Title of Invention

"A PROCESS FOR PREPARATION OF NANOPARTICLES OF HIGHER MOLECULAR WEIGHT OF POLYETHELENE"

Abstract

Accordingly to the Invention, there is provided a Process for preparation of nanoparticles of higher molecular weight of polyethylene comprising steps of:- Introduction of n-hexane into the reactor followed by introduction of specially prepared catalyst TiCl4 and trimethyl aluminum into the reactor maintained at a temperature of 300-65° under inert atmosphere; addition of ethylene into the reactor maintained at 70-150 for 0.5 to 2 hours and at a pressure of 0.1 to 2 MPa so as to cause polymerization;treatment of the solution obtained above with methanol acidified with traces of HCL to decompose and dissolve catalyst; treatment of the solution obtained above with a solvent followed by heating at -30oC to 150oC form a clear solution and cooled to get nanoparticles; and followed by the separation of nanoparticles of polyethylene as herein described.

Full Text

FBELD OF THE INVENTION: This invention relates to a process for preparation of nanoparticles of higher molecular weight of polyethylene, polypropylene and polystyrene. BACKGROUND OF THE INVENTION: Generally polymers are high molecular weight material. Its number average molecular weight is greater than 1,00,000 and available in granular form. The particle size is ~2 mm (minimum). Due to its high molecular weight, it was not possible to prepare polymers at nano scale. Polymer particles of different shapes and sizes are critical in numerous applications, including polymer blends or alloys, polymer powder spray coating, polymer powder impregnations of inorganic fibers in composites, and in polymer-supported heterogeneous catalysis. Recently, significant commercial and scientific attention has been focused on the multicomponent polymer system as a means for producing new materials on the nanometer scale. Composites, polymer particles or polymer alloys with specifically tailored properties can find many novel uses in such field as electro-optic and luminescent devices, thermoplastics and conducting materials, hybrid inorganic-organic polymer alloys, and polymer supported heterogeneous catalysis. These are dimensionally larger than so called atoms and yet smaller than the conventional polymer powders with most of the comprising species lying on the surface itself. The commercial polyethylene (low density polyethylene, high density polyethylene, liner low density polyethylene, ultra high molecular weight polyethylene, etc) is synthesized by the Ziegler process using aluminium trialkyl-TiCU complex as catalyst, Phillips process using CrOs as catalyst and Standard oil process using molybdenum as catalyst. The size of this commercial polyethylene is ~ 2-5 mm in diameter. The synthesis of commercial polypropylene became possible through the commercial utilization of co-ordination polymerization during 1957-60. Propylene, the monomer, is obtained from the cracking of petroleum products. The size of this commercial polypropylene is ~ 2-5 mm in diameter. Similarly the commercial polystyrene is synthesized by the bulk and suspension polymerization (and the emulsion process to a lesser extent). Similarly the size of this commercial polystyrene is ~ 2-5 mm in diameter. Regarding the synthesis of micron sized polymer (polyethylene) has been reported by Otaigbe et al. [Otaigbe JU, Noid DW, Sumpter BG (1998) Advances in Polymer Technol. 17:161] through the gas atomizing technique without mentioning its molecular weight. The yield is less than 0.01% and particle sizes ranging from 25-200 um. In this technique, the polymer is melted at a high temperature and passed through an orifice into a vacuum chamber. Spherical polymer particles (10-35 nm) are prepared by the chemical polymerization of aniline in an inverse water-in-oil micro emulsion process [Chan HSO, Ming L, ChewlStrMa L, Seow SH., (1993) J Mater Chem 3:1109; Xu, XJ., Chew, CH., Siow, KS., Wong, MK, and Gan, L.M., (1999), Langmuir, 15:8067; Anderson, CD., Sudol, ED., and El-Aasser, MS., (2002), Macromolecules, 35:574; Ries, MM., Araujo, PHH., Sayer, C., Giudici, R., (2003), Polymer, 44:6123, Ries, MM., Araujo, PHH., Sayer, C., Giudici, R, (2003), Polymer, 44:6123; Klein, M., US Patent 4,207,378, June 1980 and Wang, X., Foltz, VJ, Sadhukhan, P. US patent 6,689,469, February 2004]. This micro emulsion method provides a denser, more uniform and compact film of higher condensation than that produced in an aqueous medium. But the molecular weight of polymer is less than 20,000. The conventional process can be briefly summarized as follows:- (1) Microemulsion technique (2) Cryogenic grinding Commercial polymer is available in granular form and its diameter is generally greater than 2 mm. Materials developed till date: polyethylene glycol, polyvinyl alcohol, polyvinyl chloride, polystyrene. Size of the particles: Generally the minimum size is -300 nm and in case of polystyrene it is 40 nm. However, the molecular weight is less than 10,000 in all cases. Economic: Both are costly processes. Design of Process: These processes are too much complicated. Yield: Very low, less than 0.1% for micron sized low molecular weight polymer. (Maximum) Cost of production: Costly process OBJECTS OF THE PRESENT INVENTION; The object of the present invention is to prepare nano sized particles of high molecular weight engineering polymers like polyethylene, polypropylene, polystyrene, etc. Another object of the present invention is to propose a process for preparation of nano sized high molecular weight engineering polymers with molecular weight greater than 1,00,000 and particle size as low as ~ 10 nm. Still another object of the present invention is to characterize nano sized particles through atomic force microscopy, transmission electron microscopy, scanning electron microscopy, X-ray diffraction, infrared spectroscopy, particle size distribution, molecular weight, etc. Further object of the present invention is to propose a process for preparation of nanoparticles of higher molecular weight of polyethylene, polypropylene and polystyrene wherein the particle size of high molecular weight polyethylene varies from 10 to 130 nm and at least 70% of the nano polyethylene have diameter less than 25 nm. Yet further object of the present invention is to propose a process for preparation of nanoparticles of higher molecular weight of polyethylene, polypropylene and polystyrene wherein the particle size of high molecular weight polypropylene varies from 25 to 100 nm and at least 80% of the nano polypropylene have diameter less than 50 nm. Yet another object of the present invention is to propose a process for preparation of nanoparticles of higher molecular weight of polyethylene, polypropylene and polystyrene wherein the particle size of high molecular weight polystyrene varies from 20 to 40 nm and at least 75% of the nano polypropylene have diameter less than 25 nm. Yet further another object of the present invention is to propose a process for preparation of nanoparticles of higher molecular weight of polyethylene, polypropylene and polystyrene wherein the molecular weight of nano sized polyethylene is greater than 10,00,000 (viscosity average molecular weight), which is equivalent to the commercial polyethylene. Yet another further object of the present invention is to propose a process for preparation of nanoparticles of higher molecular weight of polyethylene, polypropylene and polystyrene wherein the molecular weight of nano sized polypropylene is greater than 10,00,000 (viscosity average molecular weight), which is equivalent to the commercial polypropylene. Yet further another object of the present invention is to propose a process for preparation of nanoparticles of higher molecular weight of polyethylene, polypropylene and polystyrene wherein the molecular weight of nano sized polystyrene is greater than 10,00,000 (viscosity average molecular weight), which is equivalent to the commercial polystyrene. Still another object of the present invention is to propose a process for preparation of nanoparticles of higher molecular weight of polyethylene, polypropylene and polystyrene wherein the nano sized high molecular weight polyethylene is more crystalline in nature with respect to the commercial low density polyethylene supported by the peak observed at 22° (29) through X-ray diffraction studies. Still further another object of the present invention is to propose a process for preparation of nanoparticles of higher molecular weight of polyethylene, polypropylene and polystyrene wherein the nano sized high molecular weight polyethylene is more crystalline in nature with respect to the commercial high density polyethylene supported by the peak observed at 22° (29) through X-ray diffraction studies. Still further another object of the present invention is to propose a process for preparation of nanoparticles of higher molecular weight of polyethylene, polypropylene and polystyrene wherein the nano sized high molecular weight polyethylene is more crystalline in nature with respect to the commercial low density polyethylene supported by the peak observed at 24° (29) through X-ray diffraction studies. Yet further object of the present invention is to propose a process for preparation of nanoparticles of higher molecular weight of polyethylene, polypropylene and polystyrene wherein the nano sized high molecular weight polyethylene is more crystalline in nature with respect to the commercial high density polyethylene supported by the peak observed at 24° (29) through X-ray diffraction studies. Yet further object of the present invention is to propose a process for preparation of nanoparticles of higher molecular weight of polyethylene, polypropylene and polystyrene wherein the nano sized high molecular weight polypropylene is more crystalline in nature with respect to the commercial polypropylene supported by the peak observed at 16.8° (26) through X-ray diffraction studies. Still further object of the present invention is to propose a process for preparation of nanoparticles of higher molecular weight of polyethylene, polypropylene and polystyrene wherein the nano sized high molecular weight polypropylene is more crystalline in nature with respect to the commercial polypropylene supported by the peak observed at 18.6° (26) through X-ray diffraction studies. Still further object of the present invention is to propose a process for preparation of nanoparticles of higher molecular weight of polyethylene, polypropylene and polystyrene wherein the nano sized high molecular weight polypropylene is more crystalline in nature with respect to the commercial polypropylene supported by the peak observed at 21.8° (26) through X-ray diffraction studies. Still further object of the present invention is to propose a process for preparation of nanoparticles of higher molecular weight of polyethylene, polypropylene and polystyrene wherein the nano sized high molecular weight polystyrene is more crystalline in nature with respect to the commercial polystyrene supported by the peak observed at 16.7° (26) through X-ray diffraction studies. Still further object of the present invention is to propose a process for preparation of nanoparticles of higher molecular weight of polyethylene, polypropylene and polystyrene which doesn't need any surfactant, other chemicals used in microemulsion process; and cryogenic apparatus in cryogenic grinding process, very economic and results in very good yield. STATEMENT OF THE INVENTION According to this invention there is provided a process for preparation of nanoparticles of higher molecular weight of polyethylene comprising steps of:- introduction of n-hexane into the reactor followed by introduction of TiCU and trimethyl aluminum as herein described into the reactor maintained at a temperature of 30-65°C under inert atmosphere, addition of ethylene into the reactor maintained at 70-150°C for 0.5 to 2 hours and at a pressure of 0.1 to 2 MPa so as to cause polymerization treatment of the solution obtained above with methanol acidified with traces of HC1 to decompose and dissolve catalyst, treatment of the solution obtained above with a solvent followed by heating at -30°C to 150°C to form a clear solution and cooled to get nanoparticles separation of nanoparticles of polyethylene as herein described. Further according to this invention there is provided a process for preparation of nanoparticles of higher molecular weight of polypropylene comprising steps ofintroduction of n-hexane into the reactor followed by introduction of TiCl4 and trimethyl aluminum as herein described into the reactor maintained at a temperature of40-100°C, addition of propylene and hydrogen into the reactor maintained at 70-150°C for 6 to 24 hours and at a pressure of 0.1 to 2 MPa so as to cause polymerization treatment of the solution obtained above with methanol acidified with traces of HC1 to decompose and dissolve catalyst, treatment of the solution obtained above with a solvent followed by heating at 60°C to 125°C to form a clear solution and cooled to get nanoparticles separation of nanoparticles of polypropylene as herein described. Further according to this invention there is provided a process for preparation of nanoparticles of higher molecular weight of polystyrene comprising steps of:- - Introduction of n-hexane into the reactor followed by introduction of specially prepared catalyst TiCl4 and trimethyl aluminum into the reactor maintained at a temperature of 300-65° under inert atmosphere. - Addition of ethylene into the reactor maintained at 70-150 for 0.5 to 2 hours and at a pressure of 0.1 to 2 MPa so as to cause polymerization. - Treatment of the solution obtained above with methanol acidified with traces of HCL to decompose and dissolve catalyst. - Treatment of the solution obtained above with a solvent followed by heating at -300C to 150oC form a clear solution and cooled to get nanoparticles. - Separation of nanoparticles of polyethylene as herein described. BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS; Further, objection and advantages of this invention will be more apparent from the ensuring description when read in conjunction with the accompanying drawings and wherein: Figure 1 shows: Schematic diagram of conventional simple reactor for the production of nano sized high molecular weight engineering polymers. Figure 2 shows: AFM micrographs of nano sized molecular weight polyethylene wherein the particle size of polyethylene varies from 10 to 130 nm. Figure 3 shows: AFM micrographs of nano sized high molecular weight polypropylene wherein particle size of polypropylene varies from 25 to 100 nm. Figure 4 shows: Another AFM micrographs of nano sized high molecular weight polypropylene wherein particle size of polypropylene varies from 25 to 100 nm. Figure 5 shows: AFM micrographs of nano sized high molecular weight polystyrene wherein particle size of polystyrene varies from 20 to 40 nm. Figure 6 shows: particle size distribution of nano sized high molecular weight polyethylene. Figure 13 shows: FT-IR spectra of commercial polypropylene and nano sized high molecular weight polypropylene. Figure 14 shows: FT-IR spectra of commercial polystyrene and nano sized high molecular weight polystyrene. Figure 15 shows: XRD intensity patterns for commercial high density polyethylene, commercial low density polyethylene and nano sized high molecular weight polyethylene (2 theta varies from 18 to 25°). Figure 16 shows: XRD intensity patterns for commercial polypropylene and nano sized high molecular weight polypropylene (2 theta varies from 15 to 25°). Figure 17 shows: XRD intensity patterns for commercial polystyrene and nano sized high molecular weight polystyrene (2 theta varies from 10 to 25°). Figure 18 shows: Viscosity vs concentration profile for commercial polystyrene at a temperature of 25°C. Figure 19 shows: Viscosity vs concentration profile for nano sized high molecular weight polystyrene at a temperature of 25°C. DETAILED DESCRIPTION OF THE INVENTION WITH REFERENCE TO ACCOMPANYING DRAWINGS: Reference may be made to Fig 1 which shows a reactor comprising Feeding of ingredients (1, 3, 5), Outlet of gas (environmental gas) (2), Inlet of gas (environmental gas) (4), Jacket (6) for controlling the temperature from -30 to +250°C by circulating of liquid nitrogen (below sub ambient temperature) and hot oil (above room temperature) and Magnetic stirrer (7) for controlling the shear rate in the solution. The reactor is provided with the provision to control the reaction temperatures from -30 (sub ambient) to +250°C, reaction time, different atmospheres using purge gases (nitrogen, argon, helium, carbon dioxide, oxygen, etc) and shear rates (0.2 to 200 rad/s) by magnetic stirrer. 1. A process for preparation of nano sized high molecular weight polyethylene comprising the steps of- Step-1: Drying of n-Hexane -n-hexane (75 to 90 wt%) is added to calcium chloride (25 to 10 wt%) to obtain a mixture -this mixture is heated at a temperature of 10 to 50°C for 1 to 24 hours -sodium wires are added into the above mixture until evolution of hydrogen bubbles is observed - a pinch of benzophenone (-0.1 to 1 wt%) is added to the above mixture (99.9 to 99 wt%) after 1 to 6 hours -this mixture is refluxed at a temperature of 75 to 200°C in an inert atmosphere, until it sustains dark blue colour -after sustaining the dark blue colour the mixture is refluxed for another 1 to 3 hour and cooled to room temperature under inert atmosphere -the mixture is distilled under inert atmosphere for the collection of dry n-hexane. Step-2: Purification and drying of toluene 5 to 15 wt% of 50 to 99% sulphuric acid is added into toluene (95 to 85 wt%) -this mixture is stirred using magnetic stirrer for 1 to 12 hours followed by separation of acid from the mixture using separating funnel and remaining toluene is washed with distilled water in the separating funnel -again it is washed with saturated sodium bicarbonate solution (1 to 10%) in the distilled water for complete removal of sulphuric acid -same procedure is followed for drying the toluene as mentioned in the case of n-hexane Step-3: Preparation of catalyst (TiCU) -dry hexane (50 to 70 wt%) and titanium tetra chloride (50 to 30 wt%) are added under inert atmosphere at a temperature of 10 to 50°C -the mixture is kept under inert atmosphere for 60 to 9000 seconds -the flask is cooled to a temperature of 25 to 10°C with a septum Step-4: Drying of diethylether: -85 to 97 wt% of diethyl ether is taken in a clean dry bottle flask which is added with 15 to 3 wt% of calcium chloride to obtain a mixture -this mixture is decanted after 1 to 12 hours for removal of large percentage of water. -sodium wires are pressed into the bottle until the stoppage of evolution of hydrogen bubbles -a pinch of benzophenon (0.01 to 0.05 wt%) is added to the above mixture (99.99 to 99.95 wt%) and kept for 1 to 6 hours -the mixture is refluxed until it sustains dark blue colour in the inert atmosphere -after sustaining dark blue colour the mixture is refluxed for another 2 to 4 hours at 25 to 75°C and cooled under inert atmosphere to the room temperature of 25°C to obtain dry diethylether which is distilled using a distillation condenser Step-5: Preparation of methyl magnesium iodide: -The magnesium metal (96 to 99 wt%) and a pinch of Iodine (4 to 1 wt%) are mixed together. -after flashing this system (70 to 80 wt%) by nitrogen to create inert atmosphere, diethyl ether (30 to 20 wt%) as obtained above is added to obtain a reaction mixture -the required amount of methyl iodide (75 to 90 wt% with respect to magnesium) highly diluted with ether is admitted in the dropping funnel with rapid magnetic stirring which causes vigorous reaction. As a result reddish colour of mixture becomes colourless -after being colourless, the diluted iodomethane (1 to 10 wt%) is added to the reaction mixture drop wise keeping reaction bottle flask in the ice bath -after complete addition the reaction mixture is refluxed for 2 hours at a temperature of 35 to 40°C - It is stored in the inert atmosphere as it is moisture sensitive and pyrophoric in nature Step-6: Preparation of trimethyl aluminium: - 91 to 98 wt% of dried diethyl ether is added into the bottle flask with rapid magnetic stirring followed by addition of anhydrous aluminium chloride (9 to 2 wt%) into the ether slowly at 0°C for preparing solution -freshly prepared Grignard reagent (70 to 85 wt% with respect to the aluminium chloride) is added drop wise to the solution with the help of cannula -after complete addition of Grignard reagent the reaction mixture is refluxed in the temperature range of 20 to 60°C for 1 to 4 hours circulating the chilled water through the condenser for completion of the reaction -this mixture has a clear solution of trimethyl aluminium etherate complex and solid material of magnesium chloride iodide at the bottom of the round bottle flask Step-7: Isolation of trimethyl aluminium: -the reaction mixture is heated at 20 to 70°C for 1 to 4 hours for removal of excess ether - vacuum of 30 mm Hg is created into the system and trimethyl aluminium is distilled out in the temperature range of 30 to 90°C using two ice traps between vacuum pump and bottle flask for complete condensation of trimethyl aluminium -trimethyl aluminium complexes with ether as etherate and a little amount of compound is found in the traps and collected with the help of syringe and needle Step-8: Polymerization of ethylene using TiCLf/fCH^Al catalyst to get nano sized high molecular weight polyethylene - 95 to 99.8 wt% of dried n-hexane is introduced into the dry and clean reactor fully charged with nitrogen gas, which is maintained at a temperature of 30 to 65°C -at this temperature a calculated amount of TiCU (0.1 to 3 wt%) and trimethyl aluminium (0.1 to 2 wt%) are charged into the reactor with the help of syringe and needle under inert atmosphere -the temperature of the system is then raised to 75 to 150°C -after stirring for 10 to 60 minutes ethylene is introduced into the reactor at the required pressure -ethylene (5 to 150 ml/min) is added for 0.5 to 2 hour maintaining the temperature in between 70-150°C and pressure of 0.1 to 2 MPa followed by passing of water through cooling coils -after polymerization methanol (5 to 25 wt%) is added to deactivate the unreacted catalyst and heated to 250°C to remove the unreacted ethylene followed by cooling at 50°C - a trace of HCL (1 to 5 wt%) is added to decompose and dissolve the catalyst -another solvent (70 to 95 wt%) is added into the mixture of 30 to 5 wt% and heated to - 30 °C to 150°C to form a clear solution and cooled slowly with continuous stirring over a shear rate of 0.2 to 200 rad/s for 0.1 to 12 hours. -polyethylene is separated by filtration and dried under reduced pressure of 30 mm Hg after washing with cold water to obtain the nano sized high molecular weight polymer The heating of catalyst and ethylene in the reactor under a pressure of 0.1 to 2 MPa and temperature of 75-150°C involves the following reaction CH2=CH2 + Catalyst = -(CH2-CH2)n- + Catalyst 2. A process for preparation of a nano sized high molecular weight polypropylene comprising the steps of:- Step 1: drying on n-hexane, same as for nano polyethylene Step 2: purification and drying of toluene, same as for nano polyethylene Step 3: preparation of catalyst, TiCl4, same as for nano polyethylene Step 4: synthesis of trimethyl aluminium, same as for nano polyethylene Step 5: isolation of trimethyl aluminium, same as for nano polyethylene Step 6: drying of diethyl ether, same as for nano polyethylene Step 7: preparation of methyl magnesium chloride same as for nano polyethylene. Step 8: preparation of nano sized high molecular weight polypropylene consisting the steps of -95 to 99.8 wt% of dried n-hexane is introduced into dry and clean reactor fully charged with nitrogen gas, which is maintained at a temperature of 40 to 100°C -at this temperature a calculated amount of TiCU (0.1 to 3 wt%) and trimethyl aluminium (0.1 to 2 wt%) are charged into the reactor with the help of syringe and needle under inert atmosphere -the temperature of the system is then raised to 75 to 150°C -after stirring for 10 to 60 minutes propylene (5 to 150 ml/min) and hydrogen (1 to 5 ml/min) (here hydrogen acts as a chain terminating agent) are introduced into the reactor at the required pressure -propylene and hydrogen is added for 6 to 24 hours maintaining the temperature in the range of 70-175°C and pressure of 0.1 to 2 MPa and water is allowed to pass through the cooling coils after polymerization methanol (5 to 25 wt%) is added to deactivate the unreacted catalyst and heated to the temperature range of 150 to 250°C to remove the unreacted propylene -then it is cooled to the temperature in the range of 10-50°C -after that a trace of HCL (1 to 5 wt%) is added to decompose and dissolve the catalyst -another solvent (70 to 95 wt%) is added into the mixture of 30 to 5 wt% and heated at a temperature of 60 to 125°C to form a clear solution and cooled slowly with continuous stirring over a shear rate of 0.2 to 200 rad/s for 0.1 to 12 hours -polypropylene is separated by filtration and dried under reduced pressure of 30 mm Hg after washing with water to obtain the nano sized high molecular weight polymer. The heating of catalyst, propylene and hydrogen in a reactor under a pressure of 0.1 to 2 MPa involves the following reaction CH3-CH=CH2 + H2 + Catalyst = -(CH3-CH-CH2)n- + Catalyst 3. Synthesis of nano sized high molecular weight polystyrene comprising the steps of> -90 to 99.9 wt% benzene is introduced into the dry and clean reactor fully charged with environmental gas, which is maintained at a temperature of 30 to 70°C -at this temperature a calculated amount of A1C13 (5 to 0.05 wt%) is charged into the reactor under same atmosphere -the temperature of the system is then raised to 60 to 100°C -after stirring for 10 to 300 minutes ethylene (5 to 50 ml/min) is introduced into the reactor at the required pressure -ethylene is added for 1 to 6 hours maintaining the temperature in the range of 70-130°C and pressure of 0.1 to 2 MPa and water is allowed to pass through the cooling coils -after 0.5 to 4 hours a calculated amount of magnesium oxide (5 to 0.05 wt%) is added followed by heating of the mixture at a temperature of 400 to 800°C -after 0.5 to 2 hour the mixture is cooled to a temperature of 30 to 70°C and the styrene is separated by distillation -pure styrene (95 to 99.5 wt%) and a pinch of catalyst, 5 to 0.5 wt% (hydrogen peroxide, 50 to 99.9% purity) is heated in a temperature range of 100 to 200°C in a reactor. The reactor is fitted with heating and cooling jackets to control the temperature -the melt containing polystyrene and traces of styrene is heated in a temperature range of 120 to 200°C to remove styrene monomer -the mixture is cooled to 30 to 75°C -another solvent (70 to 95 wt%) is added into the mixture of 30 to 5 wt% and heated in the temperature range of 75 to 150°C to form a clear solution followed by cooling slowly with continuous stirring over a shear rate of 0.2 to 200 rad/s for 0.1 to 12 hours -polystyrene is separated by filtration and dried under reduced pressure of 30 mm Hg after washing with water to obtain the nano sized high molecular weight polymer. Alkylation of benzene (i.e., formation of ethyl benzene) through reaction with ethylene in the presence of Friedel-Crafts catalyst (in this case we used A1C13) involves the following reaction: - C6H6 +CH2=CH2 + A1C13 = C6H5-CH2CH3 + A1C13 Dehydrogenation of Ethyl benzene to styrene in the presence of catalyst (in this case we used magnesium oxide) involves the following reaction:- C6H5-CH2CH3 + MgO = C6H5-CH=CH2 + H2 + MgO Heating of Pure styrene and catalyst (here we used hydrogen peroxide) in a reactor involves the following reaction:- C6H5-CH=CH2 + H2O2 = -(C6H5-CHCH2)n- + C6H5-CH=CH2 The solvent used in the above processes is selected from the group of toluene, xylene, 1,2,4- trichloro benzene, decalin, 1-chloronaphthalene, biphenyl, dodecanol, diphenylmethane, diphenyl ether, hexadecane, 1-octanol, isoamyl alcohol, benzene, cyclohexane, toluene, cyclohexanone, isoamyl acetate, isobutyl acetate, phenyl ether, chloroform, decahydronaphthalene, diethyloxalate, dimethylphthalate, dioxane, ethyl acetate, ethyl benzene, methyl chloride, 1-nitopropane, phosphorous trichloride, tetrahydofiiran, tributyl phosphate, acrylonitrile, chlorobenzene, acetic acid, n-butanol, isobutanol, carbon tetrachloride, dimethyl siloxane, methanol, acetophenone, paraffin liquid, water, hydroxy propyl cellulose, and mixture thereof. Theory behind the formation of nano sized polymer through thermodynamics: Partial molar free energy, AG* of a polymer during formation of nanoparticles is composed of following three forces AG" = &Gsp + AG, + AGe/ ...(1) where AG AGf and AGe/ are the contributions of solvent-polymer mixing force, polymer network elastic-retractile force and particle-sol vent interfacial tension force respectively. Partial molar free energy change by the absorption of the solvent droplets is represented by the following equation In ...(2) where 0] is the volume fraction of the solvent, 02 is the volume fraction of the polymer, J is the ratio of molar volume of polymer and solvent, x is the solvent polymer interaction parameter, y is the interfacial energy, r is the radius of the particles, and Fy is the partial molar volume of the solvent. Form Equation (2), a thermodynamics equation for the formation of particles consisting of polymer, other chemicals (if any) and mixtures is given below: where 0t is the volume fraction of the solvent, 02 is the volume fraction of the other chemicals, 0s is the volume fraction of the polymer, Ji is the ratio of molar volume of other chemicals and solvent, J3 is the ratio of molar volume of polymer and solvent, xu and %i3 are the interaction parameter of the solvent with other chemicals and polymer, respectively, and X23 is the interaction parameter of the other chemicals with the polymer. For the polymer particles system, l/j3 can be set equal to zero in Equation (3), because a polymer has limitless js value. Therefore, Equation (3) can be simplified as follows: The elastic free energy change, AGei is an entropy term associated with the change in the configuration of the polymer network, and describe as follows: where N is the effective number of chains in the network per unit volume. Consequently, the partial molar free energy, AG of the solvent in the polymer particles during formation of nano particles gives At the equilibrium state, the following thermodynamic equation can be obtained Particle radius r can be represented as follows: where r0 is the initial particle radius. F}, ¥2 and V3 are the molar volume of solvent, other solvents if any and polymer respectively. The rate of transport of solvent molecules to the polymer particles for the formation of nano sized particles can be determined as where D is the diffusion constant of solvent molecules, C is the solubility of the polymer particles, rs is the radius of the polymer particles, and Ns is the number of the particles, In Equation (9), AG can be obtained form the Equation (6). It proves that the formation of nano sized polymers is feasible through the control of thermodynamic parameters. The size of nanoparticles is analyzed through atomic force microscopy, scanning electron microscopy, transmission electron microscopy, etc. Characterization of nano sized high molecular weight polymer through atomic force microscopy: The particle size and morphology of nano sized high molecular weight polyethylene, polypropylene and polystyrene were determined by Atomic Force Microscope (AFM), Molecular Imaging, USA using acoustic AC mode, force constant of 0.6 N/m and frequency of 150 KHz. The micro graph shows that the nano sized high molecular weight polyethylene (Fig 2), polypropylene (Figs 3 and 4) and polystyrene (Fig 5) are spherical in nature. The particle size for polyethylene, polypropylene and polystyrene is within the range of 10 to 130, 25 to 100 and 20 to 40 nm respectively. The particle size distribution of high molecular weight polyethylene, polypropylene and polystyrene is shown in Figs 6, 7 and 8 respectively. Characterization of nano sized high molecular weight polymer through transmission electron microscopy: The nanopolymers were dispersed in a solvent and a drop of this solution was sprayed on the carbon-coated grid with the help of some suitable dropper or syringe. The TEM micrographs were taken with JEOL JEM 2000FX Transmission Electron Microscope, at a voltage of 120 kVA and at different magnifications. The micro graph shows that the nano sized high molecular weight polyethylene (Fig 9) and polypropylene (Fig 10) are spherical in nature. Particle size varies within the range of 10 to 130, and 25 to 100 nm for polyethylene and polypropylene respectively. Characterization of nano sized high molecular weight polymer through scanning electron microscopy: The particle size and morphology of nano sized high molecular weight polyethylene, polypropylene and polystyrene were also determined by a JEOL JSM 840A Scanning Electron Microscope (SEM). The micro graph (Fig 11) shows that the nano sized high molecular weight polypropylene is spherical in nature. To avoid the thermal degradation of polymer the photograph is taken at an accelerating voltage of 15-20 kV. The particle size of high molecular weight polypropylene is within the range of 25 to 100 nm. Characterization of nano sized high molecular weight polymer through infrared spectrosc The infrared spectrum of commercial high density polyethylene, low density polyethylene and nano sized high molecular weight polyethylene was studied by "BRUKER VECTOR 22" infrared spectrometer to find out the difference in chemical structure between these polymers. Fig 12 shows the IR spectra of commercial high density polyethylene. The peak positions at 2800-2950 cm"1 (broad peak), 1466 cm"1 (strong peak), 1365 cm"1 (strong peak) and 724 cm"1 (strong peak) are assigned to the -C-H stretching, -C-H vibration, -C-H symmetric vibration and -C-H rocking respectively. The other two peaks 730 and 720 cm"1 (strong) is orthorhombic crystalline structure of commercial high density polyethylene. The 723 cm"1 peak position is associated with the amorphous fraction of commercial high density polyethylene. But the 717 cm"1 is assigned to the monoclinic crystalline structure of commercial high density polyethylene. The JR. spectra of commercial low density polyethylene is also included in the same Fig 12 for the comparison purpose. The peak at 1462 cm"1 is assigned to the bending vibration in all trans methylene chain sequence outside the crystal structure. The 723 cm"1 is assigned to the -Cfk rocking mode. The IR spectra of nano sized high molecular weight polyethylene is also included in the same Fig 12. There is no difference in chemical structure between the commercial high density polyethylene, low density polyethylene and nano sized high molecular weight polyethylene. From this observation it is found that both are same materials. But the size of the particle for high molecular polyethylene is in nano scale, i.e., within the range of 10 to 130 nm. Again the infrared spectra of crystalline polymers are complex due to the regular structure of the macromolecules. To simplify it, all spectra are classified into the four groups related to the various molecular structures: conformational band, stereoregularity band, regularity band and crystallinity band. Some absorption bands are very sensitive to the physical state of the samples. According to different origins, these sensitive bands are classified into two categories. One of these bands is related to the intramolecular forces in the crystal lattice, where the polymer molecules pack together on a regular three dimensional arrangement. This type of band is known as crystallinity band. The other type of band is related with the intramolecular vibration coupling with in a single chain and known as regularity band or helix band. The conformational band and regularity band are easily observed for crystallized polypropylene in the mid-infrared region. Fig 13 shows the IR spectra of high molecular weight nano sized polypropylene. The positions of all these bands i.e., 1370, 1301, 1254, 1219, 1161, 1103, 994, 975, 899, 840 and 810 cm"1 belong to the regularity bands. These bands are associated with the different helical length of repeat unit (n). The minimum n values for appearance of these bands at 975, 994, 840 and 1219 cm"1 are 5, 10, 12 and 14 monomer units in helical sequence respectively. The higher is the common unit, the more is the order degree of the corresponding regularity band. Concerning the 975 cm"1 band, it is not only attributed to the polypropylene head to tail sequence of repeating units, but also associated with the presence of short helices. On the other hand the band at 1453 cm"1 is assigned to the asymmetric deformation vibration of the methyl group. The IR spectrum of commercial polypropylene is also included in the same Fig 13. There is no difference in chemical structure between the commercial polypropylene and nano sized high molecular weight polypropylene. Fig 14 shows the IR spectra of commercial polystyrene. The peak positions at 3027, 2885, 1492, 1370 and 757 cm"1 are assigned to the stretching of-C-H bond in phenyl ring, asymmetric stretching of -C-H bond, asymmetric stretching of -C-H bond, symmetric stretching of-C-H bond and rocking of-C-H bond in phenyl ring respectively. The other two peaks 901 and 851 cm"1 are associated to the a crystal form of commercial polystyrene. Another two peaks 911 and 855 cm"1 are assigned to the P crystal form of commercial polystyrene. The IR spectra of nano sized high molecular weight polystyrene is also included in the same Fig 14. There is no difference in chemical structure between the commercial polystyrene and nano sized high molecular weight polystyrene. Characterization of nano sized high molecular weight polymer through X-Ray Diffraction The XRD measurement was conducted in order to examine the crystallinity of commercial high density polyethylene, commercial low density polyethylene and nano sized high molecular weight polyethylene. It was evaluated by X- Ray Diffraction (XRD) using Rich Seifert Iso-Debyefle 202 Diffractometer with a CuKa (X,= 1.54184 A) radiation. Two major peaks i.e., 22 and 24° are identified in X-ray diffraction studies for both polymers and shown in Fig 15. The area under these peak decreases from the nano sized high molecular weight polyethylene to commercial high density polyethylene and low density polyethylene. This suggests that the nano sized high molecular weight polyethylene is more crystalline in nature. The XRD measurement was also conducted in order to examine the crystallinity of the commercial polypropylene and nano sized high molecular weight polypropylene. It is well known that the commercial polypropylene exhibits several different crystalline forms. These are monoclinic (a) form (including mesomorphic (smectic) form. The formation and their mutual phase transitions consist of a number of intermediate stages based on the rotations and transitions of chains. It is again dependent on the crystallization conditions, molecular weight and tacticity of the polymer chain. Three main peaks for the commercial polypropylene (16.7, 18.5 and 21.1) and nano sized high molecular weight polypropylene (16.8, 18.6 and 21.8) are identified for comparison of crystallinity and shown in Fig 16. It shows that the nano sized high molecular weight polymer is more crystalline in nature. Similarly the XRD measurement was also conducted in order to examine the crystallinity of the commercial polystyrene (if any) and high molecular weight nano sized polystyrene. Commercial polystyrene has four types of crystal form (a, P, y and 8) and two mesomorfic forms. It has been reported that the a- and P- forms have trans planar zigzag (tttt)n backbone configuration, where as y- and 8- forms have a helical (trans, trans, gauche, gauche, (ttg+g\) backbone configuration. The a- form with a hexagonal unit cell and P- form with an orthorhombic unit cell have an identity of c equal to 5.1 A. The y- and 8- forms (both having an identity of c = 7.8 A) are monoclinic crystal structure. Among these four crystalline forms, the a- form (with a = 26.26 A) and P- form (with a = 8.81 A, b = 28.82 A) are crystalline polymorphs. Few peaks for the commercial polystyrene (14.0, 16.7, 17.9, 18.4 and 19.7) and nano sized high molecular weight polystyrene (14.0, 16.7, 18.2, 18.5 and 19.5) are identified for comparison of crystallinity and shown in Fig 17. It also suggests that the nano sized high molecular weight polystyrene is more crystalline with respect to the commercial polystyrene. Characterization of nano sized high molecular weight polymer through molecular weight Viscosity at very low concentration is measured for commercial polystyrene (Fig 18) and nano polystyrene (Fig 19). Molecular weight is calculated using Mark-Howink equation, which is ...(10) where k = 3.7x1 0"3 dL/gm and a = 0.62 For commercial polystyrene its viscosity average molecular weight is -0.97 X106 whereas for nano polystyrene it is ~ 0.98 X106. From the measurement of viscosity average molecular weight it is concluded that the nano sized polystyrene is a high molecular weight material which is equal to the commercial polystyrene. But the size of polymer is in nano scale. Examples (1) Preparation of nano sized high molecular weight polyethylene Drying of n-Hexane 670 gm of HPLC grade n-hexane was introduced in a single necked, two liter round bottle flask. 100 gm of calcium chloride was added into it. This mixture was allowed to keep for 12 hours followed by decantation. Large percentage of water was removed during this period. Sodium wires were pressed into the round bottle flask containing n-hexane, continuing the addition of the sodium wires until evolution of hydrogen bubbles was observed. After 3 hours a pinch of benzophenone (-0.1 gm) was added to the above round bottle flask (n-hexane and sodium wires). This was refluxed at a temperature of 110 to 120°C in an inert atmosphere, until it sustains dark blue colour. After sustaining the dark blue colour the mixture was refluxed for another 1 hour and was cooled to room temperature under inert atmosphere. Finally it was distilled under inert atmosphere and the dried n-hexane was collected in another round bottle flask. Purification and drying of toluene: The main impurity in HPLC grade toluene was sulfur. It was removed by treating toluene with sulphuric acid. 430 gm of HPLC grade toluene was taken in a clean, single necked, one liter round bottle flask. 37 gm of 99% sulphuric acid was added to it. This mixture was kept for 12 hours with rapid stirring using a magnetic stirrer. Neck of the round bottle flask was closed with guard tube containing calcium chloride. After stirring, acid was separated using separating funnel from the mixture. Remaining toluene was washed with distilled water in the separating funnel. Again it was washed with saturated sodium bicarbonate solution (10%) in the distilled water for complete removal of sulphuric acid. Same procedure was followed for drying toluene as mentioned in the case of n-hexane. Preparation of catalyst (TiCl4): A 50 ml round bottle flask was purged with moisture and oxygen free nitrogen gas. A calculated amount of dry hexane (5 gm) and titanium tetra chloride (3 gm) were added under inert atmosphere at room temperature. The mixture was kept under inert atmosphere at room temperature of 25°C for few minutes. Then the flask was cooled with a septum. Catalyst activity usually changes with time and the maximum activity was often reached only after ageing periods of one to two hours. Drying of diethyl ether: 357 gm of diethyl ether was taken in a clean dry single neck one liter round bottle flask and 15 gm of calcium chloride was added into it. This mixture was allowed to keep for 12 hours followed by decantataion. Large percentage of water was removed during this process. Sodium wires were pressed into the round bottle until the evolution of hydrogen bubbled could be stopped. A pinch of benzophenon (0.1 gm) was added and kept for three hours. It was refluxed until it sustains dark blue colour in the inert atmosphere. After sustaining dark blue colour the mixture was refluxed for another two hours at 45°C and cooled under inert atmosphere to the room temperature of 25°C. And then finally dried diethyl ether was distilled in one liter round bottle flask using a condenser. Preparation of methyl magnesium iodide: The preparation of Grignard reagent was conducted in a clean dry one liter three necked round bottle flask assembled with condenser, dropping funnel and take off tube with stop cork. The theoretical amount of magnesium metal (-10 gm) and a pinch of Iodine were placed in the three necked round bottle flask. After flashing this system by nitrogen to create inert atmosphere diethyl ether was added through cannula. The required amount of methyl iodide (-58.4 gm) highly diluted with ether was placed in the dropping funnel with rapid magnetic stirring. Reaction started very vigorously, reddish colour of mixture changed very fast and became colourless. After being colourless, the diluted iodomethane was added to the reaction mixture drop wise keeping reaction round bottle flask in the ice bath. Because, the reaction is highly exothermic, after complete addition the reaction mixture was refluxed for 2 hours at a temperature of 35 to 40°C. The Grignard reagent was prepared with almost 100 f percent yield. Since it is moisture sensitive and pyrophoric in nature, it was stored in the inert atmosphere. Preparation of trimethyl aluminium: The reaction of trimethyl aluminium with a Grignard reagent was performed in a threenecked round bottle flask equipped with a condenser, dropping funnel and take off tube with stop cork, which supplies dry nitrogen continuously to the system. 285.6 gm of perfectly dried diethyl ether was added into the round bottle flask with rapid magnetic stirring and anhydrous aluminium chloride (10 gm) was added into the ether slowly at 0°C for making solution. Freshly prepared Grignard reagent was added drop wise to the solution with the help of cannula. After complete addition of Grignard reagent the reaction mixture was refluxed at a temperature of 30 to 40°C for 2 hours circulating the chilled water through the condenser for completion of the reaction. This mixture has a clear solution of trimethyl aluminium etherate complex and ^ solid material of magnesium chloride iodide at the bottom of round bottle flask. Isolation of trimethyl aluminium: A distillation condenser was fitted into the above round bottle flask carefully, ensuring that the whole system was in the nitrogen atmosphere. The reaction mixture was heated at 40 to 50°C for three hours for removal of excess ether. Vacuum of 30 mm Hg was created into the system, Trimethyl aluminium was distilled out in a single necked 100 ml round bottle flask at a temperature of 60 to 70°C using two ice traps between vacuum pump and round bottle flask for complete condensation of trimethyl aluminium. Polymerization of ethylene using TiCU/CCHa^Al catalyst to get nano sized high molecular weight polyethylene 670 gm of dried n-hexane was introduced into the completely dry and clean two liter reactor fully charged with nitrogen gas. The temperature was increased to 45°C. At this temperature a calculated amount of TiCl4 (~5 gm) and trimethyl aluminium (-1.6 gm) were charged into the reactor with the help of syringe and needle under inert atmosphere. The temperature of the system was then raised to 100°C. After stirring for 30 minutes ethylene was introduced into the reactor at the required pressure. Ethylene was added for one hour maintaining the temperature of 90-100°C and pressure of 0.1 to 2 MPa. Water was allowed to pass through the cooling coils. After polymerization methanol was added to deactivate the unreacted catalyst and heated to 170°C to remove the unreacted ethylene. Then it was cooled to 50°C. After that a trace of HCL was added to decompose and dissolve the catalyst. Xylene was added into the mixture and heated to 100°C to form a clear solution and cooled slowly with continuous stirring over a shear rate of 0.2 to 200 rad/s for 0.1 to 12 hours. Nano sized polyethylene was separated by filtration and dried under reduced pressure of 30 mm Hg. (2) Preparation of nano sized high molecular weight polypropylene The procedure for the step of (1) drying on n-hexane, (2) purification and drying of toluene, (3) preparation of catalyst, TiCU, (4) synthesis of trimethyl aluminium, (5) isolation of trimethyl aluminium, (6) drying of diethyl ether and (7) preparation of methyl magnesium chloride are already described in the section of "preparation of nano sized high molecular weight polyethylene". Same procedure is also adopted here. Next step is the preparation of nano sized high molecular weight polypropylene. Polymerization of propylene using TiCLi/CCH^Al catalyst to get nano sized high molecular weight polypropylene 670 gm of dried n-hexane was introduced into the completely dry and clean two liter reactor fully charged with nitrogen gas. The temperature was increased to 45°C. At this temperature a calculated amount of TiCU (~5 gm) and trimethyl aluminium (-1.6 gm) were charged into the reactor with the help of syringe and needle under inert atmosphere. The temperature of the system was then raised to 70°C. After stirring for 30 minutes propylene and hydrogen (here hydrogen acts as a chain terminating agent) were introduced into the reactor at the required pressure. Propylene was added for 12 hours maintaining the temperature of 70-90°C and pressure of 0.1 to 2 MPa. Water was allowed to pass through the cooling coils. After polymerization methanol was added to deactivate the unreacted catalyst and heated to 170°C to remove the unreacted propylene. Then it was cooled to 50°C. After that a trace of HCL was added to decompose and dissolve the catalyst. Xylene was added into the mixture and heated to 100°C to form a clear solution and cooled slowly with continuous stirring over a shear rate of 0.2 to 200 rad/s for 0.1 to 12 hours. Nano sized polypropylene is separated by filtration and dried under reduced pressure of 30 mm Hg. (3) Preparation of nano sized high molecular weight polystyrene 435 gm of benzene was introduced into the completely dry and clean two liter reactor fully charged with nitrogen gas. The temperature was increased to 45°C. At this temperature a calculated amount of Aids (~2 gm) was charged into the reactor under inert atmosphere. The temperature of the system was then raised to 90°C. After stirring for 30 minutes ethylene was introduced into the reactor at the required pressure. Ethylene was added for 3 hours maintaining the temperature of 90-100°C and pressure of 0.1 to 2 MPa. Water was allowed to pass through the cooling coils. After two hours a calculated amount of magnesium oxide (~1 gm) was added and heated the mixture to a temperature of 600°C. After one hour the mixture was cooled to a temperature of 50°C. The styrene was separated by distillation. Pure styrene and a pinch of catalyst, ~0.5gm (hydrogen peroxide, 99.9% purity) were heated at a temperature of 120°C in a reactor. The reactor was fitted with heating and cooling jackets to control the temperature. The melt containing polystyrene and traces of styrene was heated at a temperature of 150°C to remove styrene monomer. The mixture was cooled to the temperature of 50°C. Dimethylsiloxane was added into the mixture and heated to 100°C to form a clear solution and cooled slowly with continuous stirring over a shear rate of 0.2 to 200 rad/s for 0.1 to 12 hours. Nano sized polystyrene was separated by filtration and dried under reduced pressure of 30 mm Hg. ADVANTAGES OF THE INVENTION: ADVANTAGE 1: Applications in materials science and nano designed materials, catalysis; chemical nanotechnology; adhesives and coatings, chemistry in electronics and optics; development of mechanical, optical and atomic scale machine; environmentally benign composite structures; waste remediation; energy conversion; Investigation on the toxicity of nanomaterials; etc. Applications in catalysis, photography, substrate for microelectronics, piezoelectric devices, electronic components, electron source, etc in India. EXPECTED OUTCOME 1: All types of engineering polymer could be possible to prepare at nano scale using the proposed method. EXPECTED OUTCOME 2: Development of a method for producing nano sized high molecular weight polymers that can be used to form plastic articles into intricate shapes with precise dimensions. EXPECTED OUTCOME 3: Production of polymer alloys, self-reinforced plastic and elastomeric composites having a combination of desirable properties that can be exploited in numerous engineering applications. EXPECTED OUTCOME 4: Intimate mixing of the polymer powders with other particles at micrometer length scales which is not possible with current polymer powders. EXPECTED OUTCOME 5: Production of foams by selective leaching and selective laser sintering of parts made from the composites and/or blends of the polymer powders with other compatible organic (e.g., polyethylene) and inorganic (e.g., polyphosphates) materials. EXPECTED OUTCOME 6: High molecular weight polymers with diameters as low as less than lOnm. It is to be understood that the process of the present invention is susceptible to modification, changes, and adaptations by those skilled in the art. Such modifications, changes adaptations are intended to be within the scope of the present invention which is further set forth under the following claims: WE CLAIM; 1. A Process for preparation of nanoparticles of higher molecular weight of polyethylene comprising steps of:- - Introduction of n-hexane into the reactor followed by introduction of specially prepared catalyst TiCl4 and trimethyl aluminum into the reactor maintained at a temperature of 300-65° under inert atmosphere, - Addition of ethylene into the reactor maintained at 70-150 for 0.5 to 2 hours and at a pressure of 0.1 to 2 MPa so as to cause polymerization. - Treatment of the solution obtained above with methanol acidified with traces of HCL to decompose and dissolve catalyst, - Treatment of the solution obtained above with a solvent followed by heating at -30oC to 150oC form a clear solution and cooled to get nanoparticles. - Separation of nanoparticles of polyethylene as herein described. 2. A process as claimed inany of the preceding claims wherein the reactor is fully charges with environmental gas. 3. A process as claimed in any of the preceding claims wherein the solvents are selected from the group of toluene, xylene, 1,2,4-trichloro benzene, decalin, 1-chloronaphthalemne, biphenyl, dodecanol, diphenylmethane, diphenyl ether, hexadecane, 1-octnol, isoamyl alcohol, benzene, cyclohexane, toluene, cyclohexanone, isoamyl acetate, isobutylacetate, phenyl ether, chloroform, decahydronaphthalene, diethyloxalate, dimethylphthalate, dioxane, ethyl acetate, ethyl, benzene, methyl chloride, 1-nitopropane, phosphorous trichloride, tetrahydofuran, tributyl, phosphate. acrylonitrile, chlorobenzene, acetic acid, n-butanol, isobutanol, carbon tetrachloride, dimethyl siloxane, methanol, acetophenone, paraffin liquid, water, hydroxyl propyl cellulose, and mixture thereof. 4. A process as claimed in claim 4 wherein the environmental gas is selected from oxygen, air, nitrogen, argo, helium and mixture thereof. 5. A process as claimed in any of the preceding claims wherein the shear rate during formation n of nano polymers varies from 0.2 to 200 rad/s. 6. A process for preparation of nanoparticles of higher molecular weight of polyethylene substantially as herein described and idllustrated.

Documents:

3161-DEL-2005-Abstract-(11-01-2012).pdf

3161-DEL-2005-Abstract-(17-09-2012).pdf

3161-del-2005-Abstract-(25-09-2012).pdf

3161-del-2005-abstract.pdf

3161-DEL-2005-Claims-(11-01-2012).pdf

3161-DEL-2005-Claims-(17-09-2012).pdf

3161-del-2005-Claims-(25-09-2012).pdf

3161-del-2005-claims.pdf

3161-del-2005-Correspondence Others-(11-01-2012).pdf

3161-DEL-2005-Correspondence-Others-(17-09-2012).pdf

3161-del-2005-Correspondence-Others-(25-09-2012).pdf

3161-del-2005-correspondence-others.pdf

3161-del-2005-description (complete).pdf

3161-DEL-2005-Descrption (Complete)-(11-01-2012).pdf

3161-DEL-2005-Drawings-(11-01-2012).pdf

3161-DEL-2005-Drawings-(17-09-2012).pdf

3161-del-2005-Drawings-(25-09-2012).pdf

3161-del-2005-drawings.pdf

3161-del-2005-Form-1-(11-01-2012).pdf

3161-del-2005-form-1.pdf

3161-DEL-2005-Form-2-(11-01-2012).pdf

3161-del-2005-form-2.pdf

3161-DEL-2005-Form-3-(11-01-2012).pdf

3161-DEL-2005-GPA-(11-01-2012).pdf

3161-del-2005-gpa.pdf