APPLICATIONS OF THE OLEFIN METATHESIS REACTION TO

INDUSTRIAL PROCESSES
F. LEFEBVRE
Laboratoire LCOMS, UMR CNRS-CPE 9986, 43 Bd du 11 Novembre
1918,69626 Villeurbanne Cedex, France
1. Introduction
The industrial applications of the olefin metathesis reaction are relatively recent
although this reaction was observed about 50 years ago. Streck described in details the
historical development of this reaction in his review in a book of the same series [1].
He gave also interesting data on the industrial processes in refs. [2] and [3]. More
recently, Ivin and Mol, in their classical book on olefin metathesis, have also
developped this field in a special chapter [4]. The idea of olefin disproportionation
was first proposed by Robert Banks at Phillips [5], who had observed traces of
pentenes and propene in the reaction mixture after passing isobutane and butenes
through a bed filled with molybdenum carbonyl supported on alumina. The Ring
Opening Metathesis Polymerization was found by the Natta group at Montedison [6,
7]. Many groups studied this reaction and its mechanism was proposed by Chauvin
[8], years before the isolation of the first carbene. What is important to know is that
the development of these industrial processes was strongly related to economical
and/or special local conditions. This could be the transformation of sideproducts or
the obtaining compounds with a higher added value.
We have separated the industrial applications into two groups, depending on the
resulting product, an acyclic olefin or a polymer. Up to now, the third class of
applications, the ring closing metathesis reaction, has not been applied industrially,
despite some interesting results were obtained on the laboratory scale.
2. Processes for the Production of Acyclic Olefins
2.1. THE TRIOLEFIN PROCESS AND RELATED PROCESSES
2.1.1. Thetriolefinprocess
Historically, the triolefin process, developed by Phillips, was the first industrial
application of olefin metathesis [9 - II]. It involved the preparation of high purity
ethylene and but-2-ene from propene:
247
E. Khosravi and T. Szymanska-Buzar (eds.),
Ring Opening Metathesis Polymerisation and Related Chemistry, 247-261.
2002 Kluwer Academic Publishers.
248
It was developed in order to valorize the C
3
fraction of a local naphtha cracker.
Shawinigan Chemicals Inc. Used this process in thewir plant near Montreal (at
Varennes) in Canada from 1966 to 1972. The plant had a capacity of 50000 tons of
feedstock per year. The catalyst used was tungsten oxide supported on silica and
doped with sodium to prevent the double bond shift reaction of but-2-ene (which
should decrease the selectivity). The operating temperature was between 370 and
450C and the. conversion (40 - 43%) corresponded to near equilibrium conditions.
The selectivity towards ethylene and but-2-ene was very high (> 95%). In addition,
instead of pure propene, it was possible to use directly the C
3
fraction (propane +
propene) of the naphtha cracker.
A change of the economic data and a higher demand of propene led to the closure of
the plant in 1972. However, as it was relatively simple (see Figure 1), it could be
restarted easily, probably not for obtaining but-2-ene but for the production of high
purity but-l-ene, after treatment with an isomerization catalyst. Indeed, but-l-ene can
be used as a comonomer in polyethylene synthesis.
Propene
Propane
C4 ....
Prop>ne
Figure 1 : Scheme of the triolefin plant
2.1.2. The reverse triolefinprocess
C4
C5+
Different market conditions rendered attractive the use of the process in the reverse
direction to produce polymerization grade propene from ethylene and but-2-ene. In
this process, but-2-ene can be obtained directly from the C4 fraction of a naphthta
cracker or by dimerization of ethylene. In 1985, the Lyondell Petrochemical Co.
started to operate a plant at Channelview (Texas, U.S.A.), for the production of
135000 tons of propene per year. In this process, part of the ethylene formed by
cracking units of ethane is dimerized to but-2-ene using a homogeneous nickel catalyst
developed by Phillips. This but-2-ene reacts with the rest of ethylene, on the classical
Phillips catalyst, to produce propene.
2.1.3. The IFP Meta-4 process
The Institut F r a n ~ a i s du Petrole and the Chinese Petroleum Co. at Taiwan developped
a new process, called Meta-4 [12] for the preparation of propene from ethylene and
butene. This process was proposed to valorize the C4 fraction of steam-cracking after
249
extraction or semi-hydrogenation of the butadiene and transformation of the isobutene
into poly-isobutene or methyl tertiobutyl ether. It could also allow the
propene/ethylene ratio to be increased in the products of the steam-cracking without
changing the cracking conditions. The catalyst was rhenium oxide on alumina,
allowing the reaction to proceed at low temperature (35C). The use of pressure (60
bar) allowed it to proceed in the liquid phase. A pilot plant was built in Taiwan and
operated from 1988 to 1990, with a capacity of 15kg of propene per hour.
The process (Figure 2) can be seen as a semi-continuous counter current contact
between the reactant mixture and the catalyst. When the system operates, the stream
enters the bottom of the reactor and goes out by the top. However, the catalyst
deactivates and when it descends through the reactor, it becomes less and less active
and must be regenerated. For this purpose, a small percentage of the catalyst is taken
periodically from the bottom of the reactor and transferred into the regenerator. The
regenerated catalyst is then returned to the top of the reactor. The plant is completed
by two columns where the reactor effluents are separated. The remaining ethylene and
but-2-ene are recycled.
,...-______ C
2
C
J
c ~
Figure 2 : Scheme of the IFF Meta-4 process
Up to now, this process has not been applied industrially, even if some industrialist are
interested in introducing such a metathesis step in their refining process. The main
problem is the cost of the catalyst which does not render the process competitive with
the classical Phillips system. A decrease of the rhenium loading by a factor 2 should
allow it to be more attractive. Another problem is that the reactants must have a high
purity, in contrast to the classical process which is less sensitive to contaminants, due
to the high reaction temperature.
2.2. THE NEOHEXENE PROCESS
At the beginning of the sixties, laboratory studies showed that diisobutene (2,4,4-
trimethyl pent-2-ene) could be cleaved with ethylene over a classical metathesis
catalyst to produce neohexene and isobutene [13 - 15].
250
/\Y +
.. +
Neohexene can be a very important intermediate in the manufacture of a synthetic
musk. Hence the market for neohexene grew rapidly. Phillips started the industrial
development in 1969 with a small pilot plant producing 20kg of neohexene per year
and which worked during three years and produced 3 tons of neohexene which were
sold. As the demand increased, a larger unit, with four times the capacity of the
smaller pilot, was then constructed. As the demand for neohexene continued to
increase ( from 90 tons in 1973 to 270 tons in 1979), a commercial unit was
constructed in 1980. It is located at the Phillips petrochemical complex near Houston
(Texas, U.S.A.) and has a capacity of 1400 tons per year.
Dimcrizalion
,..=.;==:.;;.::..- E-Ih-,yl-en-e---- Isobulene
Noohc"c e
Heavies
Figure 3 : Scheme of the neohexene plant
From a practical point of view, commercial diisobutene is a mixture of 2,4,4-trimethyl
pent-2-ene, used in the cross-metathesis reaction, and of 2,4,4-trimethyl pent-l-ene
(not modified by the metathesis reaction), in a relatively large amount (20 to 25%). In
order to valorize the process, it is necessary to use commercial diisobutene and so to
convert the terminal non useful olefin into the internal useful one. This can be done by
mixing the metathesis catalyst (W0
3
/Si0
2
) with an isomerization catalyst (typically
magnesia) together in the reactor. Typically, with a 1 : 3 mixture of WOiSi0
2
and
MgO, at 370C, under a 30 bar pressure and with a ethylene to diisobutene ratio of 2.
A conversion of 65% of diisobutene is achieved with a neohexene selectivity around
85%.
A simplified scheme of the plant is shown on Figure 3. Commercial diisobutene
entering the plant is first fractionated to remove an oxidation inhibitor which poisons
the dual catalyst. The recycled diisobutene is also fractionated to remove heavies
(typically C
9
). The fractionated diisobutene, along with the ethylene stream, enters the
top of the reactor containing the dual catalyst. The ethylene stream consists of make-
up and recycle ethylene and is passed through a compressor to obtain the desired
reaction pressure. The reaction temperature is easy to maintain as the reaction is only
251
slightly exothermic. The reactor effluents are cooled and the pressure is decreased.
They are then split into a gas fraction (containing mainly ethylene and a few entrained
liquid) and a liquid part (containing mainly isobutene, neohexene and diisobutene)
which is further fractionated. Diisobutene i's recycled directly while isobutene is
recycled via its transformation into diisobutene in a dimerization reactor.
During a typical process cycle, the diisobutene conversion starts at about 75% and
gradually declines. When the conversion reaches 5 0 ~ , the catalyst system is
regenerated using an air-inert gas mixture to control the temperature of the coke burn-
off. Throughout the process, the selectivity to neohexene remains constant at c.a.
85%.
As said above, the main application of neohexene is the synthesis of musk perfume
components, in two steps. The first step is the alkylation of p-cymene by neohexene
and the second a reaction with acetyl chloride:
o
}=o
CI
Other applications such as epoxidation with H20 2, alkylation with benzene or
amination were also proposed but have not been yet applied industrially.
2.3. THE FEAST (FURTHER EXPLOITATION OF ADVANCED TECHNOLOGY)
PROCESS
This process allows the synthesis of a,w-diolefins by cross-metathesis of cycloolefins
with ethylene. The reaction was first studied by Phillips who produced multi-tons of
1,5-hexadiene [13]. Feedstocks for this process were two commercially available
butadiene derivatives, cyclooctadiene and cyclododeCairiene.
o
1,5.9-decatriene
1.5-hexadiene
1.5-hexadiene
252
The reaction was made on the classical Phillips catalyst and, by use of an excess of
ethylene, high conversions (> 99 %) and selectivities (> 65 %) to 1,5-hexadiene could
be achieved.
Phillips also proposed a route to 1,9-decadiene by homogeneous hydrogenation of
cyclooctadiene to cyclooctene and then cross-metathesis with ethylene over WOiSi0
2
(yield 75% for a conversion of 90%).
0-"' 0- 1 ,9decadiene
Shell developed a process, called FEAST [16], using these reactions but with a
different catalyst, promoted rhenium oxide on alumina. This catalyst allowed the
reaction to proceed under very mild conditions (0 to 20e, I or 2 bar). A commercial
plant, allowing the production of 3 000 tons per year of diolefins was opened in 1987
at the Etang de Berre (France). It has been closed some years ago, due to the lack of
the market.
2.4. THE SHOP (SHELL HIGHER OLEFIN PROCESS) PROCESS
To date, the largest scale industrial process containing a metathesis reaction is the
SHOP process, developped by Shell, for the preparation of detergent-range alkenes
from ethylene [17, 18].
CHr(CH2hn.rCH=CH2 n=5-lO
The entire process is schematized on Figure 4. In the first step, ethylene is
oligomerized in the presence of a homogeneous nickel phosphine catalyst. This
catalyst is a nickel hydride generated by reduction of a nickel salt in the presence of a
chelating ligand such as diphenylphosphinobenzoic acid or by reaction of nickel(O)
with a phosphorus ylide.
n CH2
--CHz cat. 100 QC, 80 bars
Cat =
CHr(CH2)zn.rCH=CH2
Ph Ph
\....... PPh
C
P,\ / 3
NI
/ "H
o
n = 2 - 20
Such a catalyst is allowed to react with ethylene in a glycol solvent such as 1,4-
butanediol at about lOOC and 80 bars. The pressure is required to attain a high
linearity. A rapid reaction occurs, leading to a mixture of a-olefins from C4 to C40 with
a Schulz-Flory distribution (40% in the C4 - C8 range, 40% in the CIO - CI8 range and
253
20% above). The olefins are immiscible in the catalyst containing glycol layer and are
separated by decantation. After washing the olefin layer with additional glycol to
remove catalyst traces, the catalyst can be reused. Originally, the CIO - CIS fraction of
the olefins was the most marketable but now octene and hexene are valuable products
and so the C
6
- CIS fraction is separated and can be further fractionated into individual
components.
EJ----+
I I ---+ [ CII - Czo I
l
1 <C6 +>C20

PL...-__ __ '---J"
I CII - C20 I
Figure 4 : Scheme of the SHOP process
The remaining lighter ( < C
6
) and heavier ( > CIS) olefins undergo, in a second step,
double bond isomerization over a potassium metal based catalyst to an equilibrium
mixture of internal olefins. This second step proceeds at 100
D
C and at 10 bars. In a
third step, the low- and high-boiling internal olefins are cross-metathesized over a
heterogeneous catalyst such as Mo0
3
or a cobalt molybdate supported on alumina.
Additional ethylene can be added at this moment for optimization of the process. Due
to the prevalence of reactions between a low and a high-boiling olefin, most of the
product is in the useful range ("" 15% in the C
ll
- C
14
range). The remaining is
recycled. The final product consists of more than 95% linear alkenes with c.a. 3%
branched olefins. Finally, these olefins can be converted into terminal alcohols by
hydroformylation with a cobalt catalyst.
Shell began large-scale production (200000 tons per year) in 1979 in Geismar
(Louisiana, U.S.A.) and the capacity was increased to 590 000 tons per year in 1989.
A second plant was also built in 1987 in Stanlow (U.K.) with a capacity of 270000 tons
per year.
2.5. NON COMMERCIAL PROCESSES
2.5.1. Synthesis of styrene from toluene
This process had been studied by Monsanto [19] and Gulf [20, 21]. Its advantage
should be to use toluene instead of benzene. In a first step, toluene is converted into
stilbene by oxidative coupling (dehydrodimerization) at 600
D
C over lead oxide
supported on alumina. The oxygen used in the reaction comes from the lead oxide
(stoichiometric reaction).
254
~ .
Dehydrodimerization Metathesis
It is then necessary to periodically regenerate lead oxide by reaction with oxygen. In
the second step, stilbene is cross-metathesized with ethylene over a classical W0
3
/Si0
2
based catalyst. In order to prevent polymerization of styrene, this second reaction is
also made at high temperature ( > 400C).
Even if this process seems attractive, it presents some problems which render it to be
improved before commercial application. The main one is the high amount of oxidant
which is required (one mole of lead per mole of toluene). The second problem is the
presence, in stilbene, of oxygenated compounds which are poisons for the metathesis
catalyst.
2.5.2. The isoamylene process
Various industrial companies have developed a process for the production of
isoamylene (2-methyl but-2-ene), which is a precursor of isoprene (obtained by
oxidative dehydrogenation). It can be produced by cross-metathesis of isobutene with
but-2-ene or propene:
+ ~
+ ~
The process has been developed by Phitlips at the pilot stage [22]. The feed entering
the reactor contained a mixture of isobutene (50%), propene and but-2-ene. The
catalyst was the classical Phillips system, W0
3
/Si0
2
.
However the process has never been commercialized, due to economic changes.
Indeed, isobutene is now mostly used for the manufacture of methyl tertiobutyl ether,
which is used as additive to gasoline.
2.5.3. Synthesis of2,2,3-trimethyl pentane from propene
2,2,3-trimethyl pentane is an additive to gasoline of which it increases the octane
number. It has been proposed to synthesize it from propene, in two steps [23, 24]. In
the first step, propene is metathesized into but-2-ene and ethylene, by the classical
Phillips triolefin process:
But-2-ene is then alkylated with isobutane, leading to the target product:
255
As for the classical triolefin process, the higher demand of propene has prevented the
development of this process.
2.5.4. Synthesis of higher olefins from propene
This process can be understood as a succession of metathesis and isomerization
reactions [25]. In a first step, propene is metathesized into ethylene and but-2-ene :
But-2-ene is then isomerized into but-I-ene:
But-I-ene is allowed to cross-metathesize with propene, leading to pent-2-ene which is
further isomerized into pent-I-ene. The sequence of these two reactions, metathesis
and isomerization, is repeated as many times as necessary:
CHr(CH2)n-CH=CH2 + CH
3
-CH=CH2 ..
CH3
CHr (CH2)n+I-CH=CHz
The main problem of this process, in addition to the fact that it uses propene as a
reagent, is that increasing the carbon length by one carbon atom requires one propene
molecule and forms one ethylene molecule. This does not render it competitive vs. the
SHOP process, for example.
2.5.5. Redistribution of alkanes
This process could be used for the modification of a distribution of alkanes [26]. It
comprises three steps. In a first step, the alkanes are dehydrogenated over a classical
catalyst such as PtlAIz0
3
. The resulting alkenes undergo then a metathesis reaction,
over a classical W0
3
/Si0
2
catalyst, allowing the redistribution of chain lengths.
Finally, alkenes are rehydrogenated into alkanes over PtlAI
2
0
3

3. Processes for the Production of Polymers
Up to now, all processes developed industrially for the production of polymers by
olefin metathesis involve ring opening metathesis polymerization of cycloalkenes.
256
n
u
3.1. POLYMERIZATION OF CYCLOPENTENE
Cyc10pentene is a relatively inexpensive compound which is obtained by thermal
cracking of dicyc10pentadiene and further hydrogenation. Its polymerization has been
widely studied:
ROMP of cyc10pentene is achieved easily with conventional metathesis catalysts such
as WClJJjtAlClz/ROH or W0
3
/AIz0
3
. The Institut Fram;ais du Petrole developed also
highly active catalysts (substrate to catalyst ratio of 500000) based on Fischer type
carbenes ((CO)sW=C(OEt)Ph + TiCI
4
) for this reaction [27]. The polymer properties
were reported to be excellent (strength higher to other synthetic rubbers, high modulus
and resilience, excellent abrasion and resistance, complete compatibility with other
elastomers [28]. Industrialist decided then to use this polymer in tyres. Unfortunately,
the tests were disastrous, the rubber crumbling and disintegrating at the shoulders. For
Breslow, this was due to a depolymerization process. Traces of WOiAI
2
0
3
, used for
the polymerization, remained in the rubber and as the shoulders are the hottest part of
the tyre, some depolymerization could occur [29]. More recently, it has been shown
that, in fact, this was due to a phase transition of the polymer [30]. But, to date, this
has prevented the commercial application of this polymer.
3.2. POLYMERIZATION OF CYCLOOCTENE (VESTENAMER)
The ring opening polymerization of cyclooctene was marketed by Chemische Werke
Hiils in 1982. The plant was implanted in Marl (Germany) and has now a capacity of
12000 tons per year.
~ n
poly-octenamer
The catalyst is the classical Calderon system, WClJJjtAlClz/EtOH. The resulting
polymers are sold under the tradename Vestenamer. Most of the production
corresponds to Vestenamer 8012. This polymer contains 80% of trans double bonds
and has a viscosity of 120cm
3
g-
1
(0.1 % solution in toluene at 25C), explaining the
acronym Vestenamer 8012 [2, 31]. This polymer has also a low molecular weight
257
(Mw = 60000 to 80000) and a high crystallinity (c.a. 33%). At room temperature, it is
hard and it has an exceptionally high viscosity. Above 60C, it becomes a fluid with a
honey-like consistency (its melting point is 55C). The hardness at room temperature
is due to the high crystallinity while the fluidity at high temperature is due to the low
molecular weight. It is especially suitable for use in blends with other rubbers since
the above properties are carried over, to some extent, into the blends, which become
stiffer at room temperature and flow more easily at 60C. Generally, 10 to 30% of
Vestenamer are sufficient to confer these technical advantages.
3.3. POLYMERIZATION OF NORBORNENE (NORSOREX)
CdF Chimie commercialized in 1976 polynorbornene under the tradename Norsorex.
The plant was located in Carling (France) and had a capacity of 5000 tons of
polynorbornene per year [32].
n
- ' ~ n
polynorbornene
The monomer is made by the Diels-Alder reaction of dicyciopentadiene with ethylene.
The catalyst for ROMP is ruthenium chloride in butanol. The process is relatively
simple as the two liquids (ruthenium chloride in butanol and norbornene) are directly
mixed in the extruder, in air. The norbornene to ruthenium ratio is very high (c.a.
25000) and the conversion reaches 50%. As the process operates in air, a small
amount of norbornene is oxidized into epoxynorbornane (the epoxide to ruthenium
ratio is c.a. 5) which can accelerate the polymerization. Indeed, mechanistic studies
have shown that the catalytic reaction passes through a ruthenium hydride (formed by
substitution of chlorine by butoxy ligands and further ~ - H abstraction) or through a
ruthenium oxametallacyciobutane (formed by reaction of the ruthenium complex with
epoxynorbornane) [33].
The polymer has a very high molecular weight (more than 2000000) and a high trans
content ( more than 80%). It can adsorb up to seven parts of extending oils or esters
plasticizers. The vulcanized product has important specialty applications, particularly
for vibration damping.
3.4. POLYMERIZATION OF DICYCLOPENTADIENE (METTON, TELENE)
The cheapness of dicyciopentadiene (DCPD), obtained as a byproduct from the
cracking of oil, makes it an attractive candidate for the production of materials by
metathesis polymerization. Its ROMP has been extensively studied and two
companies, BFGoodrich and Hercules, have commercialized the corresponding
polymer under the tradenames Telene and Metton respectively [34, 35]. Recently, a
part of BFGoodrich and APT (Advanced Polymer Technologies) formed a joint
venture to produce some related products, especially poly-DCPD. This company has
258
become the largest supplier of poly-DCPD in the United States and it can manufacture
large and complex parts, weighing up to 500 kg. On the other hand, Hercules has a
plant in Deer Park (Texas), with a capacity of 13600 tons of poly-DCPD per year.
DCPD has two double bonds which can react by ROMP. However, the norbornene-
type double bond can react much more easily than the other double bond, which
undergoes only partial ring opening polymerization, responsible of the cross-linking.
The structure of the polymer can then be shown as below:
For example, in Metton there is one cross-linkage for five monomer units. The cross-
linking will be responsible for most properties of poly-DCPD and it can be increased
by various ways such as the addition of a cationic initiator or of a comonomer (the
trimer of cyclopentadiene is used in Telene). The cis/trans ratio of the double bonds
can vary, depending on the catalysts. For Metton, it is usually about 3/2. Depending
on the company, various catalytic systems are used: Hercules used tungsten aryloxide
complexes with aluminium or tin alkyls [36], while BFGoodrich uses a
trialkyloctamolybdate with also an aluminium alkyl. Shell developped a catalyst based
on the WClJdiisopropyiphenol1R3SnH system [37].
The most interesting feature of the industrial process is that it uses the RIM (Reaction
Injection Molding) technology. A scheme of the RIM process is given on Figure 5.
Two streams arrive in a mixing chamber where they are mixed, before injection into
the preheated mold. The first mold contains the catalyst (for example the tungsten
aryloxide complex) while the second contains the cocatalyst (typically an alkyl
aluminium chloride). The DCPD is in one or the two streams. The polymerization
reaction occurs in the mould and the heat of reaction raises the temperature up to
150C in a few minutes. The main problem is to control the induction period to
prevent polymerization in the mixing chamber. This can be achieved by adding a
Lewis base (acetylacetone, benzophenone, dibutyl ether) which will act as a moderator.
Other problems are that in most cases the conversion is not complete necessitating
unconverted DCPD to be removed and that pure DCPD is a solid at room temperature
and so the stream must be heated.
The RIM process has great advantages. Indeed, it does not necessitate a high cost
equipment, due to the low molding pressure, and it allows the manufacture of large and
complex parts. It operates in air, without purge. One advantage of working in such
conditions is that the surface of poly-DCPD is oxidized, allowing an easy painting of
the resulting solids.
259
DCPD DCPD
Catalyst Cocatalyst
y-Moderator
Polymerization
Figure 5 : Scheme of a RIM process
3.5. POLYMERIZATION OF NORBORNENE DERIVATIVES (ZEONEX)
Recently, Nippon Zeon developped a process for the synthesis of polymers displaying
interesting properties and commercialized under the tradename Zeonex [38-44]. These
materials are obtained by ring opening polymerization of norbornene type derivatives
followed by a partial or total hydrogenation of the double bonds. The monomer
contains three to five cycles.
1
'R
R
n = 0 - 2 ; R, R' = H, alkyl
The catalyst is a typical norbornene polymerization homogeneous catalyst, for example
a tungsten halide with an organoaluminium compound and a tertiary amine. The
hydrogenation step is made with a classical heterogeneous catalyst such as palladium
on carbon. The molecular weight of zeonex varies between 20000 and 500000,
depending on the monomer. It is amorphous with a high glass transition temperature
(c.a. 140C). As it does not contain any polar group, it provides low water absorption
and moisture permeability. In addition, it is colorless and transparent. All these
properties make it ideal for applications such as optical disks and plastic lenses.
4. Conclusion
This overview has given industrial applications of the olefin metathesis reaction. If
most commercial applications have been listed, only some of the non-commercialized
ones were given but even so some conclusions can be drawn:
(i) Up to now all industrial applications are limited to unfunctional olefins, as
functional groups deactivate the metathesis catalysts. Search for more tolerant
catalysts, such as ruthenium, could overcome this problem.
(ii) The recently developed alkylidene catalysts suffer from a main disadvantage, their
price, due to the difficulty of their synthesis which prevents also their easy recycling.
260
They could be used only for applications where these two parameters are not a
problem, typically in the domain of pharmaceuticals. In this domain, the main
application of olefin metathesis should be the ring closing reaction.
(iii) In the domain of polymers, applications should be searched for in specialty
chemicals, probably in close contact with the other polymerization processes. As
alkylidene catalysts are often used, high turnover numbers should be needed.
5. References
1. Streck, R. (1990), in Y. Imamoglu, B. Ziimreoglu-Karan and A.1. Amass (eds.), Olefin Metathesis
and Polymerization Catalysts, NATO AS! Series Vol. 326, Kluwer Academic Publishers, Dordrecht,
pp. 439-455.
2. Streck, R. (1990), in Y. Imamoglu, B. Ziimreoglu-Karan and A.J. Amass (eds.), Olefin Metathesis
and Polymerization Catalysts, NATO AS! Series Vol. 326, Kluwer Academic Publishers, Dordrecht,
pp.457-488.
3. Streck, R. (1990), in Y. Imamoglu, B. Ziimreoglu-Karan and A.J. Amass (eds.), Olefin Metathesis
and Polymerization Catalysts, NATO AS! Series Vol. 326, Kluwer Academic Publishers, Dordrecht,
pp.489-515.
4. !vin, K.J. and Mol, J.e. (1997), Olefin Metathesis and Metathesis Polymerization, Academic Press,
San Diego.
5. Banks, RL. (1986), ChemTech 16,112.
6. Dall' Asta, G. and Mazzanti, G. (1963), Makromol. Chem. 61, 178.
7. Dall' Asta, G. (1968),1. Polym. Sci. A-i 6,2397.
8. Herisson, J.L. and Chauvin, Y. (1970), Makromol. Chem. 141, 161.
9. Peters, E.F. and Evering, B.L. (1958), US. pat. 2963471.
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