchen 1987,
Gummi Kunstst. 46 (1993) 380 – 388. pp. 47 – 66.
4 R. Zelinski, C. W. Childers, Rubber Chem. Technol. 41 35 L. Fetters, J. Polym. Sci. Part C 26 (1969) 1.
(1968) 161. 36 M. Morton: Anionic Polymerization: Principles and
5 S. Bywater in H. F. Mark (ed.): Encyclopedia of Polymer Practice, Academic Press, New York 1983.
Science and Engineering, 2nd ed., vol. 2, Wiley, New 37 Bridgestone, EP 742 232, 1993 (D. F. Lawson et al.).
York 1985, p. 1. 38 Bridgestone, EP 725 069, 1996 (D. F. Lawson et al.).
6 R. Bond, G. F. Morton, L. H. Krol, Polymer 25 (1984) 39 Bridgestone, EP 725 085, 1996 (D. F. Lawson et al.).
132 – 140. 40 P. Luijk, Kautsch. Gummi Kunstst. 34 (1981) 191 – 195.
7 A. E. Oberster, T. C. Bouton, J. K. Valaitis, Angew. 41 I. Kuntz, J. Polym. Sci. 54 (1961) 569.
Makromol. Chem. 29/30 (1973) 291. 42 L. Fetters, Macromolecules 12 (1979) 344.
8 G. Day, S. Futamara, Kautsch. Gummi Kunstst. 40 43 P. Guyot et al., Polymer 22 (1981) 1724.
(1987) 39 – 43. 44 Firestone, DE-AS 1 300 239, 1964 (N. Keckler);
9 A. Ueda, H. Watanabe, S. Akita, Int. Rubber Conf. 1985, Chem. Abstr. 61 (1964) 808.
199. 45 T. C. Buton, S. Futamara, Rubber Age (N.Y.) 106 (1974)
10 B. Kern, S. Futamara: ‘‘Solution SBR as Tread Rub- 33 – 39.
bers,’’ ACS Rubber Div. 131st Meeting, Montreal, Que- 46 H. L. Hsieh, W. H. Glaze, Rubber Chem. Technol. 43
bec, May 1987. (1970) 22.
11 D. C. Moore, G. L. Day, Elastomerics 117 (1985) no. 3, 47 T. A. Antkowiak, A. E. Oberster, H. F. Halasa, D. P.
22 – 28. Tate, J. Polym. Sci. Polym. Chem. Ed. 10 (1972) 1319.
12 H. L. Brantley, G. L. Day, Kautsch. Gummi Kunstst. 40 48 H€uls AG, EP 304 589, 1987 (W. Hellermann et al.).
(1987) 122 – 125. 49 T. Kawanaka, A. Yosioka, N. Nagata, H. Watanabe:
13 United States FDA 21, CFR 172.615. ‘‘Analysis of Chain End Modified Rubber Structure,’’
14 a) United States FDA 21, CRR 176.180. b) BGA ACS Rubber Div. Meeting, Detroit, Oct. 17 – 20, 1989.
Recommendations XX and XXI. 50 Nippon Zeon, EP 747 425, 1995 (M. Nakamura et al.).
15 United States 29 CFR 1910–1200. 51 Bridgestone/Firestone, EP 639 587, 1994 (D. F. Lawson
16 F. Tsutsumi, M. Sakakibara, N. Oshima: ‘‘Structure et al.).
and Dynamic Properties of New Solution SBR Coupled 52 IISRP: Worldwide Rubber Statistics, 1996, and own
with Tin Compound,’’ Rubber Division Meeting, capacity estimations.
American Chemical Society, Cincinati, Ohio, Oct. 53 J. A. Brydson: Rubbery Materials and their Compounds,
18 – 21 1988. Elsevier Applied Science, London 1988.
17 Japan Synthetic Rubber Co., EP 134 909, 1981 (Y. 54 Ullmann, 4th ed., 13, 595.
Takeuchi et al.). 55 A. Echti in C. K. Riew, Adv. Chem. Ser. 222 (1989) 15.
678 Rubber, 5. Solution Rubbers Vol. 31

56 H. Fries, B. Stollfuß, ACS Rubber Division Meeting, 86 Goodrich Gulf, BE 543 292, 1955 (S. E. Horne).
Cincinnati, Oct. 1988, paper no. 8. 87 Bridgestone, US 3 170 907, 1965 (K. Ueda, T. Yoshi-
57 W. Kern, S. Futamara, Polymer 29 (1988) 1801. moto, J. Hosono, K. Maeda).
58 M. Morton: Anionic Polymerization: Principles and 88 M. Gippin, Ind. Eng. Chem. Prod. Res. Dev. 4 (1965)
Practice, Academic Press, New York 1983. 160.
59 Bridgestone, EP 693 505, 1995 (D. F. Lawson et al.). 89 M. Gippin, Ind. Eng. Chem. Prod. Res. Dev. 1 (1962) 32.
60 Bridgestone, EP 622 381, 1994 (T. Katamura et al.). 90 S. Horne in R. P. Quirk (ed.): Transition Metal Catalyzed
61 Bridgestone, Japan Synthetic Rubber, EP 609 010, 1994 Polymerizations, vol. 4, ‘‘part B’’, Harwood Academic
(Y. Yamakawa et al.). Publishers, New York 1983, p. 527.
62 Bridgestone/Firestone, EP 493 839, 1991 W. Hergenr- 91 R. P. Burford, J. Macromol. Sci. Chem. A17 (1982) 123.
other et al.). 92 A. K. Bhowmick, H. L. Stevens, Handbook of Elasto-
63 W. Hergenrother et al., J. Polym. Sci. Part A: Polym mers, New Developments and Technology, Dekker, New
Chem 33 (1995) 143 – 157. York 1988.
64 Y. Kitagawa:‘‘The Industry looks outwards,’’IISRP 37th 93 J. Howell, W. Curtis, J. Solomon in R. P. Quirk (ed.):
Annual General Meeting, Bath, May 5 – 9, 1996. Transition Metal Catalyzed Polymerizations, vol. 4,
65 F. Tsutsumi, M. Sakakibara, N. Oshima, Rubber Chem. ‘‘part B’’, Harwood Academic Press, New York 1983,
Technol. 68 (1990) 8. p. 509.
66 C. A. Sierra, C. Galan, J. M. Gomeo Falou, V. Ruiz Santa 94 Phillips Petroleum, BE 551 851, 1956 (R. P. Zelinski, D.
Quitera, Rubber Chem. Technol. 68 (1995) 259. R. Smith).
67 N. Nagita et al., Rubber Chem. Technol. 60 (1987) 837. 95 Firestone, US 3 205 213, 1965 (A. Fono, R. S. Stearns).
68 H. L. Hsieh, R. P. Quirk: Anionic Polymerization Prin- 96 Bayer, GB 974 993, 1964 (N. Sch€on, G. Pampus, J.
ciples and Practical Applications, Marcel Dekker, New Witte).
York 1996. 97 W. M. Saltman, T. Link, Ind. Eng. Chem. Prod. Res. Dev.
69 R. P. Quirk, S. H. Jang, J. Kim, Rubber Chem. Technol. 3 (1964) 199.
69 (1996) 444. 98 J. F. Henderson, J. Polym. Sci. Part C 4 (1963) 233.
70 J. E. Puskas, M. Verhelst, P. Collart, J. B. Schmidt, 99 T. Yoshimoto et al., Makromol. Chem. 139 (1970) 61.
Kautsch. Gummi Kunstst. 48 (1995) no. 12, 866. 100 T. Yoshimoto et al., Makromol. Chem. 139 (1970) 73.
71 M. Fontanille, A. H. E. M€uller, S. Bywater in G. Allen, 101 M. C. Throckmorton, F. S. Farson, Rubber Chem. Tech-
J. C. Bevington (eds.): Comprehensive Polymer Sci- nol. 45 (1972) 268.
ence, vol. 3, Pergamon Press, Oxford 1989. 102 W. M. Saltman, L. J. Kuzma, Rubber Chem. Technol. 46
72 I. G. Hargis, R. A. Livigni, S. L. Aggarwal in: A. Whe- (1973) 1055.
lan, K. S. Lee (eds.): Developments in Rubber Technol- 103 M. C. Throckmorton, Kautsch. Gummi Kunstst. 22
ogy, vol. 4, Elsevier Applied Science, London 1987. (1969) 293.
73 W. Cooper in R. N. Haward (ed.): Developments in 104 Union Carbide, US 3 297 667, 1967 (W. von Dohlen
Polymerisation-1, Applied Science, London 1979. et al.).
74 The Synthetic Rubber Manual, 11th ed., International 105 Q. Jun, W. Fu-Song, H. Bao Tong in R. Quirk (ed.):
Institute of Synthetic Rubber Producers, Houston 1989. Transition Metal Catalyzed Polymerizations, vol. 4,
75 M. Morton, J. R. Rupert in F. E. Bailey (ed.): Initiation of ‘‘part A’’, Harwood Academic Press, New York 1983,
Polymerization, Americal Chemical Society, Washing- p. 265.
ton, D.C., 1983. 106 G. Marwede, G. Sylvester, IISRP, 22nd Annual Meeting
76 Worldwide Rubber Statistics 1991, International Insti- Proceedings, 1981, pp. III-3.
tute of Synthetic Rubber Producers, Houston 1991. 107 J. Witte, Angew. Makromol. Chem. 94 (1981) 119.
77 Firestone, US 3 317 918, 1956 (F. C. Foster). 108 Enichem, US 4 444 903 (A. Carbonaro, D. Ferraro, M.
78 E. W. Duck, J. M. Locke in W. M. Saltman (ed.): The Bruzzone).
Stereo Rubbers, Wiley-Interscience, New York 1977. 109 Goodyear – Enichem, US 4 663 405 (M. C.
79 H. Fries, B. Stollfuß: ACS Rubber Division, Cincinnati, Throckmorton).
Ohio, Oct. 1988. 110 Y. Takeuchi, A. Sekimoto, M. Abe: ‘‘New Industrial
80 W. Hoffmann: Rubber Technology Handbook, Hanser Polymers,’’ ACS Symp. Ser. (1974) no. 4, 15.
Verlag, M€ unchen 1990. 111 Y. Takeuchi, A. Sekimoto, M. Abe: ‘‘New Industrial
81 H. Fries, B. Stollfuß: ‘‘Structure and Properties of Buta- Polymers,’’ ACS Symp. Ser. (1974) no. 4, 26.
diene Rubber,’’ ACS Rubber Division, Cincinnati, Ohio, 112 H. Ashitaka, H. Ishikawa, H. Veno, J. Polym. Sci. Polym.
Oct. 1988, paper no. 8. Chem. 21 (1983) 1853.
82 S. N.Chakravarty, S. K. Mustafi, A. K. Mukherjee, 113 S. E. Horne: Transition Metal Catalyzed Polymeriza-
Rubber News 28 (1989) July, 33. tions, vol. 4, ‘‘part B’’, Harwood Academic Press, New
83 E. Schoenburg, H. Marsh, S. Walters, W. Saltman, York 1983, p. 527.
Rubber Chem. Technol. 52 (1977) 527. 114 W. M. Saltman, J. Polym. Sci. Part A 1 (1963) 373.
84 Phillips Petroleum, GB 848 065, 1956. 115 W. Cooper et al.: ‘‘Elastomer Stereospecific Polymeri-
85 Goodrich Gulf, US 3 117 743, 1963 (S. E. Horne). zation,’’ Adv. Chem. Ser. 52 (1966) 46.
Vol. 31 Rubber, 5. Solution Rubbers 679

116 G. J. Van: ‘‘Amerongen Elastomer Stereospecific Poly- 143 S. P. Sawin, C. J. Baas: ‘‘UNIPOL PP: A Gas-Phase
merization,’’ Adv. Chem. Ser. 52 (1966) 136. Route to Polypropylene,’’ Chem. Eng. 92 (1985)
117 W. Cooper, R. K. Smith, A. Stokes, J. Polym. Sci. Part B May 27, 42.
4 (1966) 309. 144 M. R. Rifi et al.; ‘‘FLEXOMER TM Polyolefins: Bridg-
118 E. Lovering, W. B. Wright, J. Polym. Sci. Polym. Chem. ing the Gap between Rubber and Plastics,’’ ACS Rubber
Ed. 6 (1968) 2221. Division Meeting, Las Vegas, June 1990.
119 W. Cooper et al.: ‘‘Elastomer Stereospecific Polymeri- 145 BP Chemicals Ltd., EP 409 492, 1990 (J. A. Bailly, P.
zation,’’ Adv. Chem. Ser. 52 (1966) 46. Bres).
120 F. P. Baldwin, G. Ver Strate, Rubber Chem. Technol. 45 146 Union Carbide, US 5 106 927, 1989 (M. R. Riffi, K. H.
(1972) 709. Lee, M. J. Kriss, H. T. Liu).
121 S. Cesca, Macromol. Rev. 10 (1975) 1. 147 Rubber Plast. News 4 (1991) 5.
122 G. Ver Strate: ‘‘Ethylene-Propylene Elastomers,’’ J. I. 148 F. G. Stakem, A. U. Paeglis, J. D. Collins: ‘‘Union
Kroschwitz (ed.): Encycl. Polym. Sci. Eng., 2nd ed., Carbide Gas Phase EPM and EPDM Rubber,’’ paper
vol. 6, Wiley, New York 1986, pp. 522 –564. presented at 142nd Technical Meeting, Rubber Division,
123 The Synthetic Rubber Manual, vol. 12 International American Chemical Society, Nashville, Nov. 3 – 6,
Institute of Synthetic Rubber Producers, Houston 1992.
1992, pp. 47 – 58. 149 IISRP: ‘‘Worldwide Rubber Statistics,’’ Kautsch. Gum-
124 P. S. Brown, A. J. Tinker, J. Natl. Rubb. Res. 5 (1990) mi Kunstst. 45 (1992) 334.
no. 3, 157 – 162. 150 Kirk-Othmer, 3rd ed., 8, 470 ff.
125 A. Y. Coran, Rubber Chem. Technol. 64 (1991) 801 – 151 E. N. Kresge, R. H. Schatz, H-C. Wang: Encyclopedia of
812. Polymer Science and Engineering, vol. 8, Wiley-Inter-
126 Polysar Ltd., US 4 645 793, 1985 (W. von Hellens, S. A. science, New York, 1987, pp. 423 ff.
H. Mohammed, R. Hallman). 152 R. M. Thomas, Rubber Chem. Technol. 42 (1969)
127 Bridgestone Corp., US 4 886 850, 1988 (M. Ogawa, Y. G9011.
Shiomura, T. Takizawa). 153 J. P. Kennedy: Cationic Polymerization of Olefins: A
128 H. Fries, A. Sumner, Tyre-Tech. 91, Berlin, Oct. Critical Inventory, Wiley-Interscience, New York 1976,
1991. p. 14.
129 J. Boor: Ziegler Natta Catalysts and Polymerizations, 154 L. A. Wood: ‘‘Physical Constants of Different Rub-
Academic Press, Inc., New York 1979. bers,’’ in J. Brandrup, E. H. Immergut (eds.): Polymer
130 Hoechst, EP 384 263, 1989 (D. Volker, M. Antberg, J. Handbook, 3rd ed., Wiley-Interscience, New York 1989,
Rohrmann, A. Winter). V/9 – V/10.
131 W. Kaminsky, M. Miri, J. Polym. Sci. Polym. Chem. Ed. 155 C. Y. Chu, R. Vukov, Macromolecules 18 (1985) 1423.
23 (1985) 2151 – 2164. 156 J. L. White, T. D. Schaffer, C. J. Ruff, J. P. Cross,
132 Exxon Chemical Patents Inc., US 5 001 205, 1988; Macromolecules 28 (1995) 329.
EP 347 129, 1989 (S. Floyd, E. L. Hoel). 157 Bayer XL 10000 complies with United States FDA Code
133 A. Gumboldt, J. Hellberg, G. Schleitzer, Makromol. of Federal Regulations (CFR) Title 21, Part 175.300 (b)
Chem. 101 (1966) 229. (3) (xxxi).
134 Hoechst, DE 1 495 698, 1962 (A. Gumboldt, E. Jun- 158 D. E. Smith (ed.): Blue Book 1996, Lippincott & Peto
ghans, G. Schleitzer). Inc., Ohio 1996.
135 Chem. Werke H€uls, DE 1 595 442, 1966 (H. Emde, K. 159 Bayer Butyl 101-3 complies with United States FDA
Benedikter, P. Hegenberg). Code of Federal Regulations (CFR) Title 21, Part
136 Stamicarbon B.V., EP 44 119, 1980 (G. G. Evens, E. M. 177.1420 Isobutylene polymers, 172.615 Chewing Gum
J. Pijpers, R. H. M. Seevens). base, 177.2600 Rubber Articles Intended for Repeated
137 Stamicarbon B.V., EP 44 595, 1980 (G. G. Evens, E. M. Use, and other FDA regulations.
J. Pijpers, R. H. M. Seevens). 160 I. Kuntz, K. D. Rose, J. Polym. Sci. Part A: Polym.
138 B. Schleimer, J. Wolpers, Werkz. H€ uls AG 161 (1971) Chem. 27 (1989) 107.
8 – 13. 161 Standard Oil Development Company, US 2 243 658,
139 B. Schleimer, J. Wolpers: ‘‘Ethylene-Propylene Rub- 1937 (R. M. Sparks, O. C. Slotterbeck).
ber – Bunawerke H€uls GmbH,’’ Hydrocarbon Process. 162 USSR Ministry, CA 1 019 095, 1973 (N. V. Scherba-
58 (1979) no. 11, 171. kova et al.). Also issued as DE 104 985.
140 P. Galli, F. Miliani, T. Simonazzi: ‘‘New Trends in the 163 A. Gandini, H. Cheradame, Adv. Polym. Sci. 34/35
Field of Propylene Based Polymers,’’ International (1980) .
Polymer Symposium, Kyoto, Japan, Aug. 20 – 25, 1984. 164 M. Roth, H. Mayr, Macromolecules 29 (1996) 6104.
141 Rubber Plast. News 15 (1985) no. 4, 138. 165 J. P. Kennedy: Cationic Polymerization of Olefins: A
142 D. E. James: ‘‘Linear Low Density Polyethylene,’’ in H. Critical Inventory, Wiley-Interscience, New York 1976,
Mark, C. Overberger (eds.): Encyclopedia of Polymer p. 116.
Science and Engineering, vol. 6, Wiley & Sons, New 166 L. Toman, J. Pilar, J. Spevacek, M. Marek, J. Polym. Sci.
York 1988, pp. 429 – 454. Polym. Chem. Ed. 16 (1978) 2759.
680 Rubber, 5. Solution Rubbers Vol. 31

167 F. Barsan, M. C. Baird, J. Chem. Soc. Chem. Commun 180 Michelin, FR 9 102 433, 1991 (R. Rauline). Also
(1995) 1065. issued as EP 501 227.
168 K. R. Kumar, A. Penciu, M. J. Drewitt, P. J. McInenly, 181 Goodyear, EP 598 193, 1993 (A. F. Halasa et al.).
M. C. Baird, J. Polym. Sci. Part A Polym. Chem. 40,
(2002) 3302.
169 IG Farbenindustrie, DE 641 284, 1931 (M. Otto, M. Further Reading
Mueller-Cunradi).
170 A. T. Purcell, J. V. Fusco: Butyl, The First Fifty Years, R. R. Lattime: ‘‘Styrene-Butadiene Rubber’’, Kirk Othmer
Exxon Corporation, Houston 1987, p. 10. Encyclopedia of Chemical Technology, 5th edition, John
171 R. Schuster (ed.): ‘‘Handbook of Rubber Technology’’, Wiley & Sons, Hoboken, NJ, online DOI: 10.1002/
Wiley-VCH Weinheim, Germany, in press. 0471238961.1920251812012020.a01.
172 A. A. Berlin, S. A. Wolfson, Polym. Sci. 36(4) (1994) D. Mackey, A. H. Jorgensen: ‘‘Nitrile Rubber’’, Kirk Othmer
505. Encyclopedia of Chemical Technology, 5th edition, John
173 Exxon, US 4 252 710, 1979 (K. W. Powers, R. H. Wiley & Sons, Hoboken, NJ, online DOI: 10.1002/
Schatz); US 4 474 924, 1983 (K. W. Powers, H. C. 0471238961.1409201813010311.a01.
Wang). J. E. Mark, B. Erma: Science and Technology of Rubber, 3rd
174 Bayer AG, US 5,539,065, 1996 (W. Baade, G. Lang- ed., Academic Press, London 2006.
stein, J. E. Puskas). M. Morton: ‘‘Elastomers, Synthetic, Survey’’, Kirk Othmer
175 Esso, US 2 940 960, 1957 (B. R. Tegge et al.). Encyclopedia of Chemical Technology, 5th edition, John
176 International Institute of Synthetic Rubber Producers: Wiley & Sons, Hoboken, NJ, online DOI: 10.1002/
World Wide Rubber Statistics, 2001, Houston. 0471238961.1921182213151820.a02.pub2.
177 SRI International, Chemical Economics Handbook, B. Rodgers (ed.): Rubber Compounding - Chemistry and
1999. Applications, CRC Press, Boca Raton, FL 2004.
178 United States Dept. of Transport, CFR Title 49. S. Thomas, R. Stephen: Rubber Nanocomposites, Wiley,
179 B. B. Shugaev, Arch. Environ. Health 18 (1969) 879. Singapore 2010.