ASSAINMENT SUBJECT

ORGANIC CATALYST AND

CATALYSIS ASSAINMENT TOPIC
DIMERIZATION ,OLIGOMERIZATION OF OILIFINE
SUBMMITTED TO
DR. TAHIR MEHMOOD
SUBMITTED BY
M. BILAL AFZAL
ROLL NUMBER
7601/ 25816
CLASS
BS CHEMISTRY (8TH E1)
GOVT.POST GRADUATE COLLEGE SAMANABAD
FAISALABAD
DIMERIZATION
A dimer (/ˈdaɪmər/) (di-, "two" + -mer, "parts") is an oligomer consisting of two structurally
similar monomers joined by bonds that can be either strong or weak, covalent or intermolecular.
The term homodimer is used when the two molecules are identical and heterodimer when they
are not.

Introduction
The dimerization of ethylene is an important route for the selective production of butene-1. The
considerable interest in this field by academic institutions and industry is reflected by the large
number of patents and publications covering this subject during the last few years. However, the
stimulus in this direction was provided by the pioneering studies of Karl Ziegler in the early
1950’s. He explored the use of organoaluminum compounds in the selective dimerization of
alkenes. Ever since, workers in this area have investigated many novel catalytic systems based
on transition metal complexes. These complexes afford a new attractive mean of achieving high
selectivity to butene-1 by ethylene dimerization.

REACTION CHEMISTRY AND MECHANLSM

The dimerization of ethylene is governed by three essential features that influence the formation
of butene-1. These are: the degree of polymerization, the mode of linking ethylene molecules,
and the position of the double bond. The degree of polymerization or the number of ethylene
molecules forming the hydrocarbon chain depends on the frequency of chain transfer reactions
with respect to the propagation reaction. However, the predominance of chain transfer reactions
depends on the conditions of shifting hydrogen atoms in the hydrocarbon compounds. This
dominance is frequently achieved by increas- ing the reaction temperature in order to lower the
formation of high molecular weight polymers during the dimerization reaction. Another factor
that limits the degree of polymerization is the use of high concentration of ethylene during the
reaction (limiting conversion) in order to prevent any codimeriza- tion of the formed butene-1
and ethylene. This codimerization is due to the high affmity of butene-1 to the catalyst.
Another feature that influences the formation of butene-1 is the mode of linking the ethylene
molecules during dimerization, which depends on two fundamentally different steps, initiation
and propagation. The contribution of the initiation step to the microstructure is essential to the
formation of butene-1[171. The position of the double bond in the butenes product is reflected by
the ability of the catalyst to mobilize the hydrogen atoms during the dimerization reaction. It is
defined either in the initiation or transfer step or it results from a subsequent isomerization after
the formation of butene-1 1171. Actually, the insertion step is often the limiting step in defining
the position of the double bond C151. This is due to the fact that the active center of the catalyst
is incapable of accommodating two ethylene molecules simultaneously. However, if the
isomerization occurs, it can be kept at a minimum by increasing the concentration of ethylene in
the reaction medium, consequently limiting its conversion.
The cyclic intermediate mechanism is based on the formation of metalla- cyclopetane
intermediates that are converted to the olefin complex via 1, 3 hydrogen shift. Elimination of the
product olefin and coordination of ethylene lead to the formation of the bis (ethylene) complex
[2,15,191. The course of the reaction can be significantly influenced by the nature of the metal,
the ligand supplied, and the reaction conditions. The reaction cycle is complete when the
metallacyclopentane is regenerated. This reaction does not distinguish between the two possible
modes of addition of a metal-carbon or a metal- hydrogen bond to an unsymmetrically
substituted olefin. The direction of this addition is very important for obtaining linear or
branched products. Reaction mechanisms, based on the above two schemes, are presented under
each catalytic system as discussed in Section 1.4. However, some reaction mechanisms are not
fully established yet.

CATALYTIC SYSTEMS
A large variety of catalytic systems has been used to dimerize ethylene to butene-1. Different
compounds of nickel, palladium, titanium, rhodium,
zirconium, tantalum and cobalt together with (or without) various aluminum alkyls, containing or
not containing halogen atoms, and supported (or not supported) on carriers, were used as
catalysts. The homogeneous catalytic systems used in ethylene dimerization consist of active
metal, Lewis acid or co-catalyst, additive, and solvent. Catalysts used in the presence of a
reducing agent or Lewis acid are referred to as Ziegler-Natta catalysts . However, the commonly
used active catalysts are titanium and those of Group VIII transition elements, especially the first
two series of the Group, Fe, Co, Ni and Ru, Rh, and Pd . These elements are generally active
when bonded with less than two anions or reduced to a lower oxidation state by a variety of alkyl
derivatives of aluminum and other reducing agents. The co-catalyst is usually a Lewis acid that
enhances the dimerization rate and has a profound effect on the course of the reaction . It plays
the double role as a reducing agent and as an acceptor for halide ions that are responsible for the
dimerization reaction . Catalyst modifiers or additives such as phosphines are usually added to
the catalyst system to provide better selectivity for the reaction . The modifiers influence the
mode of linkage of ethylene molecules and inhibit the formation of high molecular weight
polymers. Solvents often play an important role in enhancing the dimerization rate and
promoting the catalytic activity because of their reducing power [ZOI. ParaEnie, cyclopara~nic,
olefinic, aromatic, and chlorinated hydrocarbons are used as solvents for the homogeneous
catalytic systems . In general, the reported different approaches for the activation of the
homogeneous catalytic systems ethylene dimerization can be summarized. Catalyst formation by
reaction of transition metal complexes with orgomelic compounds, such as AlR3, 2.
Complexation of transition metal complexes with a Lewis acid (X,AlR3. BF3, where X is a
halide and n=l-. Oxidation addition of inorganic or organic acids to transition metal complexes
forming hydride species, and 4. Use of alkyl or aryl transition metal complexes stabilized by
ligands with electron donor or acceptor properties. Several papers on ethylene dimerization used
heterogeneous catalytic systems with high activity , By anchoring the active catalysts complex to
polymeric, zeolitic or ordinary supports, the high selectivity of homogeneous catalytic systems
can be combined with the easy product separation of heterogeneous systems . There is a close
relationship between homogeneous and heterogeneous catalysts systems used in ethylene
dimerization; the support of the active site in the heterogeneous system plays the role of the
ligand on a coordinated metal atom in the homogeneous system . The changes in the nature of
the support drastically alter the behavior of an active site in the same way that the ligands in the
homogeneous catalysts modify the electronegativity and the polarizability of a metal atom, and
its reactivity . The catalytic systems (both homogeneous and heterogeneous) used in ethylene
dimerization are classified and presented according to the type of transition metal used. They are
discussed in terms of activity, reaction conditions, selectivity to , and reaction mechanisms.

Oligomerization
An oligomer is a molecular complex of chemicals that consists of a few monomer units, in
contrast to a polymer, where the number of monomers is, in principle, unlimited. ... Plasticizers
areoligomeric esters widely used to soften thermoplastics such as PVC.

Heterogeneous Catalysts for Olefin Metathesis:

The Production of Light Olefins One of the more difficult type of metathesis: No driving force
(such as release of ring strain), equilibrium, difficult to control the selectivity in acyclic olefins.
First industrial metathesis process was: Phillips Triolefin Process The process was operated at
Phillips Petroleum Co. from 1966 to 1972 near Montreal, Canada for the conversion of propene
into ethane and 2-butene:

Propene is produced from naphtha steam crackers (about 65 %) as a co-product with ethene and
as a coproduct in refineries for gasoline-making. Production of ca 15 kt/a ethylene and 30 kt/a
butene from 50 kt/a propylene was achieved over a WO3/ SiO2 catalyst (doped with Na to
decrease surface acidity and prevent double bond shift reactions) at temperature of around
400°C. However, the demand for propene (60 % is used for polypropene) has increased
dramatically since then. Small amounts are obtained from propane dehydrogenation and by coal
gasification via Fischer-Tropsch chemistry.

Olefin Conversion Technology (OCT)

An alternative route to propene is the metathesis of ethane and 2-butene, that is, the inverse
Phillips process: All metathesis reactions are thermoneutral → equilibrium:

First example: Lyondell Petrochemical Co, 1985. The plant can be fed by an ethane cracker that
produces ethene. Butene is generally obtained from the dimerization of ethene with a
homogeneous Ni-catalyst (see SHOP below). The hetereogeneous catalyst is either either is
[WO3] / SiO2 or [WO3] / MgO and operates at temperatures > 260°C and 30–35 bar. Pressure is
not necessary for the reaction, but both the ethane cracker and the downstream processes require
high pressures. 1-Butene in the feedstock is isomerized to 2-butene by the acid heterogeneous
catalyst New OCT plants: BASF FINA (300 kt/a) Mitsui Chemical (140 kt/a) Korea
Petrochemical Industry (110 kt/a).

Neohexene Process
Neohexene (3,3-dimethyl-1-butene) is an intermediate in the synthesis of Tonalide® (perfume)
and Terbinafine (antifungal). Operated since 1980. Production: 1.4 kt/a.
The process is based on the dimer of isobutene, which consists of a mixture of 2,4,4-trimethyl-2-
pentene and 2,4,4-trimethyl-1-pentene.

Cross-metathesis of the former with ethene gives neohexene:

2,4,4-Trimethyl-1-pentene is isomerized by using a dual catalyst, a 1:3 mixture of WO3 / SiO2
and MgO. The catalyst operates at 370°C and 30 bar and gives an average conversion of
diisobutene of 65–70% and a selectivity to neohexene of ca. 85%.

The Vestenamer Process

Since 1980, Degussa-Hüls has been producing the metathetical polymer of cyclooctene under the
commercial name of Vestenamer 8012, also known as TOR (trans-polyoctenamer). Vestenamer
is used as as a blending material to impart greater elasticity and durability to other rubbers (see
http:// www.degussa-hpp.com/ger/produkte/kautschuk/index.shtml). The catalyst is WCl6-based
in hexane as solvent.

Two polymer fractions: – high-molecular weight fraction (> 105 Da), true polymer
– low-molecular weight fraction (25 %), different cyclic
oligomers
Explanation: Competition between propagation and intramolecular backbiting metathesis:

Different commercial products depending on the trans isomer content (controlled by

polymerization conditions):
Vestenamer 8012 → 80% trans, high crystallinity, rigid
 Vestenamer 6013 → 60% trans, lower crystallinity, softer, suitable for lower
temperature applications.

.
Reference
https://en.wikipedia.org/wiki/Oligomer
file:///C:/Users/Umar%20Israr/Downloads/Documents/homcat4-
olefins-part2-metathesis.pdf
file:///C:/Users/Umar%20Israr/Downloads/Documents/Dimeriza
tion1992.pdf
https://www.researchgate.net/publication/244320502_Ethylene_
dimerization_and_oligomerization_to_butene-1_and_linear_a-
olefins_A_review_of_catalytic_systems_and_processes