FORM 2
THE PATENT ACT, 1970
(39 of 1970)
&
THE PATENTS RULES,2003
COMPLETE SPECIFICATION
(See section 10 and rule 13 )
1 . TITLE OF INVENTION
ORGANOMETALLIC
COMPOUND IN SOLID
FORM  PROCESS
FOR PREPARING THE
SAME AND USE THEREOF
2 . APPLICANT(S)
Name Nationality Address
Indian Oil
Corporation
Limited
MUMBAI
G-9 Ali Yavar
Jung Marg
Bandra (East)
Mumbai-400 051
India
3. PREAMBLE TO THE DESCRIPTION
COMPLETE
The following specification particularly describes the
invention and the manner in which it is to performed
4. DESCRIPTION (Description shall start from next page.)
FIELD OF INVENTION The present invention relates to a
catalyst system. More particularly, the present invention
relates to a solid organomagnesium precursor for the
catalyst system and process for preparing the same. The
present invention also provides a process for preparing a
catalyst system using the solid organomagnesium
precursor and its use thereof for polymerization of olefins.
BACKGROUND OF INVENTION Ziegler-Natta catalyst
systems are well known for their capability to polymerize
olefins. They in general consist of a support which mostly
is magnesium based onto which titanium component has
been added along with organic compound known as
internal donor. This catalyst when combined with cocatalyst
and/or external donor comprise of the complete
ZN catalyst system. Ziegler-Natta catalyst system typically
consists of transition metal halide normally titanium halide
supported on metal compound which is typically
magnesium dichloride. Along with transition metal, there is
an organic component known as internal electron donor
that plays a typical role during catalyst synthesis and
polymerization. MgCl2 carrier, where the MgCl2 is in active
form, can be created by various methodologies. One of the
methods is precipitating the MgCl2 from an organic
solution where magnesium is present as a soluble
compound. The soluble magnesium compound can be
achieved by starting from a magnesium alkyl and treating it
with an alcohol. This step is then followed by chlorination
of Mg alkyl or alkoxy compounds by a chlorination agent.
The magnesium carrier can also be precipitated in the form
of ‘ready-made’ MgCl2. In that case the MgCl2 has to be
dissolved first in some suitable donor compound and then
precipitated in hydrocarbon solvent. The MgCl2 support
material can also be precipitated by chlorinating a soluble
magnesium alkyl compound simply by treating it with
chlorine gas or hydrochloric acid. Once the desired
specification of carrier is obtained, this is generally
followed by titanation procedure which finally results in the
catalyst synthesis. US4220554 of Montedison describes
the process of synthesizing the catalyst by treating Ti
compounds with a spherical carrier which consists of Mg
compound having the formula XnMg(OR)2-n. XnMg(OR)2-
n is synthesized by in reacting, in a single step, Mg metal,
the organic halide and the orthosilicic acid ester. This
product is isolated and then treated with halide of aromatic
acid which is again isolated and treated with Ti compound
for formation of catalyst. This catalyst is evaluated for
propylene polymerization. This route applies the usage of
orthosilicic ester for generation of magnesium alkoxy
halide compound and focuses on the particle shape as well
as size of the catalyst. US4727051 of Stauffer Chemical
Company discloses the process for synthesis of
XnMg(OR)2-n by preparing an alkanol adduct of a
magnesium halide, reacting the product of this step with
metallic magnesium, and drying the product. The
compositions are then evaluated for as catalysts of olefin
polymerization. The main disadvantage of this process is
the usage of magnesium halides and large amount of
alcohols. US4820672 of Lithium Corporation of America
describes the process for producing magnesium halide
alcohol complex by reacting in an ether free hydrocarbon
reaction medium, magnesium metal, dialkyl magnesium,
alkyl magnesium halide, alkyl magnesium alkoxide,
magnesium dialkoxide and alkoxy magnesium halide with
an anhydrous hydrogen halide in the presence of
chlorosubstituted alcohol. Further this complex is used for
synthesis of ZN catalyst. The main disadvantage of this
process is a large number of steps are involved for
magnesium halide alcohol synthesis and further the usage
of hydrogen halide which is difficult to handle. US4820879
further describes the process where alkoxy magnesium
halides are formed by reacting preactivated magnesium
with alcohol at higher temperatures and then treating it with
hydrogen halides. Here also usage and handling of
hydrogen halide is quite troublesome. US4792640
discloses a process for synthesis of solid
hydrocarbyloxymagnesium halides which is ether free,
where preactivated (with iodine) magnesium metal is
reacted with alkyl halide for some time and then addition of
alcohol is done dropwise and finally refluxed. The solid
product is filtered, dried and analyzed. Here the Grignard is
stabilized in hydrocarbon. These patents contains no
information on the activity of the ZN catalyst synthesized
thereof. US5081320 of Akzo NV describes the synthesis
of alkoxymagnesium halides from secondary alcohol
containing alkyl branching on the alpha carbon atom which
is soluble in inert hydrocarbon. The process involves
heating inert hydrocarbon solvent, secondary alcohol and
ethanol with magnesium halide (MgCl2) to dissolve the
magnesium halide. Magnesium metal is then added along
with additional solvent to prepare a soluble
alkoxymagnesium halide. One disadvantage of this
process is one need to prepare soluble magnesium
alkoxide in order to further react the magnesium metal.
US5108972 discloses the process of synthesis of
alkoxymagnesium halide using non Grignard route where
they react magnesium halide and magnesium alkoxide in
excess of alcohol. Further magnesium source can also be
added which is generated through dialkylmagnesium in
hydrocarbon. Main disadvantage of this process is usage
of expensive raw materials and large number of steps. The
patent describes the process of synthesizing the
magnesium compounds only. US5414158 of Witco GmbH
describes the one step synthesis of alkoxymagnesium
halides in an inert hydrocarbon by reacting preactivated
magnesium with small quantities of magnesium alkyl, with
almost equimolar mixture of an alkyl halide and an alkanol.
The obtained product is in excess of 90%. In this process
first magnesium needs to be activated with magnesium
alkyl at high temperature and then addition is carried out
dropwise to the alkylhalide and alkanol mixture. One
disadvantage of this process is requirement of expensive
magnesium alkyl for activation which is also difficult to
handle and further the extra addition of alkanol after the
reaction to reduce viscosity. This patent describes the
synthesis of alkoxymagnesium halide only and doesn’t
state the usage of the same as precursor for ZN catalyst.
EP1273595 of Borealis describes the process for synthesis
of catalyst by reacting dialkylmagnesium with monohydric
alcohol followed by dicarboxylic acid dihalide and
chlorinated hydrocarbons. After washing and isolation of
this product, it is further treated with titanium compound for
the formation of ZN catalyst which shows activity for
propylene polymerization. The main disadvantage of this
process is usage of expensive dialkylmagnesium and its
handling. This patent is mainly on the usage of emulsion
stabilizer for controlling the particle size and shape.
US7135531 of BASF discloses the process for the
synthesis of spherical catalyst which essentially contains
titanium, internal donor and a support made from a
magnesium compound, an alcohol, ether, a surfactant, and
an alkyl silicate. The magnesium compound mainly
magnesium dichloride is dissolve in alcohol at higher
temperature and then treated with ether at lower
temperature followed by addition of emulsifier at still lower
temperature. This is then treated with silicate and titanium
compound and final catalyst is ready after washing and
drying. The main disadvantage of this process is higher
alcohol content and expensive raw materials.
US2009/0306315 of SABIC discloses the process for
preparing a polymerization catalyst which is synthesized by
reacting Mg (OR1) xCl2-x, which is obtained by reacting a
Grignard compound with an alkoxy or aryloxy silane
compound, with electron donor in the presence of inert
dispersant to give an intermediate reaction product which
is then treated with titanium halide to give the final catalyst
which shows activity for olefin polymerization. This process
has main disadvantage that its involves large number of
steps which mainly consists of first solubilizing the
magnesium compound and then solidifying before making
final catalyst. Thus, it would be desirable to provide a solid
organometallic precursor compound for synthesis of a
catalyst for polymerization of olefins that could be
synthesized through a single step process using less
expensive raw materials and lower alcohol content.
Further, it would be desirable if the organometallic
compound could be isolated, without any further
purification and used as a precursor for making olefin
polymerization catalyst which is highly active with low
xylene solubility and excellent hydrogen response.
SUMMARY OF INVENTION Accordingly the present
invention provides a process for preparation of a solid
organomagnesium precursor having formula
{Mg(OR’)X}.a{MgX2}.b{Mg(OR’)2}.c{R’OH}, wherein R’ is
selected from a hydrocarbon group, X is selected from a
halide group, and a:b:c is in range of 0.01-0.5 : 0.01 – 0.5 :
0.01 - 5, said process comprising contacting a magnesium
source with a solvating agent, an organohalide and an
alcohol to obtain the solid organomagnesium precursor.
The present invention also provides a process for
preparation of a catalyst composition, said process
comprises: (a)contacting a solution of transition metal
compound represented by M(OR’”)pX4-p, where M is a
transition metal and selected from Ti, V, Zr, and Hf; X is a
halogen atom; R’’’ is a hydrocarbon group and p is an
integer having value equal or less than 4 and where M is
preferably titanium with the solid organomagnesium
precursor having formula
{Mg(OR’)X}.a{MgX2}.b{Mg(OR’)2}.c{R’OH}, wherein R’ is
selected from a hydrocarbon group, X is selected from a
halide group, and a:b:c is in range of 0.01-0.5 : 0.01 – 0.5 :
0.01 – 5, to obtain the resulting solution and contact
temperature of the solid organomagnesium precursor and
the transition metal compound is between about -50°C and
about 150°C, and preferably between about -30°C and
about 120°C; (b)adding an internal donor either to the
organomagnesium precursor component or to the titanium
component and the contact time of the said component
with the internal electron donor is either immediate or at
least 1 minutes to 60 minutes at contact temperature of
between about -50°C and about 100°C, and preferably
between about -30°C and about 90°C; (c)treating the
resulting solution obtained in the step (a) with a solution
comprising a neat titanium component or a titanium
component in a solvent and recovering a solid titanium
catalyst component and maintaining the same at a
temperature value in the range of 100 to 120oC for about
10 to 60 minutes; and (d)optionally repeating step (c) for a
predetermined number of times and then washed
sufficiently with inert solvent at temperature 20ºC to 90ºC
to obtain a solid catalysts composition. The present
invention also provides a process for preparation of a
Ziegler-Natta catalyst system, said process comprising
contacting the catalyst composition as obtained above with
at least one cocatalyst, and at least one external electron
donor to obtain a Ziegler-Natta catalyst system. The
present invention also provides a method of polymerizing
and/or copolymerizing olefins, said method comprising the
step of contacting an olefin having C2 to C20 carbon
atoms under a polymerizing condition with the Ziegler-
Natta catalyst system as obtained above. BRIEF
DESCRIPTION OF DRAWING Figure 1 illustrates NMR
spectra for the compound
{Mg(OR’)X}.a{MgX2}.b{Mg(OR’)2}.c{R’OH}. DETAILED
DESCRIPTION OF INVENTION While the invention is
susceptible to various modifications and alternative forms,
specific embodiment thereof will be described in detail
below. It should be understood, however that it is not
intended to limit the invention to the particular forms
disclosed, but on the contrary, the invention is to cover all
modifications, equivalents, and alternative falling within the
scope of the invention as defined by the appended claims.
The present invention discloses solid organometallic
compound and a process of preparation of the solid
organomagnesium compound. Further according to the
present invention the organomagnesium compound acts
as a precursor for Ziegler-Natta catalyst system and there
is provided a process for synthesis of the catalyst system
using the precursor thereof. Catalyst compositions and
systems synthesized from organomagnesium compounds
are able to polymerize olefins. The solid organomagnesium
compound according to the present invention provides
precursor based catalyst system has high activity,
excellent hydrogen response, high selectivity and better co
-monomer distribution. According to the present invention,
the solid organomagnesium compound is prepared by a
single step process first by generating Grignard reagent
followed by reacting with an alcohol. The isolated solid
organomagnesium compound when contacted with metal
compound M where M can be selected from Ti,V, Zr, Hf
and along with the internal electron donors provide the
catalyst system. The solid organomagnesium compound
synthesis according to the present invention is achieved
with reduced alcohol content without any further
purification step. This catalyst system comprising of the
said component have high activity for olefin polymerization
with excellent hydrogen response and high
stereospecificity. Further, the present invention relates to
the synthesis of Ziegler-Natta catalysts by using solid
organomagnesium compound as a precursor. The Ziegler-
Natta catalyst according to the present invention is
prepared through precipitation, physical blending of solid
mixtures, and in situ formation of halogenating agents. The
resulting catalyst exhibits high activity for olefin
polymerization with excellent hydrogen response. Further,
the invention provides a process of polymerizing and/or
copolymerizing the olefin using the catalyst produced
through the process mentioned in the invention.
Accordingly the present invention provides a process for
preparation of a solid organomagnesium precursor having
formula {Mg(OR’)X}.a{MgX2}.b{Mg(OR’)2}.c{R’OH},
wherein R’ is selected from a hydrocarbon group, X is
selected from a halide group, and a:b:c is in range of 0.01-
0.5 : 0.01 – 0.5 : 0.01 - 5, said process comprising
contacting a magnesium source with a solvating agent, an
organohalide and an alcohol to obtain the solid
organomagnesium precursor. In one of the preferred
embodiment, a solid organomagnesium precursor having
formula {Mg(OR’)X}.a{MgX2}.b{Mg(OR’)2}.c{R’OH}, can be
prepared as shown in below scheme 1: wherein, Mg –
Magnesium Metal RX – Alkyl Halide RMgX – Grignard
Reagent *Intermediates R’OH- Alcohol Ratio of a:b:c is in
range of 0.01-0.5 : 0.01 – 0.5 : 0.01 - 5 R and R’ is
selected from a hydrocarbon groups; X is halogen
selected from Cl, Br or I n is an integer having value 1 - 10
According to the present invention, the process involves
contacting magnesium source with organohalide
compound and solvating agent for particular time and at
particular temperature followed by reacting with alcohol.
The magnesium source used in the present invention
includes, not limited to, for example magnesium metal in
form of powder, granules, ribbon, turnings, wire, blocks,
lumps, chips; dialkylmagnesium compounds such as
dimethylmagnesium, diethylmagnesium,
diisopropylmagnesium, dibutylmagnesium,
dihexylmagnesium, dioctylmagnesium,
ethylbutylmagnesium, and butyloctylmagnesium; alkyl/aryl
magnesium halides such as methylmagnesium chloride,
ethylmagnesium chloride, isopropylmagnesium chloride,
isobutylmagnesium chloride, tert-butylmagnesium chloride,
benzylmagnesium chloride, methylmagnesium bromide,
ethylmagnesium bromide, isopropylmagnesium bromide,
isobutylmagnesium bromide, tert-butylmagnesium
bromide, hexylmagnesium bromide, benzylmagnesium
bromide, methylmagnesium iodide, ethylmagnesium
iodide, isopropylmagnesium iodide, isobutylmagnesium
iodide, tert-butylmagnesium iodide, and benzylmagnesium
iodide. These magnesium compounds may be in the liquid
or solid state. The magnesium compound is preferably
magnesium metal. In an embodiment of the present
invention, the organohalide which is contacted with
magnesium compound, includes, not limited to, for
example alkyl halides such as methyl chloride, ethyl
chloride, propyl chloride, isopropyl chloride, 1,1-
dichloropropane, 1,2-dichloropropane, 1,3-
dichloropropane, 2,3-dichloropropane, butyl chloride, 1,4-
dichlorobutane, tert-butylchloride, amylchloride, tertamylchloride,
2-chloropentane, 3-chloropentane, 1,5-
dichloropentane, 1-chloro-8-iodoctane, 1-chloro-6-
cyanohexane, cyclopentylchloride, cyclohexylchloride,
chlorinated dodecane, chlorinated tetradecane, chlorinated
eicosane, chlorinated pentacosane, chlorinated
triacontane, iso-octylchloride, 5-chloro-5-methyl decane, 9-
chloro-9-ethyl-6-methyl eiscosane; halognetaed alkyl
benzene/ benzylic halides, such as benzyl chloride and a,a'
dichloro xylene; wherein the alkyl radical contains from
about 10 to 15 carbon atoms, and the like as well as the
corresponding bromine, fluorine and iodine substituted
hydrocarbons. These organohalides may be used alone or
in the form of mixture thereof. The organohalide is
preferably benzyl chloride or butyl chloride or their mixtures
thereof. In an embodiment of the present invention, the
solvating agent which stabilizes the Grignard, includes,
not limited to, for example dimethyl ether, diethyl ether,
dipropyl ether, diisopropyl ether, ethylmethyl ether, nbutylmethyl
ether, n-butylethyl ether, di-n-butyl ether, diisobutyl
ether, isobutylmethyl ether, and isobutylethyl ether
and the like. Also polar solvents, including but not limited
to, dioxane, tetrahydrofuran, 2-methyl tetrahydrofuran,
tetrahydropyran, chlorobenzene, dichloromethane and the
like. Also non-polar solvents like toluene, heptane,
hexane, and the like. These solvating agents may be used
alone or in the form of mixture thereof. The preferred
solvating agent is diethyl ether or tetrahydrofuran or their
mixture. In an embodiment of the present invention, the
components may be added in any order, highly preferably,
magnesium followed by solvating agent, organohalide, and
alcohol. In an embodiment of the present invention, the
reaction process can be done as single step such as
reacting the components in one pot or multiple steps such
as reacting magnesium, organic halide and solvating agent
first and then addition of alcohol or reacting magnesium
with solvating agent followed by addition of organic halide
and alcohol, separately or as a mixture. The quantity of
organohalide depends upon the quantity of magnesium
source used. According to the preferred embodiment, the
magnesium source is reacted with the said organohalide in
a molar ratio of between 1:20 to 1:0.2, preferably between
about 1:10 to 1:0.5, more preferably, between 1:4 to 1:0.5.
In another embodiment, the magnesium source and
solvating agent are taken as molar ratio of between 1:20 to
1:0.2, preferably between about 1:15 to 1:1, more
preferably, between 1:10 to 1:1. Another embodiment of
the present invention, formation of homogeneous solution
of magnesium component in solvating agent such as ether
is desirable. For attaining this, the magnesium source,
organohalide, solvating agent are contacted at temperature
preferably between about -20°C and about 200°C, and
preferably between about -10°C and about 140°C, more
preferably between -10°C to 100°C. Usually, the contact
time is for about 0.5 to 12 h. In an embodiment of the
present invention, reaction promoters like iodine, the
organohalides, inorganic halides such as CuCl, MnCl2,
AgCl, nitrogen halides like N-halide succinimides,
trihaloisocynauric acid acompounds, N-halophthalimide
and hydrantoin compounds. In an embodiment, the
alcohol contacted includes, no limited to, for example,
aliphatic alcohols such as methanol, ethanol, propanol,
butanol, iso-butanol, t-butanol, n-pentanol, iso-pentanol,
hexanol , 2-methylpentanol, 2-ethylbutanol, n-heptanol, noctanol,
2-ethylhexanol, decanol and dodecanol, alicyclic
alcohols such as cyclohexanol and methylcyclohexanol,
aromatic alcohols such as benzyl alcohol and methylbenzyl
alcohol, aliphatic alcohols containing an alkoxy group, such
as ethyl glycol, butyl glycol; diols such as catechol,
ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-
pentanediol, 1,8-octanediol, 1,2-propanediol, 1,2-
butanediol, 2,3-butanediol 1,3-butanediol, 1,2-pentanediol,
p-menthane-3,8-diol, 2-methyl-2,4-pentanediol. The
alcohols may be used alone or in the form of mixture
thereof. The preferred alcohol is 2-ethyl-1-hexanol and its
mixture thereof. The quantity of alcohol depends upon the
quantity of magnesium compound used. According to the
preferred embodiment, the magnesium source along with
organohalide is reacted with the said alcohol in a molar
ratio of between 1:20 to 1:0.2, preferably between about
1:10 to 1:0.5, more preferably, between 1:4 to 1:0.5. In
another embodiment of the present invention, formation of
homogeneous solution of magnesium component in
alcohol is desirable. For attaining this, the solution
obtained by reacting magnesium compound, organohalide,
in solvating agent is contacted with alcohol compound at
temperature preferably between about 0°C and about
150°C, and more preferably between about 10°C and
about 120°C. The preferred contact time according to the
invention, is for about 0.5 to 12 h. The present invention
provides the process of preparation of stable solid
organomagnesium compound. In an embodiment, the
process involves contacting magnesium compound with
organohalide compound and solvating agent for particular
time and at particular temperature followed by reacting with
alcohol. In an embodiment, the addition of organohalide,
solvating agent and alcohol can be one shot, dropwise
and/or controlled. In an embodiment, the resulting stable
solid organomagnesium precursor solution can be isolated
from solvating agent either using reduced pressure with
and/or without heating, through precipitation,
recrystallization. In another embodiment, the precipitated
solid can be either used directly or in solution form for
catalyst synthesis where in the solvent used for dissolving
solid can be from the following group but not limited to
polar and non polar aliphatic and/or aromatic
hydrocarbons and combination thereof. The present
invention provides the process of preparation of stable
solid organomagnesium compound. In an embodiment, the
process involves contacting magnesium compound with
organohalide compound and solvating agent for particular
time and at particular temperature followed by reacting with
alcohol. In an embodiment, the resulting
organomagnesium compound can be dissolved in polar
organic solvents and precipitated in organic solvents for
examples not limiting to linear, branched, aromatic, cyclic,
ring substituted, halide substituted alkanes and the likes,
preferably non polar organic solvents or vice versa. In
another embodiment, the precipitation methodology can be
adopted during any stage of precursor synthesis for
example but not limiting to, reacting magnesium with
organic halide in solvating agent followed by precipitation
in the mixture of alcohol and precipitating solvent or vice
versa, or reacting magnesium with organic halide in
solvating agent followed by addition of alcohol and then
precipitating in precipitating solvent or vice versa. Further,
the present invention provides a catalyst composition. The
catalyst composition includes combination of a magnesium
moiety, other metal moiety and an internal donor. The
magnesium moiety includes the stable solid
organomagnesium compound of the present invention. The
other metal moiety can be a main group metal or a
transition metal, or a transition metal of IIIB - VIIIB element.
In an embodiment, the transition metal is selected from, Ti,
V, Zr, , and Hf, preferably, Ti. In one of the embodiment,
the present invention provides a process for preparation of
a catalyst composition, said process comprises:
(a)contacting a solution of transition metal compound
represented by M(OR’)pX4-p, where M is a transition metal
and is selected from a group comprising of Ti, V, Zr, and
Hf, preferably Ti; X is a halogen atom; R’’’ is a hydrocarbon
group and p is an integer having value equal or less than
4, with the solid organomagnesium precursor component
of present invention to obtain a resulting solution and
contact temperature of solid organomagnesium precursor
and the transition metal compound is between about -50°C
and about 150°C, and preferably between about -30°C and
about 120°C; (b)adding an internal donor either to the solid
organomagnesium precursor component or to the titanium
component, preferably to organomagnesium compound;
and the contact time of the said component with the
internal electron donor immediate or is at least 1 minutes
to 60 minutes at contact temperature of between about -
50°C and about 100°C, and preferably between about -
30°C and about 90°C; (c)treating the resulting solution
obtained in the step (a) with a solution comprising a
titanium component in a solvent and recovering a solid
titanium catalyst component and maintaining the same at a
temperature value in the range of 100 to 120oC for about
10 to 60 minutes; and (d)optionally repeating step (c) for a
predetermined number of times and then washed
sufficiently with inert solvent at temperature 20ºC to 80ºC
to obtain a solid catalysts composition. In yet another
embodiment of the present invention, the transition metal
compound represented by M(OR’’’)pX4-p is selected from
a group comprising of transition metal tetrahalide, alkoxy
transition metal trihalide/aryloxy transition metal trihalide,
dialkoxy transition metal dihalide, trialkoxy transition metal
monohalide, tetraalkoxy transition metal, and mixtures
thereof; wherein: (a)the transition metal tetrahalide is
selected from a group comprising of titanium tetrachloride,
titanium tetrabromide and titanium tetraiodide and the likes
for V, Zr and Hf; (b)alkoxy transition metal trihalide/aryloxy
transition metal trihalide is selected from a group
comprising of methoxytitanium trichloride, ethoxytitanium
trichloride, butoxytitanium trichloride and phenoxytitanium
trichloride and the likes for V, Zr and Hf; (c)dialkoxy
transition metal dihalide is diethoxy titanium dichloride and
the likes for V, Zr and Hf; (d)trialkoxy transition metal
monohalide is triethoxy titanium chloride and the likes for
V, Zr and Hf; and (e)tetraalkoxy transition metal is
selected from a group comprising of tetrabutoxy titanium
and tetraethoxy titanium and the likes for V, Zr and Hf.
The present invention also provides a process for
preparation of a Ziegler-Natta catalyst system, said
process comprising contacting the catalyst composition as
obtained above with at least one cocatalyst, and at least
one external electron donor to obtain a Ziegler-Natta
catalyst system. The present invention also provides a
method of polymerizing and/or copolymerizing olefins, said
method comprising the step of contacting an olefin having
C2 to C20 carbon atoms under a polymerizing condition
with the Ziegler-Natta catalyst system as obtained above.
The present invention provides the catalyst composition
which includes combination of magnesium moiety, titanium
moiety and an internal donor. The magnesium moiety
includes the stable solid organomagnesium compound of
the present invention. In an embodiment, the invention
provides the method of synthesis of olefin polymerizing
catalyst, comprising of reacting the organomagnesium
compound with liquid titanium compound which includes
tetravalent titanium compound represented as Ti (OR)pX4-
p where X can be halogen selected from Cl or Br or I, R is
a hydrocarbon group and p is an integer varying from 0-4.
Specific examples of the titanium compound include, not
limited to titanium tetrahalides such as titanium
tetrachloride, titanium tetrabromide, titanium tetraiodide;
alkoxytitanium trihalide/aryloxytitanium trihalide such as
methoxytitanium trichloride, ethoxytitanium trichloride,
butoxytitanium trichloride, phenoxytitanium trichloride;
dialkoxy titanium dihalides such as diethoxy titanium
dichloride; trialkoxytitanium monohalide such as triethoxy
titanium chloride; and tetraalkoxytitanium such as
tetrabutoxy titanium, tetraethoxy titanium, and mixtures
thereof, with titanium tetrachloride being preferred. The
titanium compounds may be used alone or in the form of
mixture thereof. According to the present invention, the
magnesium moiety includes the stable solid
organomagnesium compound. In an embodiment, the
contact of organomagnesium compound with titanium
compound can be either neat or in solvent which can be
chlorinated or non chlorinated aromatic or aliphatic in
nature examples not limiting to benzene, decane,
kerosene, ethyl benzene, chlorobenzene, dichlorobenzene,
toluene, o-chlorotoluene, xylene, dichloromethane,
chloroform, cyclohexane and the like, comprising from 5 to
95 volume percent. In another embodiment, the stable
solid organomagnesium compound can be used as solid or
in solvent which can be chlorinated or non chlorinated
aromatic or aliphatic in nature examples not limiting to
benzene, decane, kerosene, ethyl benzene,
chlorobenzene, dichlorobenzene, toluene, o-chlorotoluene,
xylene, dichloromethane, chloroform, cyclohexane and the
like, comprising from 5 to 95 volume percent. In an
embodiment, either the titanium compound is added to the
organomagnesium compound or vice-verse, preferably,
organomagnesium compound is added to titanium
compound. In another embodiment, this addition is either
one shot or dropwise or controlled. In another embodiment,
the contact temperature of organomagnesium and titanium
compound is preferably between about -50°C and about
150°C, and more preferably between about -30°C and
about 120°C. The liquid titanium compound helps in the
formation of amorphous MgCl2 as it acts as halogenating
agent as well as is dispersed and supported on the catalyst
surface. Moreover, the removal of alkoxy group from the
solution, results in the precipitation of the solid component,
having especially desired surface properties and particle
shape. More important, the particles are uniform in shape.
In an embodiment, the titanium compound is added in
amounts ranging from usually about at least 1 to 200
moles, preferably, 3 to 200 moles and more preferably, 5
mole to 100 moles, with respect to one mole of
magnesium. While preparing the catalyst composition,
magnesium component is contacted with the titanium
component along with the internal donor to get the solid
titanium component. In one embodiment, magnesium and
titanium component can be made to come in contact with
the internal electron donor. In another embodiment, the
solid titanium catalyst component is made by contacting a
magnesium compound and a titanium compound in the
presence of an internal electron donor compound. In still
another embodiment, the solid titanium catalyst component
is made by forming a magnesium based catalyst support
optionally with the titanium compound and optionally with
the internal electron donor compound, and contacting the
magnesium based catalyst support with the titanium
compound and the internal electron donor compound. The
present invention provides the catalyst composition which
includes combination of magnesium moiety, titanium
moiety and an internal donor. The magnesium moiety
includes the stable solid organomagnesium compound. In
an embodiment, internal electron donor is selected from
phthalates, benzoates, diethers, succinates, malonates,
carbonates, and combinations thereof. Specific examples
include, but are not limited to di-n-butyl phthalate, di-i-butyl
phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dii
octyl phthalate, di-n-nonyl phthalate, methyl benzoate,
ethyl benzoate, propyl benzoate, phenyl benzoate,
cyclohexyl benzoate, methyl toluate, ethyl toluate, pethoxy
ethyl benzoate, p-isopropoxy ethyl benzoate,
diethyl succinate, di-propyl succinate, diisopropyl
succinate, dibutyl succinate, diisobutyl succinate, diethyl
malonate, diethyl ethylmalonate, diethyl propyl malonate,
diethyl isopropylmalonate, diethyl butylmalonate, diethyl
1,2-cyclohexanedicarboxylate, di-2-ethyIhexyl 1,2-
cyclohexanedicarboxylate, di-2- isononyl 1,2-
cyclohexanedicarboxylate, methyl anisate, ethyl anisate
and diether compounds such as 9,9-
bis(methoxymethyl)fluorene, 2-isopropyl-2-isopentyl-1,3-
dimethoxypropane, 2,2-diisobutyl-l,3-dimethoxypropane,
2,2-diisopentyl-l,3- dimethoxypropane, 2-isopropyl-2-
cyclohexyl- 1 ,3-dimethoxypropane, preferably di-iso-butyl
phthalate. The “internal electron donor” is a compound
that is added during the formation of catalyst composition
where it is acting as Lewis base i.e. donating the electron
pairs to the metal present in the catalyst composition. The
internal electron donor stabilizes the primary crystallites of
magnesium dihalide which is generated in-situ. Apart from
this, the internal donor also being better Lewis base have
preferred coordination with the higher acidity coordination
sites on magnesium dihalide matrix which in turn avoid the
coordination of titanium and hence prevents the formation
of inactive sites. They also increase the activity of low
active sites. This in all enhances the catalyst
stereoselectivity. All internal electron donor compounds
commonly used in the art can be used in the present
invention. In another embodiment, the internal electron
donor is used in an amount of from 0 to 1 moles, preferably
from 0.01 to 0.5 moles, with respect to one mole of
magnesium. The present invention provides the catalyst
composition which includes combination of magnesium
moiety, titanium moiety and an internal donor. The
magnesium moiety includes the solid organomagnesium
compound. In an embodiment, the addition of internal is
either to the organomagnesium compound or to the
titanium component, preferably to organomagnesium
compound. The contact temperature of internal donor
depends upon to which component it is being added. In an
embodiment, the contact time of the desired component
with the internal electron donor is either immediate or at
least 1 minutes to 60 minutes at contact temperature of
preferably between about -50°C and about 100°C, and
more preferably between about -30°C and about 90°C. in
another embodiment, the internal donor may be added in
single step or in multiple steps. The contact procedure for
titanium and magnesium component is slowly with
dropwise addition at desired temperature and then heated
to activate the reaction between both the components. In
a preferred embodiment, this reaction system is gradually
heated to the temperature effective to carry out the
reaction, preferably about -50?C and about 150?C, and
more preferably about -30?C and about 120?C, and
heating is instigated at a rate of 0.1 to 10.0?C/minute, or at
a rate of 1 to 5.0?C/minute. The resultant is the solid
component in the solvent comprising of magnesium,
titanium and halogen components. The procedure of
contacting the titanium component may be repeated one,
two, three or more times as desired. In an embodiment, the
resulting solid material recovered from the mixture can be
contacted one or more times with the mixture of liquid
titanium component in solvent for at least 10 minutes up to
60 minutes, at temperature from about 25°C to about
150°C, preferably from about 30°C to about 110°C. The
resulting solid component comprising of magnesium,
titanium, halogen, alcohol and the internal electron donor
can be separated from the reaction mixture either by
filtration or decantation and finally washed with inert
solvent to remove unreacted titanium component and other
side products. Usually, the resultant solid material is
washed one or more times with inert solvent which is
typically a hydrocarbon including, not limiting to aliphatic
hydrocarbon like isopentane, isooctane, hexane, pentane
or isohexane. In an embodiment, the resulting solid
mixture is washed one or more times with inert
hydrocarbon based solvent preferably, hexane at
temperature from about 20°C to about 80°C, preferably
from about 25°C to about 70°C. The solid catalyst can be
separated and dried or slurried in a hydrocarbon
specifically heavy hydrocarbon such as mineral oil for
further storage or use. In an embodiment, the catalyst
composition includes from about 2.0 wt % to 20 wt % of
internal electron donor, titanium is from about 0.5 wt % to
10.0 wt% and magnesium is from about 10 wt% to 20 wt
%. The present invention provides the catalyst system for
polymerization of olefins. In the embodiment, the method
of polymerization process is provided where the catalyst
system is contacted with olefin under polymerization
conditions. The catalyst system includes catalyst
composition, organoaluminum compounds and external
electron donors. The catalyst composition includes
combination of magnesium moiety, titanium moiety and an
internal donor. The magnesium moiety includes the stable
solid organomagnesium compound. Further, the present
invention provides a method of polymerizing and/or
copolymerizing olefins where the catalyst system is
contacted with olefin under polymerization conditions. The
catalyst system includes catalyst composition, cocatalyst
and external electron donors. The catalyst composition
includes combination of magnesium moiety, titanium
moiety and an internal donor. The magnesium moiety
includes the stable solid organomagnesium compound.
The co-catalyst may include hydrides, organoaluminum,
lithium, zinc, tin, cadmium, beryllium, magnesium, and
combinations thereof. In an embodiment, the preferred cocatalyst
is organoaluminum compounds. In another
embodiment the catalyst system includes catalyst
composition, organoaluminum compounds and external
electron donors. The catalyst composition includes
combination of magnesium moiety, titanium moiety and an
internal donor. The magnesium moiety includes the stable
solid organomagnesium compound. The olefins according
to the present invention includes from C2-C20. The ratio of
titanium (from catalyst composition): aluminum (from
organoaluminum compound): external donor can be from
1: 5-1000:0-250, preferably in the range from 1:25-500:25-
100. The present invention provides the catalyst system.
The catalyst system includes catalyst component,
organoaluminum compounds and external electron donors.
In an embodiment, the organoaluminum compounds
include, not limiting, alkylaluminums such as
trialkylaluminum such as preferably triethylaluminum,
triisopropylaluminum, triisobutylaluminum, tri-nbutylaluminum,
tri-n- hexylaluminum, tri-n-octylaluminum;
trialkenylaluminums such as triisoprenyl aluminum;
dialkylaluminum halides such as diethylaluminum chloride,
dibutylaluminum chloride, diisobutylaluminum chloride and
diethyl aluminum bromide; alkylaluminum sesquihalides
such as ethylaluminum sesquichloride, butylaluminum
sesquichloride and ethylaluminum sesquibromide;
dialkylaluminum hydrides such as diethylaluminum hydride
and dibutylaluminum hydride; partially hydrogenated
alkylaluminum such as ethylaluminum dihydride and
propylaluminum dihydride and aluminoxane such as
methylaluminoxane, isobutylaluminoxane,
tetraethylaluminoxane and tetraisobutylaluminoxane;
diethylaluminum ethoxide. The mole ratio of aluminum to
titanium is from about 5:1 to about 1000:1 or from about
10:1 to about 700:1, or from about 25:1 to about 500:1.
The present invention provides the catalyst system. The
catalyst system includes catalyst component,
organoaluminum compounds and external electron donors.
The external electron donors are organosilicon
compounds, diethers and alkoxy benzoates. The external
electron donor for olefin polymerization when added to the
catalytic system as a part of co-catalyst retains the
stereospecificity of the active sites, convert nonstereospecific
sites to stereospecific sites, poisons the non
-stereospecific sites and also controls the molecular weight
distributions while retaining high performance with respect
to catalytic activity. The external electron donors which are
generally organosilicon compounds includes but are not
limited to trimethylmethoxysilane, trimethylethoxysilane,
dimethyldimethoxysilane, dimethyldiethoxysilane,
diisopropyldimethoxysilane, diisobutyldimethoxysilane, tbutylmethyldimethoxysilane,
t-butylmethyldiethoxysilane, tamylmethyldiethoxysilane,
dicyclopentyldimethoxysilane,
diphenyldimethoxysilane, phenylmethyldimethoxysilane,
diphenyldiethoxysilane, bis-o-tolydimethoxysilane, bis-mtolydimethoxysilane,
bis-p-tolydimethoxysilane, bis-ptolydiethoxysilane,
bisethylphenyldimethoxysilane,
dicyclohexyldimethoxysilane,
cyclohexylmethyldimethoxysilane,
cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane,
ethyltriethoxysilane, vinyltrimethoxysilane,
methyltrimethoxysilane, n-propyltriethoxysilane,
decyltrimethoxysilane, decyltriethoxysilane,
phenyltrimethoxysilane, gammachloropropyltrimethoxysilane,
methyltriethoxysilane,
ethyltriethoxysilane, vinyltriethoxysilane, tbutyltriethoxysilane,
n-butyltriethoxysilane, isobutyltriethoxysilane,
phenyltriethoxysilane, gammaaminopropyltriethoxysilane,
cholotriethoxysilane,
ethyltriisopropoxysilane, vinyltirbutoxysilane,
cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-
norbornanetrimethoxysilane, 2-norbornanetriethoxysilane,
2-norbornanemethyldimethoxysilane, ethyl silicate, butyl
silicate, trimethylphenoxysilane, and
methyltriallyloxysilane, cyclopropyltrimethoxysilane,
cyclobutyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-
methylcyclopentyltrimethoxysilane, 2,3-
dimethylcyclopentyltrimethoxysilane, 2,5-
dimethylcyclopentyltrimethoxysilane,cyclopentyltriethoxysil
ane, cyclopentenyltrimethoxysilane, 3-
cyclopentenyltrimethoxysilane, 2,4-
cyclopentadienyltrimethoxysilane, indenyltrimethoxysilane
and fluorenyltrimethoxysilane; dialkoxysilanes such as
dicyclopentyldimethoxysilane, bis(2-
methylcyclopentyl)dimethoxysilane, bis(3-tertiary
butylcyclopentyl)dimethoxysilane, bis(2,3-
dimethylcyclopentyl)dimethoxysilane, bis(2,5-
dimethylcyclopentyl)dimethoxysilane,
dicyclopentyldiethoxysilane, dicyclobutyldiethoxysilane,
cyclopropylcyclobutyldiethoxysilane,
dicyclopentenyldimethoxysilane, di(3-
cyclopentenyl)dimethoxysilane, bis(2,5-dimethyl-3-
cyclopentenyl)dimethoxysilane, di-2,4-
cyclopentadienyl)dimethoxysilane, bis(2,5-dimethyl-2,4-
cyclopentadienyl)dimethoxysilane, bis(1-methyl-1-
cyclopentylethyl)dimethoxysilane,
cyclopentylcyclopentenyldimethoxysilane,
cyclopentylcyclopentadienyldimethoxysilane,
diindenyldimethoxysilane, bis(1,3-dimethyl-2-
indenyl)dimethoxysilane,
cyclopentadienylindenyldimethoxysilane,
difluorenyldimethoxysilane,
cyclopentylfluorenyldimethoxysilane and
indenylfiuorenyldimethoxysilane; monoalkoxysilanes such
as tricyclopentylmethoxysilane,
tricyclopentenylmethoxysilane,
tricyclopentadienylmethoxysilane,
tricyclopentylethoxysilane,
cyclopentylmethylmethoxysilane,
dicyclopentylethylmethoxysilane,
dicyclopentylmethylethoxysilane,
cyclopentyldimethylmethoxysilane,
cyclopentyldiethylmethoxysilane,
cyclopentyldimethylethoxysilane, bis(2,5-
dimethylcyclopentyl)cyclopentylmethoxysilane,
dicyclopentylcyclopentenylmethoxysilane,
dicyclopentylcyclopentenadienylmethoxysilane,
diindenylcyclopentylmethoxysilane and ethylenebiscyclopentyldimethoxysilane;
aminosilanes such as
aminopropyltriethoxysilane, n-(3-triethoxysilylpropyl)amine,
bis [(3-triethoxysilyl)propyl]amine,
aminopropyltrimethoxysilane,
aminopropylmethyldiethoxysilane,
hexanediaminopropyltrimethoxysilane. In an
embodiment, the external electron donor, other than
organosilicon compounds include, but not limited to amine,
diether, esters, carboxylate, ketone, amide, phosphine,
carbamate, phosphate, sulfonate, sulfone and/ or
sulphoxide. The external electron donor is used in such an
amount to give a molar ratio of organoaluminum compound
to the said external donor from about 0.1 to 500, preferably
from 1 to 300. In the present invention, the polymerization
of olefins is carried out in the presence of the catalyst
system described above. The catalyst system is contacted
with olefin under polymerization conditions to produce
desired polymer products. The polymerization process can
be carried out such as by slurry polymerization using an
inert hydrocarbon solvent as a diluent, or bulk
polymerization using the liquid monomer as a reaction
medium and in gas-phase operating in one or more
fluidized or mechanically agitated bed reactors. In an
embodiment, polymerization is carried out as such. In
another embodiment, the copolymerization is carried out
using at least two polymerization zones. The catalyst of
the invention can be used in the polymerization of the
above-defined olefin CH2-CHR, the examples of said olefin
include ethylene, propylene, 1-butene, 4-methyl-1-pentene,
1-hexene, and 1-octene. In particular, said catalyst can
be used to produce, the following products such as highdensity
polyethylene (HDPE, having a density higher than
0.940 g/cm3), which includes ethylene homopolymer and
copolymer of ethylene and a-olefins having 3 to 12 carbon
atoms; linear low-density polyethylene (LLDPE, having a
density lower than 0.940 g/cm3), and very low density and
ultra low density polyethylene (VLDPE and ULDPE, having
a density lower than 0.920 g/cm3, and as low as 0.880
g/cm3), consisting of the copolymer of ethylene and one or
more a-olefins having 3 to 12 carbon atoms, wherein the
molar content of the unit derived from ethylene is higher
than 80%; elastomeric copolymer of ethylene and
propylene, and elastomeric terpolymers of ethylene,
propylene and butene-1 as well as diolefins at a small
ratio, wherein the weight content of the unit derived from
ethylene is between about 30% and 70%; isotactic
polypropylene and crystalline copolymer of propylene and
ethylene and/or other a-olefins, wherein the content of the
unit derived from propylene is higher than 85% by weight
(random copolymer); impact propylene polymer, which are
produced by sequential polymerization of propylene and
the mixture of propylene and ethylene, with the content of
ethylene being up to 40% by weight; copolymer of
propylene and 1-butene, containing a great amount, such
as from 10 to 40 percent by weight, of unit derived from 1-
butene. It is especially significant that the propylene
polymers produced by using the catalysts of the invention
have high isotactic index. The polymerization is carried out
at a temperature from 20 to 120° C, preferably from 40 to
80° C. When the polymerization is carried out in gas
phase, operation pressure is usually in the range of from 5
to 100 bar preferably from 10 to 50 bar. The operation
pressure in bulk polymerization is usually in the range of
from 10 to 150 bar, preferably from 15 to 50 bar. The
operation pressure in slurry polymerization is usually in the
range of from 1 to 10 bar, preferably from 2 to 7 bar.
Hydrogen can be used to control the molecular weight of
polymers. In the present invention, the polymerization of
olefins is carried out in the presence of the catalyst system
described in the invention. The described catalyst can be
directly added to the reactor for polymerization or can be
prepolymerized i.e. catalyst is subjected to a
polymerization at lower conversion extent before being
added to polymerization reactor. Prepolymerization can be
performed with olefins preferably ethylene and/or
propylene where the conversion is controlled in the range
from 0.2 to 500 gram polymer per gram catalyst. In the
present invention, the polymerization of olefins in presence
of the described catalyst system leads to the formation of
polyolefins having xylene solubility (XS) ranging from about
0.2% to about 15%. In another embodiment, polyolefins
have xylene solubility (XS) from about 2% to about 8%.
Here XS refers to the weight percent of polymer that get
dissolves into hot xylene generally for measuring the
tacticity index such as highly isotactic polymer will have
low XS % value i.e. higher crystallinity, whereas low
isotactic polymer will have high XS % value. In an
embodiment of the invention, the catalyst efficiency
(measured as kilogram of polymer produced per gram of
catalyst) of the described catalyst system is at least about
30. In another embodiment, the catalyst efficiency of the
described catalyst system is at least about 60. The
present invention provides the catalyst system. The
catalysts system when polymerizes olefins provides
polyolefins having melt flow indexes (MFI) of about 0.1 to
about 100 which is measured according to ASTM standard
D1238. In an embodiment, polyolefins having MFI from
about 0.5 to about 30 are produced. The present
invention provides the catalyst system. The catalysts
system when polymerizes olefins provides polyolefins
having bulk densities (BD) of at least about 0.3 cc/g. The
following non-limiting examples illustrate in details about
the invention. However, they are, not intended to be
limiting the scope of present invention in any way.
Example 1 Preparation of organomagnesium compound In
500 ml glass reactor maintained at 0°C, calculated amount
of magnesium (powder or turnings) were weighed and
added into the reactor followed by diethyl ether followed by
addition of calculated amount of organohalide. . This
mixture was stirred and after the activation of the reaction,
the mixture was allowed to be maintained at same
temperature until all magnesium has reacted. To the
resulting solution, the calculated amount of alcohol was
added dropwise over a period of 1-2 h. After the
completion of addition, the solution was allowed to stir for
another 0.5 h. Finally, the ether was evaporated and solid
compound was analyzed. The organomagnesium
compounds synthesized by the above procedure have
been tabulated in Table 1. TABLE 1 PrecursorMg
RatioBenzyl chloride RatioBuCl RatioAlcohol RatioSolvent
AlcoholMg (wt%)Cl (wt%)Remark MGP#251.3100DEE-
12.618.7 MGP#271a001DEEEHA12.618.7a MGP#25 as
starting material MGP#3711.101DEEEHA12.718.8
MGP#4211.101DEEBenzyl Alcohol14.521.2
MGP#43101.11DEEEHA12.618.7
MGP#4511.101DEEisobutanol18.226.7
MGP#5311.101DEECatechol21.230.9
MGP#5711.101DEECresol14.521.1
MGP#6111.101DEEEHA12.518.9
MGP#6311.101DEE/toluene (20:80)EHA
MGP#6411.101DEEisobutanol17.125.2Isobutanol/hexane
used as precipitating agent
MGP#6611.101DEEEHA12.718.9
MGP#67101.11DEEEHA12.518.9
MGP#6811.101DEEEHA12.518.7 MGP#7311.101DEE3-
methoxy-1-butanol12.418.7 MGP#7411.101DEE3-methoxy
-1-butanol12.518.5 MGP#7511.101DEEEHA12.518.7
MGP#7611.101DEEEHA12.718.9
MGP#83101.11DEE/chlorobenzeneEHA12.518.5
MGP#8411.101DEE/chlorobenzeneEHA12.518.7
MGP#8511.101DEE/chlorobenzeneEHA12.618.7
MGP#8711.101DEEEHA12.718.5
MGP#8811.101DEEEHA12.618.9
MGP#9011.101DEEEHA12.518.6
MGP#9111.101DEEEHA12.618.5
MGP#92101.11DEEEHA12.618.6Reaction @30?C
MGP#9311.101DEEEHA12.518.5EHA addition @ 0?C
MGP#9411.101DEEEHA12.718.5
MGP#9511.101DEEEHA12.618.9Reaction @30?C
MGP#9611.101DEEEHA12.418.6
MGP#9711.101DEEEHA12.618.9
MGP#13711.101DEEEHA12.518.7Benzyl chloride/EHA
mixture added EHA= 2-ethyl-1-hexanol ; DEE= diethyl
ether Table 1 represents the conditions for preparation of
the solid organomagnesium compound using different
alcohols and organohalides under different reaction
conditions. Example 2 Preparation of the catalyst
component To 60 ml of TiCl4 solution maintained at
desired temperature, added 100 ml of the
organomagnesium precursor along with internal donor
(ID/Mg = 0.11 moles) over a period of 10 min and stirred.
After the system has attained the desired temperature, the
resultant solution was maintained at the same temperature
for 15 min. The resultant solution was clear orange in
color. Gradually the reaction temperature was increased to
110?C and maintained for 1h. After settling and
decantation, the suspended solid was again treated with
60ml TiCl4 and 60ml chlorobenzene and after temperature
reached 110°C, the mixture was maintained under stirring
for 15 minutes. The above step was again repeated. After
the reaction was finished, the solid was decanted and
washed sufficiently with hexane at 70°C, respectively and
further dried under hot nitrogen till freely flowing. The solid
catalysts composition synthesized by the above procedure
has been tabulated in Table 2. TABLE 2
CatalystPrecursorPrecursor & TiCl4 contact temperature
°CInternal donor addition °CRemarkTi (wt%)Mg
(wt%)Donor (wt%) ZN#102MGP#2740904.515.219.3
ZN#119MGP#45-5-52.615.824.3 ZN#120MGP#37-5-
53.318.710.5 ZN#121MGP#37-5-5Three titanation
@110°C2.917.417.0 ZN#129MGP#37-5-5two titanation @
120?C 3.116.420.1 ZN#131MGP#37-5-5Three titanation
@120?C – 1st : 60 ml TiCl4 ; 2nd : 40 ml TiCl4 ; 3rd : 20
ml TiCl42.817.517.0 ZN#132MGP#37-5-5Three titanation
@120?C Two stage DIBP addition at 1st titanation – 1st @
-5?C; 2nd @ 70?C 3.816.517.0 ZN#133MGP#37-5-
5Three titanation @120?C2.716.720.5 ZN#134MGP#37-5-
5Three titanation @110?C Two stage DIBP addition at 1st
titanation – 1st @ -5?C; 2nd @ 70?C 5.218.73.1
ZN#135MGP#37-5-5Three titanation @110°C2.518.013.6
ZN#145MGP#37-5-5Three titanation @110°C; TiCl4(40
ml)3.018.212.5 ZN#146MGP#37-5-5Three titanation
@110°C; Diether as internal donor4.911.917.5
ZN#149MGP#64-5-5Three titanation @110°C2.211.511.1
ZN#150MGP#61-5-5Three titanation @110°C2.317.515.4
ZN#152MGP#37-5-5Three titanation @110°C3.317.515.2
ZN#153MGP#37-5-5Three titanation @110°C; Temp
ramping from -5?C to 110?C in 50 min2.518.614.4
ZN#154MGP#66-5-5Three titanation @110°C3.914.614.2
ZN#156MGP#67-5-5Three titanation @120°C2.515.914.4
ZN#157MGP#66-5-5Three titanation @110°C; (DIBP/Mg =
0.05moles)3.118.18.7 ZN#158MGP#67-5-5Three titanation
@110°C; (DIBP/Mg = 0.05moles)1.815.717.7
ZN#159MGP#66-5-5Three titanation @100°C; (DIBP/Mg =
0.05moles)2.817.512.2 ZN#160MGP#66-5-5Three
titanation @100°C; (DIBP/Mg = 0.05moles)3.117.112.2
ZN#161MGP#66-5-5Three titanation @110°C; (DIBP/Mg =
0.05moles)1.116.814.5 ZN#162MGP#66-5-5Three
titanation @110°C2.116.913.5 ZN#164MGP#66-5-5Three
titanation @110°C; Additional chlorobenzene washing
before hexane washing2.817.512.2 ZN#165MGP#66-5-
5Three titanation @110°C; 2.916.914.1 ZN#168MGP#66-5
-5Three titanation @110°C; (Ti/Mg = 6.7 )2.113.514.1
ZN#169MGP#66-5-5Three titanation @110°C; MGP
dissolved in decane3.615.3 ZN#170MGP#66-5-5Three
titanation @110°C; MGP dissolved in mineral oil2.717.2
ZN#171MGP#66-5-5Three titanation @110°C; (DIBP/Mg =
0.05moles)2.918.512.7 ZN#172MGP#66-5-5Three
titanation @100°C2.714.813.3 ZN#173MGP#66 filtered-5-
5Three titanation @110°C1.318.011.9 ZN#175MGP#66-5-
5Three titanation @110°C; Charging of TiCl4 to MGP/ID
solution2.617.210.4 ZN#176MGP#66-5-5Three titanation
@110°C; Charging of TiCl4 to MGP/ID solution2.616.910.8
ZN#179MGP#67-5-5Three titanation @110°C; RPM
5002.718.415.2 ZN#180MGP#67-5-5Three titanation
@110°C; RPM 2502.617.6 ZN#188MGP#75-5-5Three
titanation @110°C2.718.312.5 ZN#189MGP#75-20-
20Three titanation @110°C2.416.714.4 ZN#191MGP#75-
20-20Three titanation @110°C; Temp ramping from -20?C
to 110?C in 60 min3.417.1 ZN#192MGP#75-20-20Three
titanation @110°C; Temp ramping from -20?C to 110?C in
120 min3.117.114.6 ZN#193MGP#75-20-20Three
titanation @110°C; Temp ramping from -20?C to 110?C in
30 min3.017.413.6 ZN#194MGP#75-20-20Three titanation
@110°C; Temp ramping from -20?C to 110?C in 120 min;
RPM 2503.117.115.5 ZN#194MGP#75-20-20Three
titanation @110°C; Temp ramping from -20?C to 110?C in
120 min; RPM 1752.517.314.2 ZN#195MGP#75-20-
20Three titanation @110°C; Temp ramping from -20?C to
110?C in 120 min; RPM 7502.216.016.1 ZN#196MGP#76-
20-20Three titanation @110°C; Temp ramping from -20?C
to 110?C in 120 min2.317.514.5 ZN#207MGP#84-20-
20Three titanation @110°C; Temp ramping from -20°C to
110°C in 120 min1.315.511.2 ZN#207MGP#83-20-
20Three titanation @110°C; Temp ramping from -20°C to
110°C in 120 min1.319.111.0 ZN#209MGP#85-20-
20Three titanation @110°C; Temp ramping from -20°C to
110°C in 120 min1.818.59.3 ZN#218MGP#75-20-20Three
titanation @110°C; Temp ramping from -20°C to 110°C in
120 min2.518.612.6 ZN#288MGP#137-5-5Three titanation
@110°C; Temp ramping from -5°C to 110°C 2.419.411.8
Table 2 represents the preparation of solid catalyst using
organomagnesium compound as precursor under different
reaction conditions. Example 3 Slurry polymerization of
propylene Propylene polymerization was carried out in 1 L
Buchi reactor which was previously conditioned under
nitrogen. The reactor was charged with 250 ml of dry
hexane containing solution of 10 wt% triethylaluminum
followed by 100 ml of dry hexane containing 10 wt%
solution of triethylaluminum, 5 wt% solution of cyclohexy
methyl dimethoxysilane and weighed amount of catalyst.
The reactor was pressurized with hydrogen to 60 ml then
charged with 71 psi of propylene under stirring at 750 rpm.
The reactor was heated to and then held at 70?C for 2
hour. At the end, the reactor was vented and the polymer
was recovered at ambient conditions. Catalyst
performance and polymer properties has been tabulated in
Table 3 TABLE 3
CATALYSTPOLYMERIZATIONPOLYMER ANALYSIS Cat
NoCat wt (mg)Al/Ti ratioH2 mlAl/Do ratioActivity
kgPP/gcatMFI @2.16 kgXS wt%BD g/cc
ZN#10215.525010205.8-4.2 ZN#121 14.2500102011-
2.00.41 10.5500102013.35.33.20.40
10.5500103014.34.83.70.41 10.3500101013.24.12.10.40
10.250010512.43.65.50.42 10.2500104010.4-6.60.41
10.65000307.7-4.20.40
ZN#12910.6500102010.62.63.00.27
ZN#13110.650010206.92.52.00.36
ZN#13210.3500102015.13.93.20.35
ZN#13310.2500102013.52.42.10.43
ZN#13510.4500102010.80.51.90.38
ZN#14510.550010209.92.12.60.37
ZN#14910.850010209.52.21.60.38
ZN#15410.3500102012.86.01.90.34
ZN#15610.2500102012.71.62.50.36
ZN#15710.0500102014.75.42.50.38
ZN#15810.350010207.13.62.10.37
ZN#15910.550010208.63.42.20.39
ZN#16010.0500102011.73.02.00.40
ZN#16115.050010209.82.42.00.32
ZN#16210.350010209.02.72.00.34
ZN#16410.350010207.83.71.60.35
ZN#16510.6500102012.58.81.20.41
ZN#16810.350010209.02.61.10.33
ZN#16910.750010208.33.21.50.33
ZN#17010.850010206.35.61.10.32
ZN#17110.3500102010.82.21.30.38
ZN#17210.250020209.04.01.90.32
ZN#17310.950010201.81.62.50.31
ZN#17510.1500102013.021.80.43
ZN#17610.6500102013.73.41.30.42
ZN#17910.7500102010.22.81.90.27
ZN#18010.0500102011.22.42.30.29
ZN#18910.450010208.32.72.00.32
ZN#18810.3500102011.33.01.70.36
ZN#19110.6500102010.62.31.70.32
ZN#19210.2500102011.93.22.20.37
ZN#19310.250010209.54.71.70.33
ZN#19410.450010209.38.61.90.31
ZN#19510.7500102010.13.31.40.35
ZN#19610.0500102010.54.22.30.32
ZN#20710.850010207.67.22.90.37
ZN#20810.850010200.84.53.10.35
ZN#20910.850010209.73.12.30.37
ZN#28810.050010305.55.33.60.45 Table 3 represents the
propylene polymerization using different catalyst
synthesized using different organomagnesium compounds
as precursors. The catalysts synthesized under different
conditions were found to be active for propylene
polymerization.
5. CLAIMS (not applicable for provisional specification.)
WE CLAIM: 1.A process for preparation of a solid
organomagnesium precursor having formula
{Mg(OR’)X}.a{MgX2}.b{Mg(OR’)2}.c{R’OH}, wherein R’ is
selected from a hydrocarbon group, X is selected from a
halide group, and a:b:c is in range of 0.01-0.5 : 0.01 – 0.5 :
0.01 - 5, said process comprising contacting a magnesium
source with a solvating agent, an organohalide and an
alcohol to obtain the solid organomagnesium precursor.
2.The process as claimed in claim 1, wherein the process
is carried out in a single step or multiple steps. 3.The
process as claimed in claim 1, wherein the alcohol is
added after the reaction of magnesium source with
solvating agent and organohalide. 4.The process as
claimed in claim 1, wherein the organohalide is added after
the reaction of magnesium with solvating agent followed by
addition of alcohol. 5.The process as claimed in claim 1,
wherein a mixture or the organohalide and alcohol is
added after the reaction of magnesium with solvating
agent. 6.The process as claimed in claim 1, wherein the
solid organomagnesium precursor is stable. 7.The
process as claimed in claim 1, wherein the stable solid
organomagnesium precursor is isolated from solvating
agent either using reduced pressure with and/or without
heating, through precipitation, recrystallization to obtain the
precipitated solid organomagnesium precursor. 8.The
process as claimed in claim 7, wherein, the precipitated
solid organomagnesium precursor is either used directly or
in solution form for catalyst synthesis. 9.The process as
claimed in claim 7, wherein the precipitated solid is
dissolve in a solvent to obtain a solution form of
precipitated solid. 10.The process as claimed in claim 7,
wherein the solvent used for dissolving precipitated solid is
selected from a group comprising of polar aliphatic
hydrocarbons, non polar aliphatic hydrocarbons, polar
aromatic hydrocarbons, non polar aromatic hydrocarbons
and combination thereof. 11.The process as claimed in
claim 7, wherein the precipitation methodology is adopted
during any stage of precursor synthesis. 12.The process
as claimed in claims 7 to 11, wherein the precipitated solid
organomagnesium precursor is obtained either reacting
magnesium with organic halide in solvating agent followed
by precipitation in the mixture of alcohol and precipitating
solvent or vice versa, or reacting magnesium with organic
halide in solvating agent followed by addition of alcohol
and then precipitating in precipitating solvent or vice versa.
13.The process as claimed in claim 1, wherein the
magnesium source is selected from a group comprising of
magnesium metal, dialkyl magnesium, alkyl/aryl
magnesium halides and mixtures thereof; wherein: (a)the
magnesium metal is in form of powder, granules, ribbon,
turnings, wire, block, lumps, chips; (b)the
dialkylmagnesium compounds is selected from a group
comprising of dimethylmagnesium, diethylmagnesium,
diisopropylmagnesium, dibutylmagnesium,
dihexylmagnesium, dioctylmagnesium,
ethylbutylmagnesium, and butyloctylmagnesium; and
(c)alkyl/aryl magnesium halides is selected from a group
comprising of methylmagnesium chloride,
ethylmagnesium chloride, isopropylmagnesium chloride,
isobutylmagnesium chloride, tert-butylmagnesium chloride,
benzylmagnesium chloride, methylmagnesium bromide,
ethylmagnesium bromide, isopropylmagnesium bromide,
isobutylmagnesium bromide, tert-butylmagnesium
bromide, hexylmagnesium bromide, benzylmagnesium
bromide, methylmagnesium iodide, ethylmagnesium
iodide, isopropylmagnesium iodide, isobutylmagnesium
iodide, tert-butylmagnesium iodide, and benzylmagnesium
iodide. 14.The process as claimed in claim 1, wherein the
magnesium source is magnesium metal. 15.The process
as claimed in claim 1, wherein the organohalide is selected
from a group comprising of alkyl halides, halogenated alkyl
benzene/ benzylic halides having an alkyl radical contains
from about 10 to 15 carbon atoms and mixtures thereof;
wherein: (a)the alkyl halides is selected from a group
comprising of methyl chloride, ethyl chloride, propyl
chloride, isopropyl chloride, 1,1-dichloropropane, 1,2-
dichloropropane, 1,3-dichloropropane, 2,3-
dichloropropane, butyl chloride, 1,4-dichlorobutane, tertbutylchloride,
amylchloride, tert-amylchloride, 2-
chloropentane, 3-chloropentane, 1,5-dichloropentane, 1-
chloro-8-iodoctane, 1-chloro-6-cyanohexane,
cyclopentylchloride, cyclohexylchloride, chlorinated
dodecane, chlorinated tetradecane, chlorinated eicosane,
chlorinated pentacosane, chlorinated triacontane, isooctylchloride,
5-chloro-5-methyl decane, 9-chloro-9-ethyl-6-
methyl eiscosane; and (b)the halogenated alkyl
benzene/benzylic halides is selected from a group
comprising of benzyl chloride and a,a' dichloro xylene.
16.The process as claimed in claim 1, wherein the
organohalide is benzyl chloride or butyl chloride or their
mixture. 17.The process as claimed in claim 1, wherein
the solvating agent is selected from a group comprising of
dimethyl ether, diethyl ether, dipropyl ether, diisopropyl
ether, ethylmethyl ether, n-butylmethyl ether, n-butylethyl
ether, di-n-butyl ether, di-isobutyl ether, isobutylmethyl
ether, and isobutylethyl ether, dioxane, tetrahydrofuran, 2-
methyl tetrahydrofuran, tetrahydropyran, chlorobenzene,
dichloromethane, toluene, heptane, hexane and
combination thereof. 18.The process as claimed in claim
1, wherein the solvating agent is diethyl ether or
tetrahydrofuran or their mixture. 19.The process as
claimed in claim 1, wherein the alcohol is selected from a
group comprising of aliphatic alcohols, alicyclic alcohols,
aromatic alcohols, aliphatic alcohols containing an alkoxy
group, diols and mixture thereof; wherein: (a)the aliphatic
alcohols is selected from a group comprising of methanol,
ethanol, propanol, butanol, iso-butanol, t-butanol, npentanol,
iso-pentanol, hexanol , 2-methylpentanol, 2-
ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol,
decanol and dodecanol, (b)the alicyclic alcohols is selected
from a group comprising of cyclohexanol and
methylcyclohexanol, (c)the aromatic alcohols is selected
from a group comprising of benzyl alcohol and
methylbenzyl alcohol, (d)the aliphatic alcohols containing
an alkoxy group is selected from a group comprising of
ethyl glycol and butyl glycol; (e)the diols is selected from a
group comprising of catechol, ethylene glycol, 1,3-
propanediol, 1,4-butanediol, 1,5-pentanediol, 1,8-
octanediol, 1,2-propanediol, 1,2-butanediol, 2,3-
butanediol, 1,3-butanediol, 1,2-pentanediol, p-menthane-
3,8- diol, and 2-methyl-2,4-pentanediol. 20.The process as
claimed in claim 1, wherein the magnesium source is
reacted with the organohalide in a molar ratio of between
1:20 to 1:0.2, preferably between about 1:10 to 1:0.5, more
preferably, between 1:4 to 1:0.5. 21.The process as
claimed in claim 1, wherein the magnesium source and
solvating agent in a molar ratio of between 1:20 to 1:0.2,
preferably between about 1:15 to 1:1, more preferably,
between 1:10 to 1:1. 22.The process as claimed in claim
1, wherein the magnesium source, organohalide, and
solvating agent are contacted at temperature between
about -20°C and about 200°C, and preferably between
about -10°C and about 140°C, more preferably between -
10°C to 100°C and contact time is for about 0.5 to 12 h for
the formation of a homogeneous solution of magnesium
component in solvating agent. 23.The process as claimed
in claim 1, optionally required a reaction promoters, which
is selected from a group comprising of iodine, the
organohalides, inorganic halides, nitrogen halides, and
mixture thereof; wherein: (a)the inorganic halides is
selected from a group comprising of CuCl, MnCl2, and
AgCl; and (b)the nitrogen halides is selected from a group
comprising of N-halide succinimides, trihaloisocynauric
acid, N-halophthalimide and hydrantoin compounds. 24.A
solid organomagnesium precursor having formula
{Mg(OR’)X}.a{MgX2}.b{Mg(OR’)2}.c{R’OH}, wherein R’ is
selected from a hydrocarbon group, X is selected from a
halide group, and a:b:c is in range of 0.01-0.5 : 0.01 – 0.5 :
0.01 - 5. 25.A process for preparation of a catalyst
composition, said process comprising: (a)contacting a
solution of transition metal compound represented by
M(OR”’)pX4-p, where M is a transition metal and is
selected from a group comprising of Ti, V, Zr, and Hf; X is
a halogen atom; R’’’ is a hydrocarbon group and p is an
integer having value equal or less than 4, with the solid
organomagnesium precursor component as claimed in
claim 1 to obtain a resulting solution and contact
temperature of solid organomagnesium precursor and the
transition metal compound is between about -50°C and
about 150°C, and preferably between about -30°C and
about 120°C; (b)adding an internal donor either to the
solid organomagnesium precursor component or to the
titanium component and the contact time of the said
component with the internal electron donor immediate or is
at least 1 minutes to 60 minutes at contact temperature of
between about -50°C and about 100°C, and preferably
between about -30°C and about 90°C; (c)treating the
resulting solution obtained in the step (a) with a solution
comprising a titanium component in a solvent and
recovering a solid titanium catalyst component and
maintaining the same at a temperature value in the range
of 100 to 120oC for about 10 to 60 minutes; and
(d)optionally repeating step (c) for a predetermined number
of times and then washed sufficiently with inert solvent at
temperature 20ºC to 80ºC to obtain a solid catalysts
composition. 26.The process as claimed in claim 25,
wherein in step (a) the transition metal compound is added
to the organomagnesium compound or vice-verse,
preferably, organomagnesium compound is added to
transition metal compound. 27.The process as claimed in
claim 25, wherein step (b) preferably comprising adding
organomagnesium precursor with internal donor. 28.The
process as claimed in claim 25, wherein transition metal is
titanium metal. 29.The process as claimed in claim 25,
wherein the transition metal compound represented by
M(OR’’’)pX4-p is selected from a group comprising of
transition metal tetrahalide, alkoxy transition metal
trihalide/aryloxy transition metal trihalide, dialkoxy
transition metal dihalide, trialkoxy transition metal
monohalide, tetraalkoxy transition metal, and mixtures
thereof; wherein: (a)the transition metal tetrahalide is
selected from a group comprising of titanium tetrachloride,
titanium tetrabromide and titanium tetraiodide and the likes
for V, Zr and Hf; (b)alkoxy transition metal trihalide/aryloxy
transition metal trihalide is selected from a group
comprising of methoxytitanium trichloride, ethoxytitanium
trichloride, butoxytitanium trichloride and phenoxytitanium
trichloride and the likes for V, Zr and Hf; (c)dialkoxy
transition metal dihalide is diethoxy titanium dichloride and
the likes for V, Zr and Hf; (d)trialkoxy transition metal
monohalide is triethoxy titanium chloride and the likes for
V, Zr and Hf; and (e)tetraalkoxy transition metal is selected
from a group comprising of tetrabutoxy titanium and
tetraethoxy titanium and the likes for V, Zr and Hf. 30.The
process as claimed in claim 25, wherein the internal
electron donor used is selected from a group comprising of
phthalates, benzoates, succinates, malonates, carbonates,
diethers, and combinations thereof; wherein: (a)the
phthalate is selected from a group comprising of di-n-butyl
phthalate, di-i-butyl phthalate, di-2-ethylhexyl phthalate, din-
octyl phthalate, di-i-octyl phthalate, di-n-nonyl phthalate;
(b)the benzoate is selected from a group comprising of
methyl benzoate, ethyl benzoate, propyl benzoate, phenyl
benzoate, cyclohexyl benzoate, methyl toluate, ethyl
toluate, p-ethoxy ethyl benzoate, p-isopropoxy ethyl
benzoate; (c)the succinate is selected from a group
comprising of diethyl succinate, di-propyl succinate,
diisopropyl succinate, dibutyl succinate, diisobutyl
succinate; (d)the malonate is selected from a group
comprising of diethyl malonate, diethyl ethylmalonate,
diethyl propyl malonate, diethyl isopropylmalonate, diethyl
butylmalonate; (e)the carbonate compound is selected
from a group comprising of diethyl 1,2-
cyclohexanedicarboxylate, di-2-ethyIhexyl 1,2-
cyclohexanedicarboxylate, di-2- isononyl 1,2-
cyclohexanedicarboxylate, methyl anisate, ethyl anisate;
and (f)the diether compound is selected from a group
comprising of 9,9-bis(methoxymethyl)fluorene, 2-isopropyl-
2-isopentyl-1,3-dimethoxypropane, 2,2-diisobutyl-l,3-
dimethoxypropane, 2,2-diisopentyl-l,3- dimethoxypropane,
2-isopropyl-2-cyclohexyl- 1 ,3-dimethoxypropane. 31.The
process as claimed in claim 25, wherein in step (a) the
contact of organomagnesium compound with titanium
compound is either neat or in solvent 32.The process as
claimed in claim 25, wherein in step (a) the stable solid
organomagnesium compound is used as solid or in
solvent. 33.The process as claimed in claims 31 and 32,
wherein the solvent is selected from group comprising of
chlorinated aromatic hydrocarbon, non chlorinated
aromatic hydrocarbon chlorinated aliphatic hydrocarbon,
non chlorinated aliphatic hydrocarbon and combination
thereof. 34.The process as claimed in claims 31 to 33,
wherein the solvent is comprising from 5 to 95 volume
percent and is selected from group comprising of benzene,
decane, kerosene, ethyl benzene, chlorobenzene,
dichlorobenzene, toluene, o-chlorotoluene, xylene,
dichloromethane, chloroform, cyclohexane and
combination thereof. 35.The process as claimed in claim
25, wherein in step (b) the internal electron donor is used
in an amount of from 0 to 1 moles, preferably from 0.01 to
0.5 moles, with respect to one mole of magnesium. 36.A
catalyst composition as defined in claim 25, said catalyst
composition comprising a combination of 2.0 wt % to 20 wt
% of an internal electron donor, 0.5 wt % to 10.0 wt% of a
titanium and 10 wt% to 20 wt % of a magnesium. 37.A
process for preparation of a catalyst system, said process
comprising contacting the catalyst composition with at least
one cocatalyst, and at least one external electron donor to
obtain the catalyst system. 38.A catalyst system as
defined in claim 37, said catalyst system comprising a
combination of catalyst composition, organoaluminium
compounds cocatalyst and external electron donors,
wherein, the catalyst composition is the combination of
magnesium moiety, titanium moiety and an internal donor
and the magnesium moiety is the organomagnesium
precursor; the cocatalyst is selected from a group
comprising of hydrides, organoaluminum, lithium, zinc, tin,
cadmium, beryllium, magnesium, and combinations
thereof; the external electron donors is selected from a
group comprising of organosilicon compounds, diethers,
alkoxy benzoates, amine, esters, carboxylate, ketone,
amide, phosphine, carbamate, phosphate, sulfonate,
sulfone, sulphoxide and combinations thereof. 39.The
catalyst system as claimed in claim 38, wherein the
cocatalyst is organoaluminium compound and is selected
from a group comprising of alkylaluminums,
trialkenylaluminums, dialkylaluminum halides,
alkylaluminum sesquihalides, dialkylaluminum hydrides,
partially hydrogenated alkylaluminum, aluminoxane,
diethylaluminum ethoxide and combination thereof; the
alkylaluminums is selected from a group comprising of
triethylaluminum, triisopropylaluminum,
triisobutylaluminum, tri-n-butylaluminum, tri-nhexylaluminum,
tri-n-octylaluminum; the
trialkenylaluminums is selected from a group comprising of
triisoprenyl aluminum; the dialkylaluminum halides is
selected from a group comprising of diethylaluminum
chloride, dibutylaluminum chloride, diisobutylaluminum
chloride, diethyl aluminum bromide; the alkylaluminum
sesquihalides is selected from a group comprising of
ethylaluminum sesquichloride, butylaluminum
sesquichloride, ethylaluminum sesquibromide; the
dialkylaluminum hydrides is selected from a group
comprising of diethylaluminum hydride, dibutylaluminum
hydride; the partially hydrogenated alkylaluminum is
selected from a group comprising of ethylaluminum
dihydride, propylaluminum dihydride; and the aluminoxane
is selected from a group comprising of methylaluminoxane,
isobutylaluminoxane, tetraethylaluminoxane and
tetraisobutylaluminoxane. 40.The catalyst system as
claimed in claim 38, wherein ratio of catalyst composition
(titanium) : organoaluminum compound : external donor is
in range of 1 : 5-1000 : 0-250, preferably in the range of 1 :
25-500 : 25-100. 41.The catalyst system as claimed in
claims 38 to 40, wherein mole ratio of aluminum to titanium
is from about 5:1 to about 1000:1 or from about 10:1 to
about 700:1, or from about 25:1 to about 500:1. 42.The
catalyst system as claimed in claims 38, wherein the
external donors is organosilicon compounds and is
selected from a group comprising of
trimethylmethoxysilane, trimethylethoxysilane,
dimethyldimethoxysilane, dimethyldiethoxysilane,
diisopropyldimethoxysilane, diisobutyldimethoxysilane, tbutylmethyldimethoxysilane,
t-butylmethyldiethoxysilane, tamylmethyldiethoxysilane,
dicyclopentyldimethoxysilane,
diphenyldimethoxysilane, phenylmethyldimethoxysilane,
diphenyldiethoxysilane, bis-o-tolydimethoxysilane, bis-mtolydimethoxysilane,
bis-p-tolydimethoxysilane, bis-ptolydiethoxysilane,
bisethylphenyldimethoxysilane,
dicyclohexyldimethoxysilane,
cyclohexylmethyldimethoxysilane,
cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane,
ethyltriethoxysilane, vinyltrimethoxysilane,
methyltrimethoxysilane, n-propyltriethoxysilane,
decyltrimethoxysilane, decyltriethoxysilane,
phenyltrimethoxysilane, gammachloropropyltrimethoxysilane,
methyltriethoxysilane,
ethyltriethoxysilane, vinyltriethoxysilane, tbutyltriethoxysilane,
n-butyltriethoxysilane, isobutyltriethoxysilane,
phenyltriethoxysilane, gammaaminopropyltriethoxysilane,
cholotriethoxysilane,
ethyltriisopropoxysilane, vinyltirbutoxysilane,
cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-
norbornanetrimethoxysilane, 2-norbornanetriethoxysilane,
2-norbornanemethyldimethoxysilane, ethyl silicate, butyl
silicate, trimethylphenoxysilane, and
methyltriallyloxysilane, cyclopropyltrimethoxysilane,
cyclobutyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-
methylcyclopentyltrimethoxysilane, 2,3-
dimethylcyclopentyltrimethoxysilane, 2,5-
dimethylcyclopentyltrimethoxysilane,cyclopentyltriethoxysil
ane, cyclopentenyltrimethoxysilane, 3-
cyclopentenyltrimethoxysilane, 2,4-
cyclopentadienyltrimethoxysilane, indenyltrimethoxysilane
and fluorenyltrimethoxysilane; dialkoxysilanes such as
dicyclopentyldimethoxysilane, bis(2-
methylcyclopentyl)dimethoxysilane, bis(3-tertiary
butylcyclopentyl)dimethoxysilane, bis(2,3-
dimethylcyclopentyl)dimethoxysilane, bis(2,5-
dimethylcyclopentyl)dimethoxysilane,
dicyclopentyldiethoxysilane, dicyclobutyldiethoxysilane,
cyclopropylcyclobutyldiethoxysilane,
dicyclopentenyldimethoxysilane, di(3-
cyclopentenyl)dimethoxysilane, bis(2,5-dimethyl-3-
cyclopentenyl)dimethoxysilane, di-2,4-
cyclopentadienyl)dimethoxysilane, bis(2,5-dimethyl-2,4-
cyclopentadienyl)dimethoxysilane, bis(1-methyl-1-
cyclopentylethyl)dimethoxysilane,
cyclopentylcyclopentenyldimethoxysilane,
cyclopentylcyclopentadienyldimethoxysilane,
diindenyldimethoxysilane, bis(1,3-dimethyl-2-
indenyl)dimethoxysilane,
cyclopentadienylindenyldimethoxysilane,
difluorenyldimethoxysilane,
cyclopentylfluorenyldimethoxysilane and
indenylfiuorenyldimethoxysilane; monoalkoxysilanes such
as tricyclopentylmethoxysilane,
tricyclopentenylmethoxysilane,
tricyclopentadienylmethoxysilane,
tricyclopentylethoxysilane,
cyclopentylmethylmethoxysilane,
dicyclopentylethylmethoxysilane,
dicyclopentylmethylethoxysilane,
cyclopentyldimethylmethoxysilane,
cyclopentyldiethylmethoxysilane,
cyclopentyldimethylethoxysilane, bis(2,5-
dimethylcyclopentyl)cyclopentylmethoxysilane,
dicyclopentylcyclopentenylmethoxysilane,
dicyclopentylcyclopentenadienylmethoxysilane,
diindenylcyclopentylmethoxysilane and ethylenebiscyclopentyldimethoxysilane;
aminosilanes such as
aminopropyltriethoxysilane, n-(3-triethoxysilylpropyl)amine,
bis [(3-triethoxysilyl)propyl]amine,
aminopropyltrimethoxysilane,
aminopropylmethyldiethoxysilane,
hexanediaminopropyltrimethoxysilane and combination
thereof. 43.The catalyst system as claimed in claims 38,
wherein the molar ratio of organoaluminum compound to
the external donor from about 0.1 to 500, preferably from 1
to 300. 44.A process of polymerizing and/or
copolymerizing olefins, said method comprising the step of
contacting an olefin having C2 to C20 carbon atoms under
a polymerizing condition with the catalyst system as
obtained by claim 38. 45.The polymerization process as
claimed in claim 44, wherein polymerization is carried out
such as by slurry polymerization using an inert
hydrocarbon solvent as a diluent, or bulk polymerization
using the liquid monomer as a reaction medium and in gas
-phase operating in one or more fluidized or mechanically
agitated bed reactors. 46.The polymerization process as
claimed in claims 44 and 45, wherein the olefin is selected
from a group comprising of ethylene, propylene, 1-butene,
4-methyl-1-pentene, 1-hexene, 1-octene and combination
thereof.