CLIAMS:1. An ion exchange resin immobilized single site catalyst represented by Formula I:
Formula I
wherein,
P is cross-linked polystyrene-divinylbenzene copolymer matrix,
LY is a Schiff base adduct formed from m-phenylene diamine and 3-tert butyl salicylaldehyde or 3,5-di tert butyl salicylaldehyde; and

M is a transition metal selected from the group consisting of Hafnium (Hf), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V) and Titanium (Ti).

2. The catalyst as claimed in claim1, wherein the cationic component
of Formula I represents following single site catalyst having formula IA:

Formula IA
wherein, R1, R2, R4, R6 R8, R10 and R12 are same or different, and independently selected from the group consisting of hydrogen, aryl, hetero-aryl and halide;
R5 and R9 are tertiary alkyl groups;
R7 and R11 are same or different, and independently selected from the group consisting of hydrogen and tertiary alkyl group;
R3 is independently selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy, carboxylic and sulphonic;
M is a transition metal selected from the group consisting of Hafnium (Hf), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V) and Titanium (Ti); and
X is a halide selected from the group consisting of Cl, Br and I; and
n is an integer 2.

3. A process for the preparation of an ion exchange resin immobilized single site catalyst represented by Formula I,
Formula I
wherein,
P is a cross-linked polystyrene-divinylbenzene copolymer matrix,
LY is a Schiff base adduct formed from m-phenylene diamine and 3-tert butyl salicylaldehyde or 3,5-di tert butyl salicylaldehyde; and

M is a transition metal selected from the group consisting of Hafnium (Hf), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V) and Titanium (Ti),

said process comprises the following steps:
a. reacting at least one single site catalyst with at least one aluminium alkyl compound to obtain a cationic complex of single site catalyst; and

b. exchanging the cation of the ion exchange resin with the cationic complex of single site catalyst to obtain the ion exchange resin immobilized single site catalyst.

4. The process as claimed in claim 3, wherein said aluminium alkyl compound is at least one selected from the group consisting of methylaluminoxane (MAO) and poly methylaluminoxane (PMAO).

5. The process as claimed in claim 3, wherein the single site catalyst is a catalyst represented by Formula II:

Formula II
wherein,
LY is a Schiff base adduct formed from m-phenylene diamine and 3-tert butyl salicylaldehyde or 3,5-di tert butyl salicylaldehyde;

M is a transition metal selected from the group consisting of Hafnium (Hf), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V) and Titanium (Ti); and
X is a halide selected from the group consisting of Cl, Br and I.
6. The process as claimed in claim 3, wherein the ion exchange resin is a sulfonated polystyrene cation exchange resin represented by Formula III:

Formula III
wherein P is a cross-linked polystyrene-divinylbenzene copolymer matrix.

7. The process as claimed in claim 3, wherein the process includes formation of an intermediate represented by Formula IV:
Formula IV
8. The process as claimed in claim 3, wherein the cationic complex of single site catalyst is represented by Formula V:
Formula V
wherein, LY is a Schiff base adduct formed from m-phenylene diamine and 3-tert butyl salicylaldehyde or 3,5-di tert butyl salicylaldehyde, and
M is a transition metal selected from the group consisting of Hafnium (Hf), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V) and Titanium (Ti).

9. A process for polymerization of olefin, said process comprises subjecting said olefin to polymerization in the presence of an ion exchange resin immobilized single site catalyst of claim 1. ,TagSPECI:FIELD OF THE DISCLOSURE
The present disclosure relates to an ion exchange resin immobilized single site catalyst and its preparation. The present disclosure also relates to a process for olefin polymerization using the ion exchange resin immobilized single site catalyst.

BACKGROUND:

Ion-exchange resins are commonly utilized for water purification, metal separation and recovery, ion substitution, acid-base catalysis, as sensors or as solid electrolytes (e.g., in fuel cells, electrolyzers, electrodialysis devices), in chemical, food, and beverage industries, and in power,
nuclear, semiconductor and pharmaceutical industries. Ion-exchange resins are mainly classified into cation exchanger and anion exchanger. Most of the ion-exchange resins are based on cross-linked polystyrene-divinylbenzene copolymers bearing ion-exchanging functional groups. Other ion-exchanging materials include homopolystyrene and acrylic based resins and Nafion, a perfluorinated polymer containing sulfonic acid heads.

Polyolefins are known to be manufactured using transition metal-catalysed polymerization technology. Typically, the catalysts used in manufacturing polyolefins are usually multi-site heterogeneous Ziegler–Natta catalysts. With the advancement in polymerization technology, single-site catalysts or group (IV) metallocene catalysts are increasingly being used for manufacturing polyolefins. Single-site catalysts and metallocene catalysts are continuously being designed to suit vital manufacturing process requirements. Development of such a catalyst with composite capability to impart various desired properties to the final product requires a careful selection of a catalyst complex.
The present disclosure envisages an ion exchange resin immobilized single site catalyst, its preparation and utilization in olefin polymerization.

OBJECTS:
Some of the objects of the present disclosure, which at least one embodiment herein satisfies, are as follows:

It is an object of the present disclosure to provide an ion exchange resin immobilized single site catalyst.

It is another object of the present disclosure to provide a process for the preparation of an ion exchange resin immobilized single site catalyst.

It is still another object of the present disclosure to provide a process for olefin polymerization using the ion exchange resin immobilized single site catalyst.

Other objects and advantages of the present disclosure will be more apparent from the following description which is not intended to limit the scope of the present disclosure.

SUMMARY:
The present disclosure provides an ion exchange resin immobilized single site catalyst represented by Formula I:
Formula I
In one embodiment,
P is a cross-linked polystyrene-divinylbenzene copolymer matrix,
LY is a Schiff base adduct formed from m-phenylene diamine and 3-tert butyl salicylaldehyde or 3,5-di tert butyl salicylaldehyde, and

M is a transition metal selected from the group consisting of Hafnium (Hf), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V) and Titanium (Ti).

In one embodiment the cationic component

of Formula I generated in the reaction medium due to complexation of co-catalyst with catalyst where catalyst is represented by Formula IA:
Formula IA
wherein, R1, R2, R4, R6 R8, R10 and R12 are same or different, and independently selected from the group consisting of hydrogen, aryl, hetero-aryl and halide;
R5 and R9 are tertiary alkyl groups;
R7 and R11 are same or different, and independently selected from the group consisting of hydrogen and tertiary alkyl group;
R3 is independently selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy, carboxylic and sulphonic;
M is a transition metal selected from the group consisting of Hafnium (Hf), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V) and Titanium (Ti); and

X is a halide selected from the group consisting of Cl, Br and I; and
n is an integer 2.

In accordance with another aspect of the present disclosure there is provided a process for the preparation of an ion exchange resin immobilized single site catalyst represented by Formula I,
Formula I
the process comprising the following steps:
? reacting at least one single site catalyst with at least one aluminium alkyl compound to obtain a cationic complex of single site catalyst; and

? exchanging the cation resin of the ion exchange resin with the cationic complex of single site catalyst to obtain the ion exchange resin immobilized single site catalyst.

The aluminium alkyl compound can be at least one selected from the group consisting of methylaluminoxane (MAO) and poly methylaluminoxane (PMAO).
In one embodiment, the single site catalyst is a catalyst represented by Formula II:

Formula II
wherein,
LY is a Schiff base adduct formed from m-phenylene diamine and 3-tert butyl salicylaldehyde or 3,5-di tert butyl salicylaldehyde;

M is a transition metal selected from the group consisting of Hafnium (Hf), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V) and Titanium (Ti); and.

X is a halide selected from the group consisting of Cl, Br and I.
In one embodiment, the single site catalyst

is represented by Formula IB
Formula IB
wherein, R1, R2, R4, R6 R8, R10 and R12 are same or different, and independently selected from the group consisting of hydrogen, aryl, hetero-aryl and halide;
R5 and R9 are tertiary alkyl groups;
R7 and R11 are same or different, and independently selected from the group consisting of hydrogen and tertiary alkyl group;
R3 is independently selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy, carboxylic and sulphonic;
M is a transition metal selected from the group consisting of Hafnium (Hf), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V) and Titanium (Ti); and

X is a halide selected from the group consisting of Cl, Br and I; and
n is an integer 2.

In one embodiment, the ion exchange resin is a sulfonated polystyrene cation exchange resin represented by Formula III:

Formula III
wherein P is cross-linked polystyrene-divinylbenzene copolymer matrix.
In one embodiment, the intermediate formed is a compound represented by Formula IV:
Formula IV
In one embodiment, the cationic complex of single site catalyst is represented by Formula V:

Formula V
wherein, LY is a Schiff base adduct formed from m-phenylene diamine and 3-tert butyl salicylaldehyde or 3,5-di tert butyl salicylaldehyde; and

M is a transition metal selected from the group consisting of Hafnium (Hf), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V) and Titanium (Ti).

In accordance with still another aspect of the present disclosure there is provided a process for polymerization of olefin, said process comprises subjecting said olefin to polymerization in the presence of an ion exchange resin immobilized single site catalyst of the present disclosure.

DETAILED DESCRIPTION:

The present disclosure focuses on utilization of an ion exchange resin as an organic support for immobilization of single site catalyst, particularly single site transition metal catalyst.
According to the present disclosure the single site catalysts are converted to corresponding complexes by reacting catalyst with at least one aluminium alkyl compound. The aluminium alkyl compound acts as a co-catalyst. In one embodiment the complex is cationic complex. The obtained complexes are completely exchanged on the exchanger resin resulting in an immobilized single site catalyst.
In one embodiment the exchanger resin is a cation exchanger resin. In another embodiment the exchanger resin is anion exchanger resin.
In one embodiment the process of the present disclosure involves the following steps:
In the first step, at least one single site catalyst is reacted with at least one aluminium alkyl compound to obtain a cationic complex of the single site catalyst. The aluminium alkyl compound includes but is not limited to methylaluminoxane (MAO) and poly methylaluminoxane (PMAO).
In the next step, the cation of the ion exchange resin is exchanged with the cationic complex of single site catalyst to obtain the ion exchange resin immobilized single site catalyst.

The ion exchange resin immobilized single site catalyst of the present disclosure is represented by Formula I:
Formula I
In one embodiment,
P is a cross-linked polystyrene-divinylbenzene copolymer matrix,
LY is a Schiff base adduct formed from m-phenylene diamine and 3-tert butyl salicylaldehyde or 3,5-di tert butyl salicylaldehyde; and

M is a transition metal selected from the group consisting of Hafnium (Hf), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V) and Titanium (Ti).

In one embodiment, the cationic component

of Formula I represents the structure of single site catalyst having formula IA:
Formula IA
wherein, R1, R2, R4, R6 R8, R10 and R12 are same or different, and independently selected from the group consisting of hydrogen, aryl, hetero-aryl and halide;
R5 and R9 are tertiary alkyl groups;
R7 and R11 are same or different, and independently selected from the group consisting of hydrogen and tertiary alkyl group;
R3 is independently selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy, carboxylic and sulphonic;
M is a transition metal selected from the group consisting of Hafnium (Hf), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V) and Titanium (Ti); and
X is a halide selected from the group consisting of Cl, Br and I; and
n is an integer 2.

In one embodiment, the single site catalyst is a catalyst represented by Formula II:
Formula II
wherein,
LY is a Schiff base adduct formed from m-phenylene diamine and 3-tert butyl salicylaldehyde or 3,5-di tert butyl salicylaldehyde, and
M is a transition metal selected from the group consisting of Hafnium (Hf), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V) and Titanium (Ti); and
X is a halide selected from the group consisting of Cl, Br and I.
In one embodiment the single site catalyst of Formula II

is represented by Formula IB
Formula IB
wherein, R1, R2, R4, R6 R8, R10 and R12 are same or different, and independently selected from the group consisting of hydrogen, aryl, hetero-aryl and halide;
R5 and R9 are tertiary alkyl groups;
R7 and R11 are same or different, and independently selected from the group consisting of hydrogen and tertiary alkyl group;
R3 is independently selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy, carboxylic and sulphonic;
M is a transition metal selected from the group consisting of Hafnium (Hf), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V) and Titanium (Ti); and
X is a halide selected from the group consisting of Cl, Br and I; and
n is an integer 2.
In one embodiment, the exchange resin is a sulfonated polystyrene cation exchange resin represented by Formula III:

Formula III
wherein P is cross-linked polystyrene-divinylbenzene copolymer matrix.
In one embodiment, the intermediate formed is a compound represented by Formula IV:
Formula IV
In one embodiment, the complex is represented by Formula V:

Formula V
wherein, LY is a SchiffSchiff base adduct formed from m-phenylene diamine and 3-tert butyl salicylaldehyde or 3,5-di tert butyl salicylaldehyde; and

M is a transition metal selected from the group consisting of Hafnium (Hf), Manganese (Mn), Iron (Fe), Rhenium (Re), Tungsten (W), Niobium (Nb), Tantalum (Ta), Vanadium (V) and Titanium (Ti),

In one embodiment, the cation exchange resin is dispersed in a solvent which includes but is not limited to toluene to swell said resin. To this swollen resin a single site catalyst is added followed by addition of PMAO. The single site catalyst is added in the form of dispersion/solution in toluene. It is found that after the addition of single site catalyst there is no color change of resin and the supernatant has brown color. No ion exchange takes place.
After the addition of PMAO under nitrogen and room temperature, it is found that the supernatant slowly turns colorless and the resin residue shows dark brown color. At this stage ion exchange takes place.

In another embodiment, the cation exchange resin is dispersed in a solvent which includes but is not limited to toluene to swell said resin. To this swollen resin PMAO is added followed by addition of a single site catalyst. The single site catalyst is added in the form of dispersion/solution in toluene under nitrogen and room temperature. It is found that after the addition of PMAO under nitrogen and room temperature to said resin there is formation of gel at the initial stage which disappears at later stage. After the addition of single site catalyst, the supernatant slowly turns colorless and the resin residue shows dark brown color. At this stage ion exchange takes place.

The immobilized novel catalyst is then characterized through EDAX for elemental contour mapping followed by evaluation for their performance characteristics through olefin polymerizations.

It is found that subtle colour change takes place on the resin (intense colour formation) and as well as on the reaction medium (disappearance of colour). In the control experiments, where the single site catalyst is not treated with aluminium alkyl to generate the desired complex, shows no cationic exchange phenomenon, indicating absolute requirement of the cationic complex of the single site catalyst for cation exchange on the resin.
In accordance with still another aspect of the present disclosure there is provided a process for polymerization of olefin, said process comprises subjecting said olefin to polymerization in the presence of an ion exchange resin immobilized single site catalyst of the present disclosure.

TECHNICAL ADVANCE AND ECONOMIC SIGNIFICANCE:
• Ion exchange resin immobilized single site catalyst with a composite capability to impart various desired properties to polyolefins
• A simple and cost effective method for preparation of the ion exchange resin immobilized single site catalyst

Throughout this specification the word “comprise”, or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

The use of the expression “at least” or “at least one” suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the disclosure to achieve one or more of the desired objects or results.

Any discussion of documents, acts, materials, devices, articles or the like that has been included in this specification is solely for the purpose of providing a context for the disclosure. It is not to be taken as an admission that any or all of these matters form a part of the prior art base or were common general knowledge in the field relevant to the disclosure as it existed anywhere before the priority date of this application.

The numerical values mentioned for the various physical parameters, dimensions or quantities are only approximations and it is envisaged that the values higher/lower than the numerical values assigned to the parameters, dimensions or quantities fall within the scope of the disclosure, unless there is a statement in the specification specific to the contrary.

While considerable emphasis has been placed herein on the particular features of this disclosure, it will be appreciated that various modifications can be made, and that many changes can be made in the preferred embodiments without departing from the principles of the disclosure. These and other modifications in the nature of the disclosure or the preferred embodiments will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation.