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Acrylate
esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate form
exible copolymers. They provide enhanced adhesion, particularly in coextruded lms or
laminates.
Late transition metal complexes are more ecient in the copolymerization of ethene
and polar monomers. Nickel or palladium complexes (see strtuctures (30)(32) are
functional-group tolerant allowing the copolymerization of ethene and methyl methacry-
late or CO [224227].
III. POLYPROPENE
A. Homopolymerization
In contrast to the polymerization of ethene, only coordination catalysts are successful in
polymerizing propene to a crystalline polymer. The cationic polymerization of propene
with concentrated sulfuric acid leads to oily or waxy amorphous polymers of low
molecular weight [228]. Next to strong acids, catalysts such as complex Lewis acids
may serve as initiators in the cationic polymerization of propene. The polymerization
is conducted at temperatures between 100 and 80
C) 160171 130160
Crystallinity (%) 5565 5075 0
Tensile strength (kP/cm
2
) 320350 0
Table 14 Heterogeneous catalysts for the propene polymerization.
Catalyst
a
Activity
(g PP/g Ti h atm)
Part of isotactic
PP (%)
Refs
TiCl
4
/Al(C
2
H
5
)
3
(1:3) 30 27 231
a-TiCl
3
/Al(C
2
H
5
)
2
Cl 25 87 232
a-TiCl
3
/AlCl
3
Al/(C
2
H
5
)
2
Cl 120 80 233
b-TiCl
3
/Al(C
2
H
5
)
3
/H
2
15 234
TiCl
3
/LiAlH
4
235
TiCl
3
/LiAl
2
H
7
/NaF 70 90 236
b-TiCl
3
/Al(C
2
H
5
)
2
Cl/LB
1
99 95 237
b-TiCl
3
/AlCl
3
/Al(C
2
H
5
)
2
Cl/LB
2
520 98 238
TiCl
3
/TiCl
3
CH
3
Low Low 239
Ti/I
2
Low Low 240
a
LB
1
Lewis base 1, methylmethacrylate; LB
2
Lewis base 2, diisoanyl ether.
Copyright 2005 by Marcel Dekker. All Rights Reserved.
The nature of the ligands and the valency of the transition metal atoms essentially
govern activity, productivity, and stereospecity. Another strong inuence is exerted by
the nature of the cocatalyst. It consists of organometallic compounds of the main groups 1
and 3 of the periodic table. For the propene polymerization, alkyls of lithium [64],
beryllium [240], magnesium [240], zinc [241], aluminum [64], and gallium [10] have been
used. Aluminum alkyls have been proven to be particularly suitable. Nowadays they
are used exclusively as cocatalysts since they are superior to all other organometallic
compounds as far as activity, stereospecity, accessibility, and availability are concerned.
Only lithium alanate is an exception to this. It possesses higher thermostability and is
therefore preferred for solution polymerization at temperatures between 150 and 200
C.
Heterogeneous catalysts are suspended in the solvent. The Ziegler catalyst TiCl
4
/
Al(C
2
H
5
)
3
aords polypropene with very low stereospecity (compare Table 14). One
criterion for the determination of stereospecity is the isotacticity index, which is dened
as the percentage of polymer that is insoluble in boiling heptane [10]. Natta achieved
a substantial increase in stereoselectivity by using TiCl
3
instead of TiCl
4
[240].
3TiCl
4
Al ! 3TiCl
3
AlCl
3
49
The aluminum halogenide content of TiCl
3
leads to the formation of defects in
the crystal lattice, thereby eecting an increase in activity. At temperatures up to 100
C,
b-TiCl
3
is formed, which upon tempering assumes the layered structure of -TiCl
3
. Above
200
C, a-TiCl
3
is formed. Today, TiCl
3
in combination with Al(C
2
H
5
)
2
Cl is still used as a
catalyst for the polymerization of propene. It is referred to as a rst-generation catalyst.
The use of Al(C
2
H
5
)
3
decreases the stereospecity and Al(C
2
H
5
)Cl
2
drastically lowers the
catalytic activity [242]. Table 15 gives the inuence of various ligands on stereoregularity
for the system TiCl
3
/Al(C
2
H
5
)
2
X [243].
The preferred metal alkyls possess ethyl and isobutyl ligands. Typical examples
are AlEt
3,
AliBu
3
, AlEt
2
Cl, and Al-(i-Bu)
2
Cl. The stereoregularity of the polypropene
decreases with increasing size of R in AlR
3
[244]. Vanadium salts attracted much attention
because they led predominantly to statistical copolymers, as opposed to block copolymers
produced with titanium salts.
Depending on reaction temperatures, rst-generation catalysts produce increasing
amounts of atactic polypropene (8 to 20%) next to the isotactic main product. By
modication with electron donors (Lewis bases; see also Table 14) of the desired
complexation tendency, the atactic polymerization sites can be largely deactivated, thus
raising the isotaxy index to 94 to 98% [245]. It is obvious that atactic polymerization
Table 15 Varying X in Al(C
2
H
5
)
2
X/TiCl
3
catalysts polymerizing.
X Rate of polymerization
(relative to XC
2
H
5
)
Stereoregularity
I.I. (%)
C
2
H
5
100 85
F 30 83
Cl 33 93
Br 33 95
I 9 98
Source: Ref. 243.
Copyright 2005 by Marcel Dekker. All Rights Reserved.
centers have a greater tendency towards complexation than do isotactic ones. Catalysts
that are modied in this manner are also known as second-generation catalysts.
The partial blocking of active sites leads to a decrease of catalytic activity. Due to
a tremendous increase in surface area of the TiCl
3
the activity of the modied catalyst can
be increased by a factor of 2 to 5.
1. Kinetic Aspects
To date, numerous papers dealing with the kinetics of propene polymerizations have been
published [246263]. Since in the course of the polymerization the TiCl
3
crystallites break
into smaller pieces, thereby exposing new active centers, the kinetical investigation of the
reaction is made more dicult. For the majority of systems, however, it was found that the
polymerization rates are proportional to the concentrations of catalyst and monomer but
do not depend on the aluminum organic component as long as a threshold concentration
is maintained.
r k
p
TiCl
3
1
C
3
H
6
1
AlC
2
H
5
2
Cl
50
This means that there is practically no dependence of the propene polymerization
rate on the Al(C
2
H
5
)
3
/TiCl
3
ratio over a wide range. However, a dependence of the
reaction rate on the metal component ratio was observed by Tait [264] and Zakharov et al.
[265] in the presence of AlR
3
/VCl
3
and Al(C
2
H
5
)
3
/AlCl
3
/TiCl
3
systems. It must be
remarked that extremely high aluminum alkyl concentrations of 0.3 mol/l were used,
whereas these are normally 0.005 mol/l. The authors introduced kinetic models of the
LangmuirHinshelwood type with reversible adsorption of aluminum alkyl on the
transition metal halogenide surface.
Other dierences in behaviour between the investigated catalytic systems concern the
dependence of the polymerization rate on time. In the rst minutes the activity increases
until it reaches a maximum value, which keeps constant for several hours [266,267].
2. Active Sites
To measure the activity of the catalyst, it is necessary to know something about the
portion of titanium atoms that form active sites. A lot of studies have been carried out to
evaluate the concentration of active sites and their location [268]. Such studies are
facilitated by the fact that the rst polymer chains forming on active sites preserve only a
trace of their origin as well as by the fact that the variation of their molecular weight with
polymerization time depends on the number of active sites. On the other hand, a correct
determination of the active sites is made complex by the nature of the phenomena
occurring during the polymerization.
There are two parameters linked to the concentration of active sites, the poly-
merization rate (propagation rate) and the growing time (average lifetime) of the polymer
chains. The various methods are summarized as follows:
1. Variation of the molecular weight as a function of polymerization time [268278]
(kinetic method). This could only be obtained at low temperatures and low
monomer conversions.
2. Determination of the number of labeled alkyl groups bound to the polymer
chains (end groups) of polymers obtained with catalysts prepared in the presence
of
14
C-labeled aluminum alkyls [268,279].
Copyright 2005 by Marcel Dekker. All Rights Reserved.
3. Inhibition of the active sites with compounds such as methanol, iodine, or
allenes [280]. Since it is most unlikely for these compounds to react with active
sites only, the method gives too high values.
4. Reaction between the transition metalcarbon bonds present in the polymeriza-
tion system and a labeled quenching agent such as
131
I
2
, tritiated alcohols or
water [276], deuterated methanol or water, and
14
CO or
14
CO
2
[281,282].
Table 16 summarizes some results of the propagation rate k
p
and the number of active
sites for various TiCl
3
catalysts. It can be seen that 0.33.6% of the total titanium atoms
form active sites.
Polymerization does not seem to involve proper kinetic chain termination
phenomena, but polymer chain transfer processes, making the active site available to
initiate a new polymer chain. These can be formulated as a chain transfer process with
the monomer M:
CatM
n
H M ! CatMH M
n
51
or as a transfer process with the organometallic compound:
CatM
n
H AlR
3
! CatR AlR
2
M
n
H 52
There is evidence that many polymer chains are bound to aluminum at the end of
polymerization [283]. Very important is a spontaneous termination process by b-hydride
extraction:
CatCH
2
CHCH
3
M
n
H ! CatH CH
2
CCH
3
M
n
H 53
When operating in the presence of H
2
as molecular weight regulator, saturated polymer
chains are formed:
CatM
n
H H
2
! CatH HM
n
H 54
Table 16 Percentage of active sites (C*) and propagation constants (k
p
) for propene
polymerization with TiCl
3
catalysts.
Catalyst system Temp.
(
C)
k
p
(L mol
1
s
1
)
C*
(% Ti active/Ti total)
Method
a
Refs
a-TiCl
3
/AlEt
3
70 0.71.7 MW,
14
C 268
a-TiCl
3
/AlEt
2
Cl 70 0.30.6 MW,
14
C 268
a-TiCl
3
/Al(I-Bu)
3
80 2.9 0.54 K 273
a-TiCl
3
/AlEt
3
70 0.54 I 269
a-TiCl
3
/AlEt
2
Cl 70 1.1 3.6
14
CO 274
d-TiCl
3
/0.3AlCl
3
/AlEt
3
70 100 0.58
14
CO 275
d-TiCl
3
/AlEt
2
Cl 70 124 2.8 T 276
d-TiCl
3
/0.3AlCl
3
/Al(i-Bu)
3
70 90 0.8
14
CO 275
-TiCl
3
/AlEt
2
Cl 50 80 1.5 MW,K 277
a
MW, molecular weight variation method; K, kinetic method; I, inhibitor method;
14
C, ratoactive alkyl method;
T, tritiated quenching agent method;
14
CO, radioactive carbon monoxide method.
Copyright 2005 by Marcel Dekker. All Rights Reserved.
Dividing the chain propagation rate constant k
p
by the average transfer rate constant k
t
gives the average molecular weight M
n
of the polymer chain. M
w
/M
n
was assumed to be
in the range 5 to 10 [284].
3. Mechanism
Various models of catalytic centers and of monomeric unit addition mechanism have been
proposed to interpret the isospecic polymerization of a-olens with ZieglerNatta
catalytic systems [285293]. For the a-olens the combination of x-ray diraction and IR
analysis showed very early that the polymers obtained with the Ziegler catalytic system
[294] are substantially linear polymers with head-to-tail enchainments. The regioselectivity
of the amorphous product is slightly lower than that of the crystalline polymer. a-Olen
polymerization is shown to occur through a cis-insertion reaction by using deuterated
propene. The cis addition to the double bond was proven when Miyazawa and Ideguchi
[295] and Natta et al. [296] established that the polymer of cis-ld1-propene is erythro-
diisotactic, whereas the polymer from trans-ld1-propene is threo-diisotactic. The metal
atom of the catalyst bearing the growing chain and the growing chain end are added
simultaneously to the double bond of the incoming monomer:
55
To synthesize isotactic polypropene, the catalytic center must sharply discriminate
between the two prochiral faces of the a-olen. To do this, the catalytic system must
possess one or more chirality centers.
Considering the simplest model of a monometallic catalytic center (55), there cer-
tainly is a chiral carbon atom in the growing chain in a-position with respect to the metal
atom; furthermore, the metal atom itself can be a center of chirality [297], which being
bound to a solid surface could maintain its absolute conguration during the insertion
reaction. Therefore, stereoselectivity is caused by the chirality of the catalytically active
center and not by chiral atoms in the growing chain.
One model for the active center, proposed by Arlmann and Cossee [298,299], is based
on monometallic catalytic centers (56) with hexacoordinated transition metal:
56
The Ti atoms close to the TiCl
3
surface have a vacant octahedral site, one chlorine
ligand singly bonded and four chlorine ligands bridge bonded with neighboring Ti atoms.
By reaction with the aluminum alkyl, the singly bonded chlorine atom is substituted by
an alkyl group with the formation of a TiC bond. The olen is complexed on the vacant
Copyright 2005 by Marcel Dekker. All Rights Reserved.
site with the double bond parallel to an octahedral axis. Two orientations are therefore
possible, giving rise to the stereospecity. After monomeric unit insertion, the TiR bond
enters the vacant site and another olen molecule is coordinated.
This model is modied by Pino [300,301], Corradini [302], Kissin [303], Keii [304],
Terano [305], Cecchin [306] to other titanium complexes. Bimetallic models between the
titanium compound and the cocatalyst were discussed by Sinn and Patat [137], Pino [301],
and Zakharov [307]. Others suggest that the growing polymer chain is bound to the
transition metal through a double bond (carbene complex) and that the insertion reaction
occurs through formation of a metal-cyclobutane intermediate [308,309].
4. Supported Catalysts
The traditional ZieglerNatta catalyst, based on TiCl
3
and aluminum alkyls (rst
generation), is not active enough to do without the removal of catalyst residues from the
polymer. This is why only a small part of the titanium present on the side surface of
TiCl
3
crystallites is deemed to be active in propene polymerization. Researchers have
endeavored to obtain better utilization of the titanium halogenide by trying to attach it to
the surface of proper supports. Great industrial interest is evidenced by the numerous
patent applications following the initial Shell patent [310319]. Commonly used supports
are MgCl
2,
CoCl
2
, SiO
2
, Mg(OH)
2
, Mg(OH)Cl, MgR(Cl), MgO, MgCO
3
, SiO
2
, and SiO
2
/
Al
2
O
3
[320333]. The preferred halides are those having the same layered lattice structure
as d-TiCl
3
. The dimensions of MgCl
2
and COCl
2
(ionic radii of Mg
2
and Co
2
are 0.066
and 0.072 nm) make them particularly suitable carriers for TiCl
4
(ionic radius of Ti
4
,
0.068 nm). These catalysts were demonstrated to substantially increase the activity in
propene polymerizations using AlEt
3
or AlEt
2
Cl as cocatalysts (second generation).
Furthermore, the use of electron donors, notably esters of carbocylic acids such as
ethylbenzoate, was demonstrated to increase stereoselectivity (third generation) [334347].
With TiCl
4
supported on SiO
2
, the activity is low but the crystallinity of the resulting
polypropylene is high [348]. The addition of NaCl, CaCl
2
, or BaCl
2
increases the activity
by a factor of up to 5.
Soga studied propene polymerizations with catalytic systems based on Mg(OH)
2
,
Mg(OH)Cl, or MgCl
2
/TiCl
4
/AlEt
3
[94,322]. Unlike the TiCl
4
/AlEt
3
system, these catalysts
exhibit an almost constant overall rate of polymerization (4.1 g PP/g Cat hatm) for at least
2 h. Catalysts obtained by reaction of Ti benzyl and cyclopentadienyl derivates with
Mg(OH)Cl have been investigated as well as Grignard reagents together with TiCl
4
at
varying ratios have been investigated [317].
The most important catalysts are obtained by supporting titanium halides on
activated MgCl
2
. By combination with the cocatalyst AlR
3
, a very high activity is given,
although the stereospecity is low (Table 17) [321]. The discovery of catalysts sup-
ported on activated MgCl
2
and modied Lewis bases has solved the problems of low
stereospecity.
5. Role of Lewis Base Esters
The catalyst can be prepared on dierent routes such as ball milling, vibration milling, or
chemical conversions [349]. First, commercially available anhydrous MgCl
2
is ball milled
with ethyl bonzoate over 20 h to aord active MgCl
2
. By this process the dimensions of the
agglomerated primary MgCl
2
crystallites (60 30 nm) are broken (3 2 nm) and stabilized
by ethyl benzoate. The support develops a surface area of 50 to 300 m
2
/g [334]. Second, the
ball milled support is mixed with TiCl
4
by further ball milling of the catalyst support in
Copyright 2005 by Marcel Dekker. All Rights Reserved.
the presence of TiCl
4
or by suspending the MgCl
2
/EB in hot undiluted TiCl
4
. The resulting
solid is washed to remove soluble titanium complexes. The catalyst contains 1 to 5 wt% Ti
and 5 to 20 wt% ethyl benzoate or diisobutylphthalate. The Lewis base used in this
procedure is called an internal Lewis base.
Therefore the function of the internal donor in MgCl
2
-supported catalysts is
twofold. One function is to stabilize small primary crystallites of magnesium chloride; the
other is to control the amount and distribution of TiCl
4
in the nal catalyst. Activated
magnesium chloride has a disordered structure comprising very small lamellae.
An essential part of every Ziegler catalyst is the cocatalyst. Supported MgCl
2
/TiCl
4
or MgCl
2
/EB/TiCl
4
are combined with AlEt
3
or AlEt
3
/EB/ to give high polymerization
activities. The donor used for this procedure is called an external Lewis base. Carboxylic
acid esters or aromatic silanes, preferably alkoxisilane or derivatives such as para-ethyl
anisate, are described as external Lewis bases [338,345]. Silyl ethers R
n
Si(OR
0
)
4n
such as
Ph
3
SiOCH
3
, Ph
2
Si(OCH
3
)
2
, PhSi(OCH
3
)
3
, and (C
2
H
5
)Si(OCH
3
) have also been found to
be highly active promoters in stereospecic olen polymerization [350,351].
Both internal and external Lewis bases react with aluminum alkyls forming a 1:1
complex in the rst step (57) [352,353]. The second step is an alkylation reaction aording
a new alkoxyaluminum species (58).
57 58
Kashiwa found that suitable amounts of ethenebenzoate increased the yield of iso-
tactic polymers; at the same time, the production of atactic polymer is strongly decreased.
So the aromatic ester simultaneously acts as a poison of the aspecic sites and as an
activator of the isospecic sites: It is reasonable to assume that a highly active and
stereospecic catalyst can be obtained by selectively using only the stereospecically active
Table 17 Polymerization of propene with supported MgCl
2
/TiCl
4
catalysts by 70
C.
Catalyst Ti
(%)
Cocatalyst Activity
(kg PP/mol Ti h)
I.I.
(%)
MgCl
2
/TiCl
4
3.6 AlEt
3
870 49
MgCl
2
/TiCl
4
3.6 AlEt
2
Cl 45 33
MgCl
2
/TiCl
4
/EB 2 AlEt
3
650 98
TiCl
3
0.3 AlCl
3
24 AlEt
3
23 76
Copyright 2005 by Marcel Dekker. All Rights Reserved.
centers in the MgCl
2
/TiCl
4
/AlEt
3
catalyst system. The Lewis base increase M
n
for isotactic
polymers and slightly decrease M
n
for atactic ones. Such catalyst yields 100 to 2000 kg/g Ti
of polypropene containing 95 to 98% isotactic polymer in about 3 h. The high activity
makes it possible to leave the titanium (0.5 to 2 ppm) in the polymer. The concentration
of active sites reaches values of 5 to 20% measured by the
14
CO method [354,355].
A new type of catalysts contain a diether such as 2,2-disubstituted-1,3-dimethoxy-
propane and have high stereospeccity even in the absence of an external donor [356]. The
polypropene yield obtained under typical polymerization conditions (liquid monomer,
70
C, 12 h) has increased from 3080 kg PP/g cat for the third generation to
80160 kg PP/g cat [342,357].
Giannini [358] has indicated that, on preferential lateral cleavage surfaces, the
magnesium atoms are coordinated with 4 or 5 chlorine atoms, as opposed to 6 chlorine
atoms in the bulk of the crystal. These lateral cuts correspond to (110) and (100) faces of
MgCl
2
. It has been proposed that bridged dinuclear Ti
2
Cl
8
species can coordinate to the
(100) face of MgCl
2
and on contact with an alkylaluminum cocatalyst these species
are reduced to Ti
2
Cl
6
units in which the environment of the Ti atoms is chiral [358],
a necessary condition for isospecic polymerization. In the absence of a Lewis base, TiCl
4
will coordinate to both the (100) and the (110) faces of MgCl
2
. In the presence of an
internal donor, however, there will be a competition between the donor and TiCl
4
for the available coordination sites. One possible function of the internal donor is that,
due to the higher acidity of the coordination sites on the (110) face, preferential
coordination of the donor on these sites will avoid the formation if Ti species having poor
selectivity.
The requirement for an external donor when using catalysts containing an ester
as internal donor is due to the fact that, when the catalyst is brought into contact with the
cocatalyst (most commonly AlEt
3
), a large proportion of the internal donor is lost as a
result of alkylation and/or complexation reactions. In the absence of an external donor,
this leads to poor stereoselectivity due to increased mobility of the titanium species on the
catalyst surface [360].
In contrast to ester internal donors, the diethers, having greater anity towards
MgCl
2
than towards AlR
3
, are not displaced from the catalyst surface on contact with the
cocatalyst [361]. Consequently, highly isotactic poly(propene) can be obtained even in the
absence of an external donor.
Studies by Busico et al. [362] have indicated that active species in MgCl
2
-supported
catalysts can isomerize very rapidly (during the growth time of a single polymer chain)
between three dierent propagating species. The chain can therefore contain, in addition
to highly isotactic segments, sequences that can be attributed to weakly isotactic
(isotactoid) and to syndiotactoid segments.
For the production of isotactic polypropene, dierent processes can be used (see
production of polyethene). In the laboratory, the catalyst is suspended in dry pure heptane
(or other hydrocarbons) in inert gas atmosphere and then bubble in propane gas at 30 to
60
C]
Isotacticity
[% mmmm]
[En(Ind)
2
ZrCl
2
188 24 132 78.5
[Me
2
Si(Ind)
2
]ZrCl
2
190 36 137 81.7
[Me
2
Si(IndH
4
)
2
]ZrCl
2
48 24 141 84.5
[Me
2
Si(2Me-Ind)
2
]ZrCl
2
99 195 145 88.5
[Me
2
Si(2-Me-4iPr-Ind)
2
]ZrCl
2
245 213 150 88.6
[Me
2
Si(2,4Me
2
-Cp)
2
]ZrCl
2
97 31 149 89.2
[Me
2
Si(2Me-4tBu-Cp)
2
]ZrCl
2
10 19 155 94.3
[Me
2
(2Me-4,5Benzlnd)
2
]ZrCl
2
403 330 146 88.7
[Me
2
Si(2Me-4Ph-Ind)
2
]ZrCl
2
755 729 157 95.2
[Me
2
Ge(2Me-4Ph-Ind)
2
]ZrCl
2
750 1135 158
[Me
2
Si(2Me-4Naph-Ind)
2
]ZrCl
2
875 920 161 99.1
Copyright 2005 by Marcel Dekker. All Rights Reserved.
can produce polypropenes with properties comparable to the ones reached by using
supported TiCl
4
catalysts [389391].
Systematic investigation of bis(indenyl)zirconocenes showed that the main chain
termination reaction is b-hydrogen transfer with the monomer [392,393]. This reaction is
very eectively suppressed by substituents (Me, Et) in position 2 of the indenyl-ring
[394,395]. Substituents in position 4 also cause an enhancement in molecular weight by
reducing 2,1-misinsertions which preferably result in chain termination by b-hydrogen
elimination. Due to the fact that primary insertion is sterically hindered after a regioerror
occurs and therefore the catalyst is in a resting state after a 2,1-insertion, suppression
of this type of misinsertion also leads to enhanced activities. Using aromatic substituents
in position 4 results in additional electronic eects. Thus the most active catalysts
feature a methyl or ethyl group in position 2 and an aromatic group in position 4 of the
indenyl rings.
Besides the bis(indenyl) ansa compounds, C
2
symmetric bridged bis(cyclopenta-
dienyl) metallocenes of zirconium and hafnium (structure (59)) were found to be able
to produce isotactic
59
polypropene (Table 20) [396]. The key for high isotacticity are substituents in positions
2,4,3
0
and 5
0
generating a surrounding of the transition metal similar to the one in
bis(indenyl) metallocenes.
In this type of metallocenes the chirality is due to the chirality of the ligand and the
two chlorines (e.g. the position of the growing chain and the coordinating monomer) are
Table 20 Polymerization behavior of metallocenes based on bridged biscyclopentadienyl com-
pounds. All polymerizations were performed at 30
C]
Isotacticity
[% mmmm]
[Me
2
Si(2,3,5Me
3
Cp)
2
]ZrCl
2
1.6 134 162 97.7
[Me
2
Si(2,4Me
2
Cp)
2
]ZrCl
2
11.1 87 160 97.1
[Me
2
Si(3tBuCp)
2
]ZrCl
2
0.3 10 149 93.4
[Me
2
Si(3MeCp)
2
]ZrCl
2
16.3 14 148 92.5
[Me
2
Si(2,3,5Me
3
Cp)
2
]HfCl
2
0.30 256 163 98.7
[Me
2
Si(2,4Me
2
Cp)
2
]HfCl
2
0.10 139 162 98.5
[Me
2
Si(3tBuCp)
2
]HfCl
2
0.03 17 157
[Me
2
Si(3MeCp)
2
]HfCl
2
1.61 67 148
Copyright 2005 by Marcel Dekker. All Rights Reserved.
homotopic. According to a model of Pino et al. [397400] the conformation of the growing
polymer chain is determined by the structure of the incoming monomer and is forced
into a distinct orientation by steric interactions of its side chain with the polymer chain
(Figure 9) [401406].
The C
2
-symmetric metallocenes give polypropylenes with a high melting point
(162
C) and
13
C-NMR spectroscopically measured tacticities (mmmm pentades) of 97 to
99%. The properties and melting point of isotactic polypropenes prepared by metallocene
catalysts are determined by the amount of irregularities (stereo- and regioerrors) randomly
distributed along the polymer chain. Thus the term stereospecicity does not refer to
extractable aPP as for conventional PP always having a melting point of 160165
C.
Metallocene catalysts depending on their substitution pattern can give a wide range of
homopolymers having melting points between 125 and 165
C (Table 21).
The molecular weight distribution of these iPPs (M
w
/M
n
22.5) is lower than that
of conventional produced PP (M
w
/M
n
520). For applications demanding broader
molecular weight distributions, two or more metallocenes may be combined to give
a tailor-made molecular weight distribution. Compared with conventional iPP grades,
metallocene products show enhanced mechanical strength which can be improved by
tailoring the molecular weight distribution.
The low melting points obtained with some metallocene catalysts, even at high
pentad isotacticities, are caused by 2,1- and 1,3-misinsertions [408,409]. Low melting point
polymers with conventional catalysts are obtained by copolymerization with small
amounts of ethene.
The excellent performance of metallocenes in copolymerizations also oer improve-
ments in impact copolymers. In the wide variety of properties of impact copolymers, the
stiness of the material is determined by the matrix material, while the impact resistance
Figure 9 Mechanism of the isotactic polymerization of propene using an alkylzirconocenium ion
generated from a C
2
symmetric bis(indenyl)zirconocene. The orientation shown for the first inserted
propene with the methyl group down is favored over the other possibility with the methyl group up.
Copyright 2005 by Marcel Dekker. All Rights Reserved.
largely depends on the elastomeric phase. While conventional catalysts show some
inhomogeneities in the ethene/propene rubber phase due to crystalline ethene rich
sequences, the more homogeneous comonomer distribution obtained with metallocene
catalysts results in a totally amorphous phase [410].
Using highly stereoselective metallocenes, highly crystalline, sti polypropene types
are produced. These polymers exhibit a stiness 2530% above that of conventional
polypropenes, resembling that of polypropenes lled with talcum or other minerals [411].
Packages made from these polypropenes may have reduced thickness of the walls, are
easier recycled, show enhanced impact strength, heat resistance, lower density and less
aging.
Metallocenes are also interesting for the production of new iPP waxes for use as
pigment dispersants, toner or lacquer surfaces [412]. The molecular weight of about 10 000
to 70 000 g/mol combined with melting points between 140 and 160
C is easily obtained by
the choice of the metallocene
The homogeneous system is capable of producing isoblock polypropene (see
Figure 8). More stereoerrors shown as lower isotacticity are formed. [En(Ind)
2
]ZrCl
2
(see Table 19) produces a polypropene with an isotacticity of only 78.5%. This means that
about 15 propene units are incorporated in the same stereospecic structure, one is
reversed and the following one has the same orientation as the previous block. The block
of 15 same oriented units is called isotactic sequence length.
A dierent structure is obtained when 4 to 12 propene units have the same
stereospecic structure; then there is a change and the following block of propene units
has the opposite stereospecic structure. This results in a stereoblock polypropene
(see Figure 8). Such structures of polypropene can be synthesized with a catalyst in which
the chirality is further or the rotation of the ligands is hindered away from the transition
metal [411]. Bis(neomenthyl)zirconium dichloride is an example of this type. The catalyst
possesses three chiral carbons at the neomethyl group bonded to the cyclopentadienyl ring.
The stereoblock length depends on the polymerization temperature. With increasing
temperature, the stereoblock length increases. Products with smaller isotactic block length
have a lower melting point and are more exible.
The methylaluminoxane as cocatalyst can be replaced by a mixture of trimethyl-
aluminum and dimethyluoroaluminum, or by N,N-dimethylanilineumtetrakis(penta-
uorophenyl)boron, showing similar polymerization activities [412,413]. Cocatalyst-free
propene polymerization systems are found by Watson [414] like (C
5
Me
5
)
2
LuCH
3,
but the
activity and the molecular weights are low and there is no stereotacticity. Homogeneous
Table 21 Comparison of isotactic polypropenes prepared by different metallocene/MAO catalysts
[En(IndH
4
)
2
]ZrCl
2
(I), [Me
2
Si(4,5Benzlnd)
2
]ZrCl
2
(II), [Me
2
Si(4,6iPrlnd)
2
]ZrCl
2
(III) at 70
C in a
bulk polymerization at Al/Zr 15 000 to conventional isotactic PP prepared by a TiCl
4
/MgCl
2
catalyst (IV) [407].
(I) (II) (III) (IV)
Melting point [
/min] 2 2 2 2
Copyright 2005 by Marcel Dekker. All Rights Reserved.
vanadium catalysts are not able to produce isotactic polypropene but yield a syndiotactic
polymer.
C. Syndiotactic Polypropylene
Syndiotactic polypropene was rst isolated by Natta [415] through separation of polymer
obtained with a- or -TiCl
3
and Al(C
2
H
5
)
2
F or LiC
4
H
9
and on TiCl
4
and LiC
4
H
9
. The
yield of boiling hexane-soluble polypropene was only 1 to 10%. Higher yields are obtained
with homogeneous catalyst based on vanadium compounds (Table 22). For highly
syndiotactic polypropene the Al/V ratio is between 2 and 10; when a weak Lewis base such
as anisole is added, it is 1:1 [416421].
The syndiospecic increases as the polymerization temperature is lowered and as the
steric hindrance of the alkyl groups of the cocatalyst increases. Higher syndiospecicity
is attainable when operating in n-heptane instead of toluene. The viscosimetric molecular
weight of polymers obtained in the presence of anisole increases almost linearly with
polymerization time and is in the range of 10 000 units (intrinsic viscosity in tetralin at
35
C0.5 to 1). The polymerization rate is low; the resulting polymer amounts to only
a few percent of the converted monomer [417].
Experiments with various deuterated propenes have shown that syndiospecic
polymerization with vanadium catalysts takes place via cis addition of the monomeric
units to the growing chain [423]. The polymerization is not thoroughly regiospecic; that
is, 12 insertions are possible [424,425]. Next to syndiotactic stereoblocks, the polymer
also contains irregular stereoblocks [426428].
In 1988, Ewen and Razavi developed a catalyst for the syndiotactic polymerization
of propene based on C
s
-symmetric metallocenes (Table 23) [429431].
From these prochiral metallocenes, chiral metallocenium ions can be produced in
which chirality is centred at the transition metal itself. Due to the ipping of the polymer
chain, the metallocene alternates between the two enantiomeric congurations and pro-
duces a syndiotactic polymer [432437].
Syndiotactic polypropene produced by metallocene catalysts shows a higher level
of irregularities than isotactic ones. Comparing samples of the same degree of tacticity,
the syndiotactic polymer exhibits a lower melting point, lower density (strongly)
depending on the tacticity, ranging from 0.87 to 0.89 g/cm
3
, lower crystallinity, and a
lower crystallization rate [438]. The small crystal size in syndiotactic polypropene causes a
higher clarity of the material but is also responsible for its inferior gas barrier properties
Table 22 Syndiotactic polypropene produced with vanadium catalysts
a
.
Vanadium compound Cocatalyst Al:V:An (Mot) Solvent Temp. (
C) I.S.
VCl
4
Al(C
2
H
5
)Cl 5:1:1 Toluene 78 1
VCl
4
Al(C
2
H
5
)Cl 10:1:1 Toluene 78 0.9
VCl
4
Al(i-C
4
H
9
)
2
Cl 5:1:1 Toluene 78 1.3
VCl
4
Al(i-C
4
H
9
)
2
Cl 5:1:1 n-Heptane 78 2.4
VCl
4
Al(C
2
H
5
)Cl 5:1:1 n-Heptane 78 1.9
VCl
4
Al(C
2
H
5
)Cl 2:1:1 n-Heptane 78 1.3
Source: Ref. 422.
a
Conditions: time 1820 h, vanadium concentration 12.6 mmol in 100 mL of solvent, temperature 78
C,
I.S. crystallinity index due to syndiotactic polymer, determined by IR methods.
Copyright 2005 by Marcel Dekker. All Rights Reserved.
preventing applications in food packaging. However, the resistance against radiation
allows medical applications. Other advantages of sPP are the higher viscous and elastic
moduli at higher shear rates and its outstanding impact strength which disappears at low
temperatures due to the independence of the glass transition temperature on the tacticity.
Commercial product of syndiotactic polypropene utilizes a silica supported metallo-
cene in a bulk suspension process at 5070
C in 1 l of liquid propene.
Metallocene Productivity
[kg PP/(gMh)]
M
w
[kg/mol)
m.p.
[
C]
Syndiotacticity
[rrrr %]
[Me
2
C(Flu)(Cp)]ZrCl
2
180 90 0.82
[Me
2
C(Flu)(Cp)]HfCl
2
3 778 0.73
[En(Flu)(Cp)]ZrCl
2
50 171 111 0.71
[Ph
2
C(Flu)(Cp)]ZrCl
2
3138 478 133 0.87
[Ph
2
C(Flu)(Cp)]HfCl
2
28 1950 102 0.74
Copyright 2005 by Marcel Dekker. All Rights Reserved.
by the meso rotamer) and isotactic (produced by the chiral rotamer) sequences. The block
length was strongly dependent on the temperature.
C
1
-symmetric metallocenes are able to produce also elastomeric polypropene if
consecutive insertions take place on the same active site in addition to chain migratory
insertion. Polypropenes containing blocks of atactic and isotactic sequences are produced,
the block lengths depending on the rate of chain stationary insertion or site isomerization
vs. chain migratory insertion [447,455458]. Rieger [455] used bridged indenyl-uorenyl
metallocenes (structure (61)) to catalyze polypropenes with tailored isotacticities between
20 and 80%.
61
D. Atactic Polypropene
Atactic polypropene (aPP) is a head-to-tail polymer that is incapable of crystallizing, due
to the statistically irregular sequence of sterical orientations of methyl groups connected
Table 24 Properties of enastomeric polypropenes prepared by [MeHC(Ind)(C
5
Me
4
)]TiCl
2
(1),
[Me
2
C(Ind)(Cp)]HfCl
2
(2), [Me
2
C(Ind)(Cp)]ZrCl
2
(3), and (2PhInd)
2
ZrCl
2
(4).
Catalysts 1 2 3 3 4
M
w
(kg/mol) 127 30 50 380 889
Isotacticity (mmmm %) 40 38 54 52 28
Melting point (
C. (I) [En(IndH
4
]
2
, (II) [Me
2
C(Flu)Cp)]ZrCl
2
, (III) Cp
2
ZrCl
2
.
Catalyst Cocatalysts Activity
(kg/molZr h)
Tm
(
C)
M
n
(kg/mol)
M
w
/M
n
Tacticity
(I)/homogeneous MAO
3 mmol
2070 111 3.3 1.9 71%mmmm
(I)IMAO/SiO
2
TEA
1 mmol
77 140 5.3 2.5 90%mmmm
(I)/MAO/SiO
2
TIBA
2 mmol
382 105 6.6 1.8 69%mmmm
(II)/homogeneous MAO
13 mmol
758 123 39.3 1.8 77% rrrr
(II)/MAO/SiO
2
TIBA
2 mmol
141 133 45.2 1.9 83% rrrr
(III)/homogeneous MAO
10 mmol
132 0.3
(III)/MAO/SiO
2
TIBA 99 1.8
Copyright 2005 by Marcel Dekker. All Rights Reserved.
With the system ethylenebis(indenyl)zirconium dichloride/methylaluminoxane, 6%
of 1,5-hexadiene could be incorporated [499,500]. The copolymerization parameter r
1
for
this reaction is in the range of 14 to 19. The polymerization rate decreases with increasing
1,5-hexadiene concentration in the reaction mixture. The block copolymers are mostly
mixtures of the copolymer and both homopolymers [501].
1. Polymer Characterization and Compounding
Isotactic and syndiotactic polypropene are partly crystalline polyolens. Therefore,
their properties largely depend on their degree of crystallinity and crystal structure. These
parameters can be inuenced by crystallization temperature, cooling rate, tensile
stress, tempering, molecular weight, and molecular weight distribution. Isotactic poly-
propene forms a 3.1 helix with identical conguration at every tertiary carbon atom,
whereas in syndiotactic polypropene the conguration of the tertiary carbon atoms
is alternating. The helix conformations are states of particularly low energy and are
therefore favored by the system. In the helix the pendant methyl groups have a
well-dened tilt pointing up and down, but they are always oriented toward the outside
(away from the center) [502]. The helical phase is a racemic mixture consisting of pairs
of dextrogyric and levogyric helices. This is responsible for the high melting point of
162175
C.
In contrast to this, atactic polypropene is amorphous even at room temperature.
The degree of crystallinity of iso- or syndiotactic polypropene is normally on the
order of 60 to 70%. There are several modications of isotactic polypropene. The most
important is the monoclinic a type. Its unit cell, with dimensions of 0.67, 2.10, and
0.65 nm, contains three monomeric units of four polymer chains, respectively [503]. Next
to this, the trigonal a and triclinic g-modications occur. They are best characterized
by spectroscopical methods IR [502,503], x-ray diraction [504],
1
H-NMR, and
13
C-NMR
[505,506].
Stabilizers and additives are blended into the crude product to prevent the polymer
chains from degrading. The tertiary carbon atoms bearing the pendant methyl groups
are fairly sensitive to oxidation. That is why the processing must proceed under exclusion
of air with antioxidants present in the polymer.
Substituted phenols that act as scavengers for radicals formed in the course of the
degradation reaction as well as thio compounds and organophosphites are added as
antioxidants. Benzophenone and carbon black act as UV stabilizers. Calcium stearate or
other carboxylic acids are added to bind chloride originating from the catalyst. Further
additives can be acceptors for coloring, anti-electrostatics, nucleating agents to promote
crystallization, lubricants, or ame retardants [507,508]. Polypropene can also be blended
with other polymers as rubbers (EPDM) or polyethene [509511]. In these products the
Table 26 Copolymerization of propene (1) with various a-olefins (2).
Comonomer (2) Catalyst r
1
r
2
Ref.
1-Butene TiCl
3
/AlEt
3
4.6 0.5 484
1-Hexene TiCl
3
/AlEt
2
Cl 4.18 0.16 485
1-Methyl-1-pentene TiCl
3
/AlEt
2
Cl 6.4 0.31 486
Styrene TiCl
3
/AlEt
3
20.5 0.3 487
Vinyl cyclohexane TiCl
3
/AlEt
2
Cl 80 0.049 488
Copyright 2005 by Marcel Dekker. All Rights Reserved.
mixed phase is embedded in a continuous polypropene matrix. No genuine solution is
obtained. Additional new properties can be achieved by compounding the polypropene
with solid inorganic or organic lling materials [512]. Rigidity and hardness, especially,
can be improved in this way. Possible lling materials are glass bers, glass balls, talcum,
chalk, aluminum oxide, metal powder, wood our, or carbon bers [513]. Up to 50 wt% of
these lling materials can be directly worked in as a master batch.
IV. POLYMERS OF HIGHER a-OLEFINS
Higher a-olens are less easily polymerized, as they pose more steric hindrance. Propene
is about three times more active than 1-butene, depending on the catalyst system. The
polymerization rate is progressively decreased with increasing size of the linear alkyl
group. On the other hand, 2-olens cannot be homopolymerized. On the other hand,
2 olens cannot be homopolymerized by Ziegler catalysts. Nickel-diimine/MAO or borate
systems are able to homopolymerize trans-2-butene to polymers with low glass-transition
temperatures until 53
C for poly(1-hexene).
Campbell observed a decrease in activity for a-olens with branched alkyl groups
[527]. A signicant decrease in olene activity takes place when the branch moves closer to
the double bond. 3-Methylpentene is three times less active than 4-methylpentene. When
the branch is moved away from the double bond to carbon 5 or 6, however, the olen
activities increase. The olen activity is drastically decreased when both carbons in
position 3 or 4 are substituted (the activity of 3,4-dimethyl-1-pentene is ve times less than
that of 3-methyl-1-pentene). Lower activities are also found with growing size of the
substituent at the branch. The poly(4-methyl-1-pentene) has drawn most interest in this
group [528,529]. It has a higher melting point of 235
C)
Propene 1 170
1-Butene 0.220.62 140
1-Pentene 0.20.45 80
1-Hexene 0.160.36 20
1-Heptene 0.20.45 18
1-Octene 0.10.3
1-Nonene 0.10.3 19
1-Decene 0.120.28 34
1-Dodecene 0.10.2 49
1-Tetradecene 0.10.2 57
1-Hexadecene 0.10.2 68
1-Octadecene 0.10.15 71
Copyright 2005 by Marcel Dekker. All Rights Reserved.
63
As of the steric hindrance and the possibility to form allylic intermediates, cyclopentene
inserts by metallocene catalysts with a 1,3-structure while polynorbornene shows a
1,2-structure (structure (64)) [544].
64
When polymerization occurs by double-bond opening, the product can be
syndiotactic, isotactic, or atactic.
The ring opening polymerization can give two structures, the trans-poly(cyclopen-
tenamer) or the cis-poly(cyclopentenamer). Both pathways were found to be followed
with Ziegler catalysts. Table 28 gives results of cycloolen polymerizations. Cyclopropene
polymerized spontaneously above 80
C
for polycyclobutene, 395
C for polycyclopentene.
Table 29 compares the activities for the homopolymerization with dierent
transition metal [M] catalysts using MAO as cocatalyst [551].
Nickel-O- and palladium-O-complexes are very active catalysts for the polymeriza-
tion of norbornene and also for cyclopentene [552554]. Nickel catalysts produce soluble
polymers with a molecular weight of over one million while polymers obtained with
palladium or metallocene complexes are insoluble. The soluble polymers have an atactic
structure. The microstructure of the polynorbornene depends on the catalyst used and is
isotactic by synthesis with chiral metallocenes.
The processing of homopolynorbornene would be extremely dicult, due to a
melting point higher than the decomposition, especially if the polymer is insoluble.
Dimethanooctahydronaphthalene [DMON] is more rigid than norbornene. The copoly-
merization product of norbornene or DMON with ethene is amorphous, featuring high T
g
values of 160
C with FriedelCrafts
catalysts (e.g., AlCl
3
, BF
3
) in chloromethane or other solvents [564573]. The Lewis
acid as initiator is activated incombination with a proton sosurce which is usually present
Table 29 Polymerization of norbornene with different catalysts at 20
C.
Catalyst [M]
(mol/l)
Polymerization
time (
C)
Al:M
molar ratio
Activity
(kg Pol/mol M)
Molecular
weight (g/mol)
Ni(acac)
2
5 10
6
0.5 9 400 11 000 2.4 10
6
Pd(acac)
2
2 10
6
0.5 25 000 27 000 Insoluble
Ni(cod)
2
5 10
6
0.5 9 400 3 800 1.7 10
6
(Pd-Allyl-Cl)
2
5 10
6
0.3 10 000 44 000 Insoluble
Cp
2
ZrCl
2
7 10
4
72 5 1.6 Insoluble
[En(Ind)]
2
ZrCl
2
10
5
48 5 000 40 Insoluble
CpTiCl
3
6 10
4
2 603 400 Insoluble
Co(acac)
2
2 10
5
1 2 600 220 Insoluble
Copyright 2005 by Marcel Dekker. All Rights Reserved.
as a trace impurity (e.g. water, hydrogen chloride). The mechanism includes the
following reactions [558,574]:
65
66
67
68
To obtain high molecular weights, the polymerization temperature and with it the
rate of the transfer reactions must be lowered. At 100
C poly(isobutylene) of molecular
weight 300 000 g/mol is obtained [575].
The reaction is strongly exothermic with a reaction enthalpy of 356 kJ/mol and is
usually nished within seconds or a few minutes, even at low temperatures. The molecular
mass is kept low by adding a-olens and diisobutene. Addition of 0.25% of diisobutene,
for instance, reduces the molecular weight from 260 000 to 45 000. In contrast, the addition
Table 30 Copolymerization of isobutene (M
1
) with different comonomers (M
2
); copolymerization
parameters r
1
and r
2
.
Comonomer r
1
r
2
Refs.
Styrene 1.82.8 1.45.5 577
4-Chlorostyrene 1.01.7 1.014.7 578
a-Methylstyrene 0.201.2 1.45.5 579,580
Indene 1.1 2.2 580
1,3-Butadiene 43 0 581
trans-1,3-Pentadiene 2.3 582
cis-1,3-Pentadiene 5.0 582
Cyclopentadiene 0.20.8 1.56.3 583
Copyright 2005 by Marcel Dekker. All Rights Reserved.
of organometallic amides [e.g., zinc bis(di-ethylamide), titanium tetra(diethylamide)]
has the opposite eect, raising the molecular weight to more than 1 million [576].
1. Copolymers of Isobutene
Isobutene can be copolymerized with numerous unsaturated compounds via a cationic
route [577586]. Table 30 lists various comonomers and copolymerization parameters. The
isobutene portion in the copolymers usually exceeds 90%. The use of aluminum organic
compounds (e.g., AlEt
2
Cl) as opposed to aluminum trichloride permits better control
of the copolymerization, as they are weaker Lewis acids. Hydrogen chloride or halogens
must be added as cocatalysts that are capable of regenerating the carbocations. The
organoaluminum catalysts are produced at 78
C for the
poly(isobutene) block and 96