Title of Invention

"A PROCESS FOR PREPARATION OF MICRON SIZED HIGH MOLECULAR WEIGHT POLYMER"

Abstract The present invention relates to a process for preparation of high molecular weight micron sized polymer, having improved processing characteristics including high surface to volume ratio, more particularly the present process relates to process of preparation of high molecular weight PE/PP and PS having particle size in the range of 0.17 to 50 µm in diameter.
Full Text A PROCESS FOR PREPARATION OF MICRON SIZED HIGH MOLECULAR WEIGHT POLYMER
FIELD OF INVENTION
The present invention relates to a process for preparation of high molecular weight micron sized polymer, having improved processing characteristics including high surface to volume ratio from millimeter sized polymer.
BACK GROUND AND PRIOR ART OF INVENTION
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 multicomponent polymer system as a means for producing new material on the micrometer and nanometer scale. Composites, polymer particles or polymer alloys with specifically tailored properties could 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.
Significance of nano or micron sized polymers: The importance of nano or micron sized polymers is primarily due to their novel properties and small size. In fact, 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. To be precise, the unique properties of these materials arise due to their low dimension and large surface to volume ratios.
A variety of methods are available to produce nanomaterials (not for polymers). The coating with organic molecules keeps the nature of metal clusters intact. It is now possible to deposit two- and three- dimensional arrays of clusters on substrates and at specific sites/intervals. Ligand and stabilized metal cluster in size range of 1-2 nm behave like quantum dots where a few electrons are locked up. Their special character opens up applications in nano- and optoelectronics, photo voltaics, etc. A lithography process with accelerated clusters has been developed to modify surfaces of silicone, quartz and diamond through erosion/reaction.
Ultrafine metal particles based polymers and amorphous films of cage-structured clusters (e.g., metcars, bucky balls) can now be produced. Metal clusters isolated in zeolites show
interesting photochromic and magnetic properties. The use of scanning tunnelling and atomic force microscopes (STM and AFM) to rearrange atoms and clusters on substrates and manipulate them to draw nanowires is well demonstrated. Further, cluster deposited multilayers have found to develop nanowires that are characterized by giant magnetoresistance.
The ultra fast response time and photochemical inertness of nanocluster composites of metal quantum dots make them ideal non-linear materials for optical switching and electro-optical devices. Their linear wave-guide qualities allow them to transmit as many as five modes. The resonance absorption in visible and near infrared region observed in metal island film is attributed to optical anisotropy in the critical condition-making them potential candidate for ultrathin optical polarizers. Aligned carbon nanotube films in the polymer matrix may find application as a large area field emission electron source.
Newer theoretical approaches can now simulate large size cluster. The geometrical optimization process becomes faster with use of genetic algorithm in directing the growth of clusters in minimum energy configurations. The growth of cluster is found to depend largely upon the nature of the substrate and accompanying magic numbers differ completely from usual gas phase situations. Real time simulations of cluster melting, growth, dynamics, etc are now possible. There exists a basis to believe now that quasicrystals are results of packing small atomic clusters.
The most important question arises is about the possibility of cluster assembly in a way similar to atoms/molecules in crystals and thereby forming a new class of periodic structures exhibiting unique structural and electronic properties. The key lies in suppressing coalescence of atomic clusters and preventing possible reactions with the environmental species to ensure their stability.
The commercial polyethylene (low density polyethylene, high density polyethylene, liner low density polyethylene, etc) is synthesized by the Ziegler process using aluminium trialkyl-TiCLt complex as catalyst, Phillips process using CrO3 as catalyst and Standard oil process using molybdenum as catalyst. 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. Similarly the commercial polystyrene is synthesized by the bulk and suspension polymerization (and the emulsion process to a lesser extent). Hence, the knowledge about synthesis, properties and uses of commercial polymers such as polystyrene/ polypropylene / polyethylene existed since 1960. The size of this commercial polyethylene is ~ 2-5 mm in diameter.
Regarding the synthesis of polymer (polyethylene) at the micron sized has been reported by Otaigbe et al. through gas atomizing technique [Otaigbe JU, Noid DW, Sumpter BG (1998) Advances in Polymer Technol. 17:161] without mentioning its molecular weight. The yield is less than 0.01% and particle sizes ranging from 25-200 urn. In this technique, the polymer is melted at a high temperature and passed through an orifice into a vacuum chamber. Spherical ultra-fine polymer particles (10-35 nm) are prepared by chemical polymerization of aniline in an inverse water-in-oil micro emulsion [Chan HSO, Ming L, Chew CH, Ma L, Seow SH., (1993) J Mater Chem 3:1109 ,Xu, XL, 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 , Klein, M., US Patent 4,207,378, June 1980, 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. However, the synthesis of high molecular weight micron/nano sized polystyrene was not known due to the lack of sufficient knowledge about the controlling factors which are responsible for the formation of single polymeric chain.
Generally number average molecular weight of polymers is exist greater than 1,00,000 and available in granular form having diameter is more than 2 mm. Due to its high molecular weight, it was not possible to prepare polymers at nano or micro scale. The afore-said mentioned processes were unable to prepare a high molecular weight polymer having a dimension of micron/nano sized particles.
The present process provides a solution to the above-said problems for preparation of high molecular weight polymers of micro sized particles through the close control of thermodynamic parameters. The present invention report the controlled preparation of spherical and high molecular weight micron sized polymer such as polyethylene, polypropylene and polystyrene. These are widely used through out our life including biomedical, aerospace and automobile industries. In spite of that the molecular theories to explain the unusual behavior of long chain molecules are limited. Because these long chain molecules are exist in coil form. It was not possible to prepare single polymer chain. At the same time the inexpensive production techniques suitable for down to earth industries are not available. This new high molecular weight micron sized polyethylene will help the researcher to establish a new molecular theories for the unusual behavior of long chain molecules. The technique adopted to prepare the high molecular weight micron sized polyethylene will help the researchers to prepare all type of polymers. The high molecular weight micron sized polyethylene has promise for wide range of applications, viz., catalysis,
photography, substrate for microelectronics, piezoelectric devices, electronic components, electron source, etc in India. Considering the current and future needs it is our interest to initiate a strong research programme in this area to foster our industries to adopt newer processing routes for manufacturing their products with superior specifications and also introduce new products based on unique properties of this class of new generation materials. Again due to the availability of various types of high molecular weight micron sized polymers in near future this proposed technique is likely to increase the production of fiber reinforced plastic components satisfactorily. This will in turn enhance the interest of laboratories and industries.
A qualitative comparison of new process for synthesis of high molecular weight micron sized polymer with conventional techniques.

(Table Removed)
I
OBJECTIVES OF THE INVENTION:
The objective of the present invention is to prepare micron sized high molecular weight homo polymer and copolymer.
Yet another objective of the present invention relates to process of preparation of high molecular weight micron sized polymer (viscosity average molecular weight is approximately 1,00,000) by controlling thermodynamic parameters".
Yet one another objective is to characterize the particle size of high molecular weight micron sized polymer.
SUMMARY OF THE INVENTION:
Accordingly, the present invention relates to a process for preparation of high molecular micron sized polymer (SRPHMWMSP). More particularly, polymers are homo polymer and / or copolymer which are selected from the group comprising polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), polyvinylchloride (PVC), polymethyl methacrylate (PMMA), polyamide (PA), acrylonitrile butadiene styrene (ABS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyoxymethylene (POM), polyphenylene ether (PPE), polysulfone (PSF), polyphenylene oxide (PPO), polyamide-imide (PAI), liquid crystal polymer (LCP), poly ether ether ketone (PEEK) in a compatible solvent/solvents system. More particularly, in the present invention polymers have been prepared by using various solvents in different atmospheric conditions. Further, the micron sized polymers are characterized through the particle size, BET surface area, scanning electron microscopy (SEM), infrared spectroscopy (IR) and storage modulus value and compare with commercial available PE, PP and PS
BRIEF DESCRIPTION OF DRAWINGS AND TABLES:
Figure 1 shows schematic diagram of simple reactor for production of high molecular weight micron sized polymers wherein (1, 3, 5: Feeding of ingredients, 2: Outlet of gas (environmental gas), 4: Inlet of gas (environmental gas), 6: Jacket for controlling the temperature from -30 to +250°C by circulating of liquid nitrogen (below sub ambient temperature) and hot oil (above room temperature), 7: Magnetic stirrer for controlling the shear rate in the solution).
Figure 2: Particle size distribution of high molecular weight micron sized
polyethylene
Figure 3: Particle size distribution of high molecular weight micron sized
polypropylene
Figure 4: Particle size distribution of high molecular weight micron sized
polystyrene.
Figure 5 shows the effect of relative pressure on volume absorbed for high molecular
weight micron sized polyethylene
Figure 6: Effect of relative pressure on volume absorbed for polypropylene
Figure 7: Effect of relative pressure on volume absorbed for high molecular weight
micron sized polystyrene
Figure 8 shows the effect of pore diameter on pore volume for high molecular weight
micron sized polyethylene.
Figure 9: Effect of pore diameter on pore volume for high molecular weight micron
sized polypropylene
Figure 10: Effect of pore diameter on pore volume for high molecular weight micron
sized polystyrene
Figure 11 shows the effect of pore diameter on pore area for high molecular weight
micron sized polyethylene
Figure 12: Effect of pore diameter on pore area for high molecular weight micron
sized polypropylene
Figure 13: Effect of pore diameter on pore area for high molecular weight micron
sized polystyrene
Figure 14 shows the BET isotherm of high molecular weight micron sized
polyethylene
Figure 15: BET isotherm of high molecular weight micron sized polypropylene
Figure 16: BET isotherm of high molecular weight micron sized polystyrene
Figure 17 shows the SEM micrograph of high molecular weight micron sized
polyethylene at a magnification of 550.
Figure 18: SEM micrograph of high molecular weight micron size polypropylene
Figure 19: SEM micrograph of high molecular weight micron sized polystyrene
Figure 20: FT-IR spectra of commercial high density polyethylene, commercial low
density polyethylene and high molecular weight micron sized polyethylene
Figure 21: FT-IR spectra of commercial polypropylene and high molecular weight
micron sized polypropylene.
Figure 22: FT-IR spectra of commercial polystyrene and high molecular weight
micron sized polystyrene.
Figure 23 XRD intensity patterns for commercial high density polyethylene,
commercial low density polyethylene and high molecular weight micron sized
polyethylene (2 theta varies from 25 to 80°)
Figure 24: XRD intensity patterns for commercial polypropylene and high molecular
weight micron sized polypropylene (2 theta varies from 24 to 78°)
Figure 25: XRD intensity patterns for commercial polystyrene and high molecular
weight micron sized polystyrene (2 theta varies from 25 to 80°.
Figure 26: XRD intensity patterns for commercial high density polyethylene,
commercial low density polyethylene and high molecular weight micron sized
polyethylene (2 theta varies from 18 to 25°)
Figure 27: XRD intensity patterns for commercial polypropylene and high molecular
weight micron sized polypropylene (2 theta varies from 15 to 25°)
Figure 28: XRD intensity patterns for commercial polystyrene and high molecular
weight micron sized polystyrene (2 theta varies from 10 to 25°)
Figure 29 Storage modulus of commercial high density polyethylene and high
molecular weight micron sized polyethylene at a frequency of 10 Hz.
Figure 30: Storage modulus of commercial polypropylene and high molecular
weight micron sized polypropylene at a frequency of 10 Hz.
Figure 31: Storage modulus of commercial polystyrene and high molecular weight
micron sized polystyrene at a frequency of 10 Hz.
Figure 32 Loss modulus of commercial high density polyethylene and high molecular
weight micron sized polyethylene at a frequency of 10 Hz
Figure 33: Loss modulus of commercial polypropylene and high molecular weight
micron sized polypropylene at a frequency of 10 Hz.
Figure 34: Loss modulus of commercial polystyrene and high molecular weight
micron sized polystyrene at a frequency of 10 Hz.
Figure 35 Loss tangent of commercial high density polyethylene and high molecular
weight micron sized polyethylene at a frequency of 10 Hz
Figure 36: Loss tangent of commercial polypropylene and high molecular weight
micron sized polypropylene at a frequency of 10 Hz.
Figure 37: Loss tangent of commercial polystyrene and high molecular weight
micron sized polystyrene at a frequency of 10 Hz.
Figure 38: TGA thermogram of commercial high density polyethylene and high
molecular weight micron sized polyethylene in nitrogen atmosphere.
Figure 39: TGA thermogram of commercial polypropylene and high molecular
weight micron sized polypropylene in nitrogen atmosphere.
Figure 40: TGA thermogram of commercial polystyrene and high molecular weight
micron sized polystyrene in nitrogen atmosphere.
Figure 41: Derivative of TGA thermogram of commercial high density polyethylene and high molecular weight micron sized polyethylene in nitrogen atmosphere Figure 42: Derivative of TGA thermogram of commercial polypropylene and high molecular weight micron sized polypropylene in nitrogen atmosphere. Figure 43: Derivative of TGA thermogram of commercial polystyrene and high molecular weight micron sized polystyrene in nitrogen atmosphere
LIST OF TABLES:
Table 1: Peak position of FT-IR spectra for high molecular weight micron sized polyethylene and commercial high density polyethylene
Table 2: Peak position of high molecular weight micron sized polypropylene and commercial
polypropylene
Table 3: Peak position of high molecular weight micron sized polystyrene and commercial
polystyrene
Table 4: XRD peak of high molecular weight micron sized polypropylene and commercial
polypropylene.
Table 5: XRD peak of high molecular weight micron sized polystyrene and commercial
polystyrene
DETAILED DESCRIPTION OF THE INVENTION:
Accordingly, the present invention relates to a process for preparation of high molecular weight micron sized polymer, having improved processing characteristics including high surface to volume ratio, from millimeter sized polymer granule, said process comprising the steps of
a) mixing catalysts namely titatinium chloride and trimethyl aluminium in a amount in the range 0.5 gm to 10 gm in a solvent of amount 500 cc to 1500 cc, maintaining at a temperature in the range of-30°C to 45°C in inert atmosphere, stirring the same for a predetermined time period to obtain solution,
b) mixing the solution of step (a), with millimeter sized high molecular weight polymer in a amount of 10 to 500 gm at a pressure in the range of 0.1 to 2.0 MPa and at a temperature in the range of-30°C to 100°C, to obtain a mixture comprises monomer residue or traces thereof,
c) heating the mixture of step (b) for removing monomer residues and traces thereof,
d) treating the mixture with solvent in a ratio 1:1 to 1:0.1 such as mentioned herein and acidifying with traces of HC1 so as to decompose and to dissolve the catalyst in a solution,
e) heating the solution of step (d) up to 100°C to form a clear solution,
f) cooling the clear solution and stirring the same at a shear rate in the range of 0.2 to 200 rad/s for a predetermined time to obtain a precipitate,
g) filtering the precipitate and drying the same in order to get the micron sized high molecular weight polymer.
One embodiment of the present invention, wherein the solvent is selected from the group
comprising from 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, tetrahydofuran, tributyl phosphate, acrylonitrile,
chlorobenzene, acetic acid, n-butanol, isobutanol, carbon tetrachloride, dimethyl siloxane, methanol, acetophenone, paraffin liquid and water.
Another embodiment of the present invention, wherein in step (a) the ratio of catalysts titatinium chloride and trimethyl aluminium is in the range of 0.5 to 7 gm.
One another embodiment of the present invention wherein in step (a), the time period is in the range of 0.5 to 10 hours.
One another embodiment of the present invention wherein in step (a), the time period is in the range of 1 to 5 hours.
Yet another embodiment of the present invention wherein in step (b), the monomer residues and traces are unreacted catalysts such as titatinium chloride and trimethyl aluminium.
Yet one another embodiment of the present invention wherein in step (c), the mixture is being heated up to 170°C.
Yet another embodiment of the present invention wherein in step (f), the time period is in the range of 0.5 to 10 hours.
One another embodiment of the present invention wherein in step (a), the time period is in the range of 1 to 10 hours.
Still another embodiment of the present invention, wherein in step (f), the clear solution is being cooled up to 25°C.
Still one another embodiment of the present invention, wherein the molecular weight of millimeter sized polymer is in the range of 1,00,000 to 1,50,000 (Viscosity average molecular weight).
Still another embodiment of the present invention wherein the millimeter sized high molecular weight polymer are homo polymer or copolymer.
Yet another embodiment of the present invention wherein the homo polymer and copolymer are selected from the group comprising polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), polyvinylchloride (PVC), polymethyl methacrylate (PMMA), polyamide (PA), acrylonitrile butadiene styrene (ABS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyoxymethylene (POM), polyphenylene ether (PPE), polysulfone (PSF), polyphenylene oxide (PPO), polyamide-imide (PAI), liquid crystal polymer (LCP), poly ether ether ketone (PEEK).
Yet one another embodiment of the present invention wherein the millimeter sized high molecular weight polymer are selected from polypropylene / polyethylene / polystyrene.
Yet one another embodiment of the present invention wherein high molecular weight micron sized polyethylene is prepared in the range 0.17 to 50 urn in diameter.
Yet another embodiment of the present invention wherein in step (g), the micron sized high molecular weight polypropylene is prepared in the range 0.17 to 40 µm in diameter.
Yet another embodiment of the present invention wherein in step (g), the micron sized high molecular weight polystyrene is prepared in the range 0.17 to 47 µm in diameter.
Yet another embodiment of the present invention wherein in step (g), the micron sized high molecular weight polyethylene is prepared in the range 0.17 to 50 µm in diameter.
Yet another embodiment of the present invention wherein the micron sized high molecular weight polypropylene having minimµm BET surface area is 16.2 m2/gm in presence of xylene at a temperature of 30°C and shear rate of 150 rad/s.
Yet another embodiment of the present invention wherein the micron sized high molecular weight polystyrene having minimµm BET surface area is 17.7 m /gm in presence of solvent of dimethyl siloxane at a temperature of 30°C and shear rate of 175 rad/s.
Yet another embodiment of the present invention wherein the micron sized high molecular weight polyethylene having minimµm BET surface area is 16.2 m /gm in presence of xylene, at a temperature of 30°C, shear rate of 175 rad/s and in the nitrogen/ argon atmosphere.
Yet another embodiment of the present invention wherein the micron sized high molecular weight polyethylene / polypropylene / polystyrene are spherical in nature.
Yet another embodiment of the present invention wherein loss modulus and loss tangent of high molecular weight polyethylene / polypropylene / polystyrene are low as compare to commercial available polyethylene / polypropylene / polystyrene.
Yet another embodiment of the present invention wherein the micron sized high molecular weight polyethylene / polypropylene / polystyrene having crystallinity in the range of 40 to 60 % .
Yet another embodiment of the present invention wherein the glass transition temperature of high molecular weight micron sized polyethylene / polypropylene / polystyrene increase in the range of 5 to 25°C as compare to commercial polyethylene / polypropylene / polystyrene.
Yet another embodiment of the present invention wherein the thermal stability of high molecular weight micron sized polyethylene / polypropylene / polystyrene increase in the range of 10 to 30°C as compare to commercial polyethylene / polypropylene / polystyrene.
A reactor (Fig. 1) is used for the synthesis of high molecular weight micron sized polymers, i.e., polyethylene, polypropylene and polystyrene. There is a provision to control the reaction temperatures from -30 (sub ambient) to +250°C, reaction time, different atmospheres using purge gases (nitrogen, argon and oxygen) and shear rates (0.2 to 200 rad/s) by magnetic stirrer.
The process for preparing of micron sized high molecular weight polymer is described herewith following examples which should not be construed to limit the scope of invention.
Synthesis of high molecular weight micron sized polyethylene: The synthesis of high molecular weight micron sized polyethylene involves the following steps
Step 1: The catalyst for the preparation of high molecular weight micron sized polypropylene is prepared from TiCU and trimethyl alµminiµm in n-hexane.
Step 2: The above catalyst and ethylene is charged into the reactor under slightly elevated pressure of 0.1 to 2 MPa and at a temperature of 90-100°C.
CH2=CH2 + Catalyst = (CH2-CH2)n- + Catalyst
Step 3: The mixture containing polyethylene and n-hexane; and traces of ethylene and catalyst is heated at a temperature of 170°C to remove ethylene monomer. The lower limit is not essential for this process and it can be worked out by any person who has average skill in this art. The critical part of this step is higher limit of temperature and applicant found that if the higher limit exceed from the 170°C the process shall not be worked out.
Step 4: The solution is then treated with methanol acidified with traces of HCl to decompose and dissolve the catalyst.
Step 5: The solution is treated over a range of solvents (toluene, xylene, 1,2,4-trichIoro 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, tetrahydofuran, tributyl phosphate, acrylonitrile, chlorobenzene, acetic acid, n-butanol, isobutanol, carbon tetrachloride, dimethyl siloxane, methanol, acetophenone, paraffin liquid and water), temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s.
Step 6: The mixture is heated until the formation of clear solution.
Step 7: The clear solution is cooled slowly and continuous stirring at a shear rate of 0.2 to 200 rad/s for 2 hrs.
Step 8: The mixture is filtered to collect the high molecular weight micron sized polyethylene
Step 9: The residue (high molecular weight micron sized polyethylene) is washed with cold water and dried under pressure of 30 Hg to get the high molecular weight micron sized polymer.
Synthesis of high molecular weight micron sized polypropylene: The synthesis of high molecular weight micron sized polypropylene involves the following steps
Stepl: The catalyst for the preparation of high molecular weight micron sized polypropylene is prepared from TiCl4 and trimethyl alµminiµm in n-hexane.
Step 2: The above catalyst, propylene and hydrogen (here hydrogen acts as a chain terminating agent) are charged into the reactor at a pressure of 0.1 to 2 MPa for a time of 12 hours and temperature of 70 to 90°C.
CH3-CH=CH2 + H2 + Catalyst = -(CH3-CH-CH2)„- + Catalyst
Step 3: The mixture containing polypropylene and n-hexane; and traces of propylene and catalyst is heated at a temperature of 170°C to remove propylene monomer.
Step 5: The residue is then treated with methanol acidified with traces of HCl to decompose and dissolve the catalyst.
Step 6: The polymer is then centrifuged and washed with water
Step 7: The pure polystyrene is dissolved over a range of solvents (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, tetrahydofuran, tributyl phosphate, acrylonitrile, chlorobenzene, acetic acid, n-butanol, isobutanol, carbon tetrachloride, dimethyl siloxane, methanol, acetophenone, paraffin liquid and water), temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s.
Step 8: The mixture is heated until the formation of clear solution
Step 9: The clear solution is cooled slowly and continuous stirring at a shear rate of 0.2 to 200 rad/s for 2 hrs.
Step 10: The mixture is filtered to collect the high molecular weight micron sized polypropylene
Step 11: The residue (high molecular weight micron sized polypropylene) is washed with cold water and dried under pressure of 30 Hg to get the high molecular weight micron sized polymer.
Synthesis of high molecular weight micron sized polystyrene: The synthesis of high molecular weight micron sized polyethylene involves the following steps
Step 1: It involves 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 AICI3) at a temperature of 90°C
C6H6 +CH2=CH2 + AICI3 = C6H5-CH2CH3 + + AICI3
Step 2: Ethyl benzene is dehydrogenated to styrene at a temperature of 600°C in presence of catalyst (in this case we used magnesiµm oxide)
C6H5-CH2CH3 + MgO = C6H5-CH=CH2 +H2 + MgO
Step 3: Styrene is isolated from the dehydrogenated products by distillation
Step 4: Pure styrene and catalyst (here we used hydrogen peroxide) is heated at a temperature of 120°C in a reactor. The reactor is fitted with heating and cooling jackets to control the temperature.
C6H5-CH=CH2 + H202 = -( C6H5-CHCH2)n- + C6H5-CH=CH2
Step 5: The melt containing polystyrene and traces of styrene is heated at a temperature of 150°C to remove styrene monomer.
Step 6: The pure polystyrene is dissolved over a range of solvents (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, tetrahydofuran, tributyl phosphate, acrylonitrile, chlorobenzene, acetic acid, n-butanol, isobutanol, carbon tetrachloride, dimethyl siloxane, methanol, acetophenone, paraffin liquid, water), temperatures from -30 to +150°C, shear rates (0.2 to 200 rad/s) and environments (oxygen, air, nitrogen and argon).
Step 7: The mixture is heated until the formation of clear solution.
Step 8: The clear solution is poured in to the cold water of 10°C and continuous stirring at a shear rate of 0.2 to 200 rad/s for 2 hrs.
Step 9: The mixture is filtered to collect the high molecular weight micron sized polystyrene
Step 10: The residue (high molecular weight micron sized polystyrene) is washed with cold water and dried under pressure of 30 Hg to get the high molecular weight micron sized polymer.
JUSTIFICATION FOR THE PREPARATION OF NANO OR MICRON SIZED POLYETHYLENE THROUGH THERMODYNAMICS
Partial molar free energy, AG* of a polymer in the polymer particles during swelling composed of following three conditions:
where AGsp, AG, and AGe/ are the contributions of solvent-polymer mixing force, polymer network elastic-retractile force and particle-solvent interfacial tension force respectively.
Partial molar free energy change by the absorption of the solvent droplets is represented by the following equation

(Equation Removed)
where 0] is the volµme fraction of the solvent, 02 is the volµme fraction of the polymer, J is the ratio of molar volµme of polymer and solvent, % is the solvent polymer interaction parameter, y is the interfacial energy, r is the radius of the particles, and Vj is the partial molar volµme of the solvent.
Form Equation (2), we propose a thermodynamics equation for the swelling of the particles consisting of polymer, swelling agent and mixtures. The partial molar free energy is given as follows:
(Equation Removed)
where 0j is the volµme fraction of the solvent, 02 is the volµme fraction of the swelling agent , 03 is the volµme fraction of the polymer, J2 is the ratio of molar volµme of water-insoluble swelling agent and solvent, J3 is the ratio of molar volµme of polymer and solvent,
Xn and xn axe the interaction parameter of the solvent with swelling agent and polymer, respectively, and X23 is the interaction parameter of the swelling agent with the polymer.
For the polymer particles system, 1//3 can be set equal to zero in Equation (3), because a polymer has limitlessyj3 value. Therefore, Equation (3) can be simplified as follows:


The elastic free energy change, AGe/ is an entropy term associated with the change in the configuration of the polymer network, and describe as follows:
where N is the effective nµmber of chains in the network per unit volµme.
Consequently, the partial molar free energy, AG* of the solvent in the polymer particles
during swelling gives

At the equilibriµm state, the following thermodynamic equation can be
Particle radius r can be represented as follows:

where r0 is the initial particle radius.


The rate of transport of the solvent molecules to the polymer particles can be determined by considering that the transport solvent molecules is the rate determining process of molecular diffusion as follows:
(Equation Removed)
where D is the diffusion constant of the solvent molecules, C is the solubility of the swollen
polymer particles, rs is the radius of the swollen polymer particles, and Ns is the nµmber of
the swollen particles, In Equation (9), AG* can be obtained form the Equation (6). It proves
the formation of nano or micron sized polymers. So thermodynamically it is feasible.
Characterization of high molecular weight micron sized polyethylene, polypropylene and polystyrene through the distribution of particle size:
The measurements of particle size's distribution were done by Laser particle sizer-
Analysette 22. Ethyl alcohol was used as a solvent for this experiment. The particle size
distribution of high molecular weight micron sized polyethylene, polypropylene and
polystyrene obtained using the novel technique is shown in Figs 2, 3 and 4 respectively. It is
clear from the Fig. 2 that the novel technique produces high molecular weight micron sized
polyethylene within a range of 0.17 to 47 µm. It also suggests that 5% high molecular weight
polyethylene have a diameter of less than 1 µm and 55% high molecular weight polymer less
than 30 µm. In addition to this it is also worth to mention here this technique produces
micron sized polymer with a yield of 100%.
From the Fig 3 it is also clear that the novel technique produces high molecular weight micron sized polypropylene within a range of 0.17 to 40 µm. It suggests that 11% high molecular weight polypropylene have a diameter of less than 1 µm and 49% high molecular weight polymer less than 20 µm. Again it is also worth to mention here this technique produces micron sized polymer with a yield of 100%.
Fig. 4 shows that the novel technique produces high molecular weight micron sized polystyrene within a range of 0.17 to 51 µm. This suggests that 9% high molecular weight polystyrene have a diameter of less than 1 µm and 37% high molecular weight polystyrene are less than 9 µm. Similarly it is also worth to mention here this technique produces micron sized polystyrene with a yield of 100%.
Characterization of high molecular weight micron sized polyethylene, polypropylene and polystyrene through the surface area:
The surface area of high molecular weight micron sized polyethylene, polypropylene and polystyrene was measured by "COULTER™ SA 3100™ Series Surface Area and Pore Size
^Analyzers". The BET surface area is calculated for high molecular weight micron sized polyethylene using the following Equations (10) and (11) and Figs 5, 8,11 and 14:
My
where VM, VA, PS, P0, C and SBET are the volµme of the mono-layer, volµme adsorbed, sample pressure, saturation pressure and constant related to the enthalpy of adsorption and BET surface area respectively. The BET surface area reveals its minimµm surface area of 16.2 m2/gm (calculated from Figs 5, 8, 11 and 14). Similarly the BET surface area for high molecular weight micron sized polypropylene is 16.2 m2/gm (calculated from Figs 6, 9, 12, and 15 and Equations (10) and (11)). Figs 7, 10, 13 and 16 reveal its minimµm surface area of 17.7 m2/gm (calculated by Equations (10) and (11)).
Characterization of high molecular weight micron sized polyethylene, polypropylene and polystyrene through scanning electron microscopy:
The particle size and morphology of high molecular weight micron sized polyethylene, polypropylene and polystyrene were also determined by using a JEOL JSM 840A Scanning Electron Microscope (SEM). Prior to SEM studies, the samples were sputter coated with gold without touching the surface. The micro graph (Fig. 17) shows that the high molecular weight micron sized polyethylene is spherical in nature. To avoid the thermal degradation of high molecular weight micron sized polyethylene the photograph is taken at an accelerating voltage of 10 kV and magnification of 550. Fig. 18 shows the micrograph of high molecular weight polypropylene at a magnification of 550 and an accelerating voltage of 10 kV. The micrograph of high molecular weight polystyrene at a magnification of 800 is shown in Fig. 19. The accelerating voltage was 5 kV.
Characterization of high molecular weight micron sized polyethylene, polypropylene and polystyrene through infrared spectroscopy analysis
The infrared spectrµm of commercial high density polyethylene, low density polyethylene and high molecular weight micron sized polyethylene was studied by "BRUKER VECTOR 22" infrared spectrometer. Infrared (IR) spectra were used to find out the difference in chemical structure between the commercial high density polyethylene, low density polyethylene and high molecular weight micron sized polyethylene. Fig. 20 shows the IR spectra of commercial high density polyethylene. The positions of all peaks are sµmmarized in Table 1. 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 the commercial high density polyethylene. But the 717 cm-1 is assigned to the monoclinic crystalline structure of commercial high density polyethylene. The IR spectra of commercial low density polyethylene is also included in the same Fig. 20 for the comparison purpose. The peak at 1462 cm-1 is assigned to bending vibration in all trans methylene chain sequence outside the crystal structure. The 723 cm-1 is assigned to the -CH2 rocking mode. The IR spectra of high molecular weight micron sized polyethylene is also included in the same Fig. 20. It is very interesting to note that there is no difference in chemical structure between the commercial high density polyethylene and high molecular weight micron sized polyethylene. From this observation we can claim that both are same materials. But the size of the particle is in micro scale.
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 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. 21 shows the IR spectra of high molecular weight micron sized polypropylene. The position of all peaks are sµmmarized in Table 2. All of the 1370, 1301, 1254, 1219, 1161, 1103, 994, 975, 899, 840 and 810 cm-1 bands are belong to the regularity bands. They are associated with the different helical length of repeat unit (n). The minimµm n values for appearance of 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 spectrµm of commercial polypropylene is also included in the same Fig. 21. It is very interesting to note that there is no difference in chemical structure between the commercial polypropylene and high molecular weight micron sized polypropylene.
Fig. 22 shows the IR spectra of commercial polystyrene. The position of all peaks is sµmmarized in Table 3. The peak positions at 3027 cm-1, 2885 cm-1, 1492 cm-1, 1370 cm-1
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 ß crystal form of commercial polystyrene. The IR spectra of high molecular weight micron sized polystyrene is also included in the same Fig. 22. It is very interesting to note that there is no difference in chemical structure between the commercial polystyrene and high molecular weight micron sized polystyrene.
Characterization of high density polyethylene and high molecular weight micron sized polyethylene, polypropylene and polystyrene through X-Ray Diffraction
The XRD measurement was conducted in ordered to examine the crystallinity of the commercial high density polyethylene, commercial low density polyethylene and high molecular weight micron sized polyethylene. It was evaluated by X- Ray Diffraction (XRD) using Rich Seifert Iso-Debyefle 202 Diffractometer with a CuKa (X= 1.54184 A) radiation. Fig. 23 shows the X-ray diffraction pattern of commercial high density polyethylene, commercial low density polyethylene and high molecular weight micron sized polyethylene. Two major peaks are identified in Fig. 23 for both polymers. These are 22 and 24° and shown in Fig. 26. The area under these peak increases from high molecular weight micron sized polyethylene to commercial high density polyethylene and low density polyethylene. This suggests that the high molecular weight micron sized polyethylene is more crystalline in nature
The XRD measurement was also conducted in ordered to examine the crystallinity of the commercial polypropylene and high molecular weight micron sized polypropylene. It is well known that the commercial polypropylene exhibits several different crystalline forms. These are monoclinic (a) form (including ai and (X2), trigonal (P) and triclinic (y) form and mesomorphic (smectic) form. The formation and their mutual phase transitions consist of a nµmber of intermediate stages based on rotations and transitions of the chains. It is again dependent on the crystallization conditions, molecular weight and tacticity of the polymer chain. Fig. 24 shows a characteristic X ray diffraction pattern of commercial polypropylene and high molecular weight micron sized polypropylene. In this Figure the diffraction peaks of (300) plane of the p form and those of the (110), (040) and (130) planes of the a form are evident. These peak positions are tabulated in Table 4. Three main peaks for the commercial polypropylene (16.7, 18.5 and 21.1) and high molecular weight micron sized polypropylene (16.8, 18.6 and 21.8) are identified for comparison of crystallinity and shown in the Fig. 27. The relative amount of p form is also determined by calculating K value (using Equation 12).
(Equation Removed)
It shows that the high molecular weight micron sized polymer is more crystalline in nature.
Similarly the XRD measurement was also conducted in ordered to examine the crystallinity of the commercial polystyrene and high molecular weight micron sized polystyrene. Fig. 25 shows the X-ray diffraction pattern of commercial polystyrene and high molecular weight micron sized polystyrene. Commercial polystyrene has four types of crystal form (a, P, y and 5) and two mesomorfic forms. It has been reported that the a- and ß- forms have trans planar zigzag (tttt),, backbone configuration, where as y- and 8- forms have a helical (trans, trans, gauche, gauche, (ttg+g+)n) backbone configuration. The a- form with a hexagonal unit cell and ß- form with an orthorhombic unit cell have an identity of c equal to 5.1 . The y- and 8- forms (both having an identity of c = 7.8 ) are monoclinic crystal structure. Among these four crystalline forms, the a- form (with a = 26.26 ) and p- form (with a = 8.81 , b = 28.82 ) are crystalline polymorphs. Few peaks for the commercial polystyrene (14.0, 16.7, 17.9, 18.4 and 19.7) and high molecular weight micron sized polystyrene (14.0, 16.7, 18.2, 18.5 and 19.5) are identified for comparison of crystallinity and shown in the Table 5. The Fig. 28 also suggests that high molecular weight micron sized polystyrene is more crystalline with respect to the commercial polystyrene.
Characterization of high molecular weight micron sized polyethylene, polypropylene and polystyrene through viscoelastic properties i.e., storage modulus
The viscoelastic property, storage modulus was measured by Rheometric Scientific RDA III Dynamic Mechanical Analyzer. The samples were analyzed in tension mode over a range of temperature from 35 to 125°C, frequency of 1, 2,5 and 10 Hz and heating rate of 5°C/min. The storage modulus describes the elastic behavior of the materials. The storage modulus at a frequency of 10 Hz for commercial high density polyethylene and high molecular weight micron sized polyethylene as a function of temperature are shown in Fig. 29. It is very interesting to report that the storage modulus increases from commercial high density polyethylene to the high molecular weight micron sized polyethylene at each temperature. These findings are important because small diameter high molecular weight micron sized polymer is proved to be able to show good material properties without any confinement that limits its dimension.
The storage modulus at a frequency of 10 Hz for commercial polypropylene and high molecular weight micron sized polypropylene as a function of temperature is shown in Fig. 30. It is very interesting to report that the storage modulus increases from commercial polypropylene to the high molecular weight micron sized polypropylene at each temperature. This finding is also important because small diameter high molecular weight micron sized polymer is proved to be able to show good material properties without any confinement that limits its dimension.
Similarly the storage modulus at a frequency of 10 Hz for commercial polystyrene and high molecular weight micron sized polystyrene as a function of temperature is shown in Fig. 31. It is very interesting to report that the storage modulus increases from commercial polystyrene to the high molecular weight micron sized polystyrene at each temperature. Similarly this finding is also important because small diameter high molecular weight micron sized polymer is proved to be able to show good material properties without any confinement that limits its dimension.
Characterization of high molecular weight micron sized polyethylene, polypropylene and polystyrene through viscoelastic properties i.e., loss modulus
Another viscoelastic property i.e., loss modulus was measured by Rheometric Scientific RDA III Dynamic Mechanical Analyzer in tension mode over a range of temperature from 35 to 125°C, frequency of 1, 2,5 and 10 Hz and heating rate of 5°C/min. From these two parameters, the complex modulus and loss tangent are calculated. The loss modulus describes the viscous component of the materials. The loss modulus at a frequency of 10 Hz for commercial high density polyethylene and high molecular weight micron sized polyethylene as a function of temperature is shown in Fig. 32. It is very interesting to report that the loss
modulus decreases from the high molecular weight micron sized polyethylene to the commercial high density polyethylene.
Again the loss modulus at a frequency of 10 Hz for commercial polypropylene and high molecular weight micron sized polypropylene as a function of temperature is shown in Fig. 33. It is also very interesting to report the same behaviour i.e., the loss modulus decreases from the high molecular weight micron sized polypropylene to the commercial polypropylene.
Similarly the loss modulus at a frequency of 10 Hz for commercial polystyrene and high molecular weight micron sized polystyrene as a function of temperature is shown in Fig. 34. Similarly the loss modulus decreases from the high molecular weight micron sized polystyrene to the commercial polystyrene. Again these findings are important because small diameter high molecular weight micron sized polymer is proved to be able to show good material properties without any confinement that limits its dimension.
Characterization of high molecular weight micron sized polyethylene, polypropylene and polystyrene through viscoelastic properties i.e., loss tangent
The loss tangent (another viscoelastic properties) was measured by Rheometric Scientific RDA III Dynamic Mechanical Analyzer in tension mode over a range of temperature from 35 to 125°C, frequency of 1, 2,5 and 10 Hz and hearing rate of 5°C/min. The loss tangent is a measure of the "damping or dissipation factor", defined as the ratio of the loss modulus, E" to the storage modulus, E\ Fig. 35 shows the effect of temperature on loss tangent for both commercial high density polyethylene and high molecular weight micron sized polyethylene. It is also very interesting to report that the loss tangent decreases from the high molecular weight micron sized polyethylene to the commercial high density polyethylene. Again these findings are important because small diameter high molecular weight micron sized polymer is proved to be able to show good material properties without any confinement that limits its dimension.
Fig. 36 shows the effect of temperature on loss tangent for both commercial polypropylene and high molecular weight micron sized polypropylene. It is also very interesting to report that the loss tangent decreases from the high molecular weight micron sized polypropylene to the commercial polypropylene. Again it is claimed that small diameter high molecular weight micron sized polymer is proved to be able to show good material properties without any confinement that limits its dimension
The effect of temperature on loss tangent for both commercial polystyrene and high molecular weight micron sized polystyrene is shown in Fig. 37. It is also very interesting to report that the loss tangent decreases from the high molecular weight micron sized polystyrene to the commercial polystyrene.
Characterization of high molecular weight micron sized polyethylene, polypropylene and polystyrene through thermogravimetric analysis
*f hermogravimetric analysis (TGA) was carried out in a high resolution TGA 2950 of TA Instrµments, New Castle, USA over a range of temperature from 30°C to 550°C with a heating rate of 10°C/min in the nitrogen atmosphere. Thermal stability of commercial high density polyethylene and high molecular weight micron sized polyethylene is measured by TGA in the nitrogen atmosphere. Figs. 38 and 41 show that the commercial high density polyethylene starts to degrade at 250°C whereas the high molecular weight micron sized polyethylene starts to degrade at 243°C. These two figures also suggest the multiple steps of degradation. These multi steps degradation temperature for commercial high density polyethylene are 370, 395 and 427°C. But these multi steps degradation temperatures for high molecular weight micron sized polyethylene are 327,423, 454 and 485°C.
Similarly thermal stability of commercial polypropylene and high molecular weight micron sized polypropylene is measured by TGA in the nitrogen atmosphere. Fig. 39 shows that the commercial polypropylene starts to degrade at 256°C whereas the high molecular weight micron sized polypropylene starts to degrade at 228°C. The maximµm rate of degradation for commercial polypropylene and high molecular weight micron sized polypropylene are at temperature of 280 and 244°C respectively (Fig. 42). Fig. 40 shows that the TGA analysis of Commercial polystyrene and high molecular weight micron sized polystyrene. Commercial polystyrene starts to degrade at 300°C whereas the high molecular weight micron sized polystyrene starts to degrade at 288°C. But the maximµm rate of degradation for commercial polystyrene and high molecular weight micron sized polystyrene are 325 and 343°C respectively (Fig. 43).
Examples
EXPERIMENT 1
Preparation of High molecular weight micron sized polyethylene
Drying of n-Hexane
One liter of HPLC grade n-hexane was placed in a single necked, two liter round bottle flask. 100 gm of calciµm chloride was added into it. This mixture was allowed to keep for 12 hours and then decanted. Large percentage of water was removed during this period. Pressed sodiµm wires were pressed into the round bottle flask containing n-hexane, continuing the addition of the sodiµm 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 + sodiµm 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 it 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. 500 ml of HPLC grade toluene was taken in a clean, single necked, one liter round bottle flask. 20 ml of 99% sulphuric acid was added to it. This mixture was kept for 12 hours with rapid stirring using magnetic stirrer. Neck of the round bottle flask was closed with guard tube containing calciµm 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 sodiµm bicarbonate solution (10%) in the distilled water for complete removal of sulphuric acid. Same procedure was followed for drying the toluene as mentioned in the case of n-hexane.
Preparation of catalyst (TiCLi):
A 50 ml round bottle flask was purged with moisture and oxygen free nitrogen gas. A calculated amount of dry hexane (5 gm) and titaniµm 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. The mixture was kept under inert atmosphere for few minutes. Then the flask was cooled with a septµm. Catalyst activity usually changes with time and the maximµm activity was often reached only after ageing periods of one to two hours.
Synthesis of Trimethyl Alµminiµm:
Trimethyl alµminiµm is widely used as a co catalyst with Ziegler-Natta catalyst for the
polymerisation of olefins whose involvement is crucial in the formation of active centers
during the polymerisation. It is also used in the synthesis of methylalµminoxane, which is
used as a co catalyst with metallocene catalyst in the polymerisation of olefins. All
trialkylalµminiµm compounds are colourless liquids at room temperature and generally
trimethyl alµminiµm exists in the form of dimer. Trialkyl alµminiµms are strong Lewis acids
and cooredinate electron donors to form complexes, in which an alµminiµm atom requires a
stable octate of electrons. These complexes are usually stable enough to be purified by
distillation under vacuµm. That's why ether is always present in trimethyl alµminiµm as an
etherate complex.
(Equation Removed)
Drying of diethylether:
Ether is highly flammable and extremely volatile organic solvent, having low boiling point 35 to 37°C. It is very sensitive to moisture and catches water very fast when it is exposes to atmosphere. That's why it has to contain little water as an impurity. Water reacts in the reaction mediµm to form impurities like magnesiµm hydroxide during the formation of
Grignard reagent and forms alµminiµm hydroxide in subsequent reaction of trimethyl alµminiµm. Ether should be kept in a dark and cold place and air is to be avoided.
500 ml of diethyl ether was taken in a clean dry single neck one liter round bottle flask and 15 gm of calciµm chloride was added into it. This mixture was allowed to keep for 12 hours and decanted. Large percentage of water was removed during this process. Sodiµm 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 distillation condenser.
Preparation of methyl magnesiµm chloride:
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 magnesiµm 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 starts very vigorously, reddish colour of mixture changes very fast and to being 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 percent yield. Since it is moisture sensitive and pyrophoric in nature, it was stored in the inert atmosphere.
Preparation of trimethyl alµminiµm:
The reaction of trimethyl alµminiµm with a Grignard reagent was performed in a three-necked round bottle flask equipped with a condenser, dropping funnel and take off tube with stop cork, which supplies dry nitrogen continuously to the system. 400 ml of perfectly dried diethyl ether was added into the round bottle flask with rapid magnetic stirring and anhydrous alµminiµm chloride (10 gm) is 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 alµminiµm etherate complex and solid material of magnesiµm chloride iodide at the bottom of the round bottle flask.
Isolation of trimethyl alµminiµm:
A distillation condenser was fitted into the above round bottle flask carefully, ensuring that the whole system is in the nitrogen atmosphere. The reaction mixture was heated at 40 to 50°C for three hours for removal of excess ether. Vacuµm of 30 mm Hg was created into the system, Trimethyl alµminiµm 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 vacuµm pµmp and round bottle flask for complete condensation of trimethyl alµminiµm. Trimethyl alµminiµm complexes with ether as etherate, a little amount of compound was found in the traps and collected with the help of syringe and needle. It was observed that the decomposition of trimethyl alµminiµm into gases of methane and ethane takes place with distillation is performed without vacuµm.
Polymerization of ethylene using TiCl4(CH3)3 catalyst to get high molecular weight micron sized polyethylene
One liter of perfectly 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 alµminiµm (~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 two hours. Polyethylene is separated by filtration and dried under reduced pressure of 30 Hg to get the high molecular weight micron sized polymer.
EXPERIMENT 2
Preparation of High molecular weight micron sized polypropylene
The procedure for the step of (1) drying on n-hexane, (2) purification and drying of toluene, (3) preparation of catalyst, TiCl4, (4) synthesis of trimethyl alµminiµm, (5) isolation of trimethyl alµminiµm, (6) drying of diethyl ether and (7) preparation of methyl magnesiµm chloride are already described in the section of "preparation of high molecular weight micron sized polyethylene". Same procedure is also adopted here. Next step is the preparation of high molecular weight micron sized polypropylene.
Polymerization of propylene using TiCl4/(CH3)3Al catalyst to get high molecular weight micron sized polypropylene
One liter of perfectly 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 alµminiµm (-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 two hours. Polyethylene is separated by filtration and dried under reduced pressure of 30 Hg to get the high molecular weight micron sized polymer.
EXPERIMENT 3
Preparation of High molecular weight micron sized polystyrene
500 ml 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 AICI3 (~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 magnesiµm oxide (~1 gm) was added and heated the mixture to a temperature of 600°C. After one hour the mixture is cooled to a temperature of 50°C. The styrene is separated by distillation. Pure styrene and a
pinch of catalyst, ~0.5gm (hydrogen peroxide, 99.9% purity) is heated at a temperature of 120°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 at a temperature of 150°C to remove styrene monomer. The mixture is 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 two hours. Polystyrene is separated by filtration and dried under reduced pressure of 30 Hg to get the high molecular weight micron sized polymer.
High molecular weight micron sized poly isoprene, styrene butadiene copolymer, butadiene polymers are not possible to prepare by the above-said process.
Experiment 4: The novel technique produces high molecular weight micron sized polyethylene within a range of 0.17 to 47 µm using the solvent of xylene at a temperature of 30°C, shear rate of 175 rad/s and in the nitrogen/ argon atmosphere.
Experiment 5: The novel technique produces 5% high molecular weight polyethylene having a diameter of less than 1 µm using the solvent of xylene at a temperature of 30°C, shear rate of 175 rad/s and environment of nitrogen/ argon.
Experiment 6: The novel technique produces 55% high molecular weight polyethylene having a diameter within the range of 1 to 30 µm using the solvent of xylene at a temperature of 30°C, shear rate of 175 rad/s and environment of nitrogen/ argon.
Experiment 7: Again it is also worth to mention here this technique produces micron sized polyethylene with a yield of 100% using the solvent of xylene at a temperature of 30°C, shear rate of 75 rad/s and environment of nitrogen/ argon.
Experiment 8: The novel technique produces high molecular weight micron sized polyethylene within a range of 0.3 to 0.8 µm using the solvent of 1,2,4 trichloro benzene at a temperature of 30°C, shear rate of 175 rad/s and in the nitrogen/ argon atmosphere.
Experiment 9: Similarly the novel technique produces high molecular weight micron sized polyethylene within a range of 0.4 to 0.9 µm using the solvent of decalin at a temperature of 0°C, shear rate of 150 rad/s and in the nitrogen/ argon atmosphere.
Experiment 10: Similarly the novel technique produces high molecular weight micron sized polyethylene within a range of 0.4 to 1.0 µm using the solvent of 1-
chloronaphthalene at a temperature of 10°C, shear rate of 175 rad/s and in the nitrogen/ argon atmosphere.
Experiment 11: Similarly the novel technique produces high molecular weight micron sized polyethylene within a range of 0.2 to 1.3 µm using the solvent of biphenyl at a temperature of 100°C, shear rate of 150 rad/s and in the nitrogen/ argon atmosphere.
Experiment 12: Similarly the novel technique produces high molecular weight micron sized polyethylene within a range of 0.4 to 0.7 µm using the solvent of dodecanol at a temperature of 25°C, shear rate of 150 rad/s and in the nitrogen/ argon atmosphere.
Experiment 13: Similarly the novel technique produces high molecular weight micron sized polyethylene within a range of 0.2 to 0.9 µm using the solvent of diphenyl methane at a temperature of 40°C, shear rate of 150 rad/s and in the nitrogen/ argon atmosphere.
Experiment 14: Similarly the novel technique produces high molecular weight micron sized polyethylene within a range of 0.4 to 1.1 µm using the solvent of diphenyl ether at a temperature of 50°C, shear rate of 175 rad/s and in the nitrogen/ argon atmosphere.
Experiment 15: Similarly the novel technique produces high molecular weight micron sized polyethylene within a range of 0.4 to 0.9 µm using the solvent of hexadecane at a temperature of 30°C, shear rate of 150 rad/s and in the nitrogen/ argon atmosphere.
Experiment 16: The particle size distribution of high molecular weight micron sized polyethylene increases from the range of 0.17-47 to 0.5-1.1 µm, when the experiment is carried out using the solvent of xylene at a temperature of 30°C, shear rate of 175 rad/s and in the oxygen atmosphere.
Experiment 17: The particle size distribution of high molecular weight micron sized polyethylene increases from the range of 0.3-0.8 to 0.4-1.2 jam, when the experiment is carried out using the solvent of 1,2,4 trichloro benzene at a temperature of 30°C, shear rate of 175 rad/s and in the oxygen atmosphere.
Experiment 18: Similarly the particle size distribution of high molecular weight micron sized polyethylene increases from the range of 0.4-0.9 to 0.4-1.1 µm, when the experiment is carried out using the solvent of decalin at a temperature of 0°C, shear rate of 150 rad/s and in the oxygen atmosphere.
Experiment 19: Similarly the particle size distribution of high molecular weight micron sized polyethylene increases from the range of 0.4-1.0 to 0.7-1.5 urn, when the experiment is carried out using the solvent of 1-chloronaphthalene at a temperature of 10°C, shear rate of 175 rad/s and in the oxygen atmosphere.
Experiment 20: Similarly the particle size distribution of high molecular weight micron sized polyethylene increases from the range of 0.2-1.3 to 0.5-1.8 µm, when the experiment is carried out using the solvent of biphenyl at a temperature of 100°C, shear rate of 150 rad/s and in the oxygen atmosphere.
Experiment 21: Similarly the particle size distribution of high molecular weight micron sized polyethylene increases from the range of 0.4-0.7 to 0.6-1.7 urn, when the experiment is carried out using the solvent of dodecanol at a temperature of 25°C, shear rate of 150 rad/s and in the oxygen atmosphere.
Experiment 22: Similarly the particle size distribution of high molecular weight micron sized polyethylene increases from the range of 0.2-0.9 to 1.2-1.9, when the experiment is carried out using the solvent of diphenyl methane at a temperature of 40°C, shear rate of 150 rad/s and in the oxygen atmosphere.
Experiment 23: Similarly the particle size distribution of high molecular weight micron sized polyethylene increases from the range of 0.4-1.1 to 1.4-2.1 µm, when the
experiment is carried out using the solvent of diphenyl ether at a temperature of 50°C, shear rate of 175 rad/s and in the oxygen atmosphere.
Experiment 24: Similarly the particle size distribution of high molecular weight micron sized polyethylene increases from the range of 0.4 -0.9 to 1.4-3.1 µm, when the experiment is carried out using the solvent of hexadecane at a temperature of 30°C, shear rate of 150 rad/s and in the oxygen atmosphere.
Experiment 25: Again the particle size distribution of high molecular weight micron sized polyethylene increases from the range of 0.4-0.9 to the higher size, when the experiment is carried out at a temperature of greater than 0°C, shear rate of less than 175 rad/s and greater than 175 rad/s using the solvent of decalin and nitrogen/argon/oxygen atmosphere.
Experiment 26: Again the particle size distribution of high molecular weight micron sized polyethylene increases from the range of 0.4-1.0 to the higher size, when the experiment is carried out at a temperature of greater than 10°C, shear rate of less
than 175 rad/s and greater than 175 rad/s using the solvent of 1-chloronaphthalene and oxygen/argon/oxygen atmosphere.
Experiment 27: Again the particle size distribution of high molecular weight micron sized polyethylene increases from the range of 0.2-1.3 µm to the higher size, when the experiment is carried out at a temperature of greater than 100°C, shear rate of less than 175 rad/s and greater than 175 rad/s using the solvent of biphenyl and oxygen/argon/oxygen atmosphere.
Experiment 28: Again the particle size distribution of high molecular weight micron sized polyethylene increases from the range of 0.4-0.7 µm to the higher size, when the experiment is carried out at a temperature of greater than 25°C, shear rate of less than 175 rad/s and greater than 175 rad/s using the solvent of dodecanol and oxygen/argon/oxygen atmosphere.
Experiment 29: Again the particle size distribution of high molecular weight micron sized polyethylene increases from the range of 0.2-0.9 µm to the higher size, when the experiment is carried out at a temperature of greater than 40°C, shear rate of less than 175 rad/s and greater than 175 rad/s using the solvent of diphenyl methane and oxygen/argon/oxygen atmosphere.
Experiment 30: Again the particle size distribution of high molecular weight micron sized
polyethylene increases from the range of 0.4-1.1 µm to the higher size, when the experiment is carried out at a temperature of greater than 50°C, shear rate of less than 150 rad/s and greater than 150 rad/s using the solvent of diphenyl ether and oxygen/argon/oxygen atmosphere.
Experiment 31: Again the particle size distribution of high molecular weight micron sized polyethylene increases from the range of 0.4 -0.9 µm to the higher size, when the experiment is carried out at a temperature of greater than 30°C, shear rate of less than 150 rad/s and greater than 150 rad/s using the solvent of hexadecane and oxygen/argon/oxygen atmosphere.
Experiment 32: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of 1-octanol in oxygen/argon/oxygen atmosphere.
Experiment 33: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of isoamyl alcohol in oxygen/argon/oxygen atmosphere.
Experiment 34: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of cyclohexane in oxygen/argon/oxygen atmosphere.
Experiment 35: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of toluene in oxygen/argon/oxygen atmosphere.
Experiment 36: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of cyclohexanone in oxygen/argon/oxygen atmosphere.
Experiment 37: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of isoamyl acetate in oxygen/argon/oxygen atmosphere.
Experiment 38: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of isobutyl acetate in oxygen/argon/oxygen atmosphere.
Experiment 39: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of phenyl ether in oxygen/argon/oxygen atmosphere.
Experiment 40: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of chloroform in oxygen/argon/oxygen atmosphere.
Experiment 41: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of decahydronaphthalene in oxygen/argon/oxygen atmosphere.
Experiment 42: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of diethyloxalate in oxygen/argon/oxygen atmosphere.
Experiment 43: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of dimethylphthalate in oxygen/argon/oxygen atmosphere.
Experiment 44: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of dioxane in oxygen/argon/oxygen atmosphere.
Experiment 45: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of ethyl acetate in oxygen/argon/oxygen atmosphere.
Experiment 46: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of ethyl benzene in oxygen/argon/oxygen atmosphere.
Experiment 47: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of methyl chloride in oxygen/argon/oxygen atmosphere.
Experiment 48: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of 1-nitopropane in oxygen/argon/oxygen atmosphere.
Experiment 49: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of phosphorous trichloride in oxygen/argon/oxygen atmosphere.
Experiment 50: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of tetrahydofuran in oxygen/argon/oxygen atmosphere.
Experiment 51: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of tributyl phosphate in oxygen/argon/oxygen atmosphere.
Experiment 52: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of acrylonitrile in oxygen/argon/oxygen atmosphere.
Experiment 53: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of chlorobenzene in oxygen/argon/oxygen atmosphere.
Experiment 54: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of acetic acid in oxygen/argon/oxygen atmosphere.
Experiment 55: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of n-butanol in oxygen/argon/oxygen atmosphere.
Experiment 56: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of isobutanol in oxygen/argon/oxygen atmosphere.
Experiment 57: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of carbon tetrachloride in oxygen/argon/oxygen atmosphere.
Experiment 58: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of acetophenone in oxygen/argon/oxygen atmosphere.
Experiment 59: It was not possible to synthesis micron sized polyethylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of paraffin liquid in oxygen/argon/oxygen atmosphere.
Experiment 60: The novel technique produces high molecular weight micron sized polypropylene within a range of 0.17 to 47 urn using the solvent of xylene at a temperature of 30°C, shear rate of 150 rad/s and environment of nitrogen/argon.
Experiment 61: The novel technique produces 11% high molecular weight polypropylene having a diameter of less than 1 µm using the solvent of xylene at a temperature of 30°C, shear rate of 150 rad/s and environment of nitrogen/argon.
Experiment 62: The novel technique produces 49% high molecular weight polypropylene having a diameter within the range of 1 to 20 µm using the solvent of xylene at a temperature of 30°C, shear rate of 150 rad/s and environment of nitrogen/argon.
Experiment 63: Again it is also worth to mention here this technique produces micron sized polypropylene with a yield of 100% using the solvent of xylene at a temperature of 30°C, shear rate of 150 rad/s and environment of nitrogen/argon.
Experiment 64: The novel technique produces high molecular weight micron sized polypropylene within a range of 0.3 to 0.8 urn using the solvent of 1-octanol at a temperature of 0°C, shear rate of 175 rad/s and in the nitrogen/ argon atmosphere.
Experiment 65: Similarly the novel technique produces high molecular weight micron sized polypropylene within a range of 0.2 to 1.0 µm using the solvent of isoamyl alcohol at a temperature of -10°C, shear rate of 150 rad/s and in the nitrogen/ argon atmosphere.
Experiment 66: Similarly the novel technique produces high molecular weight micron sized polypropylene within a range of 0.4 to 1.1 urn using the solvent of benzene at a temperature of 25°C, shear rate of 175 rad/s and in the nitrogen/ argon atmosphere.
Experiment 67: Similarly the novel technique produces high molecular weight micron sized polypropylene within a range of 0.2 to 1.9 µm using the solvent of cyclohexane at a temperature of 30°C, shear rate of 150 rad/s and in the nitrogen/ argon atmosphere.
Experiment 68: Similarly the novel technique produces high molecular weight micron sized polypropylene within a range of 0.2 to 0.5 µm using the solvent of toluene at a
temperature of-30°C, shear rate of 175 rad/s and in the nitrogen/ argon atmosphere.
Experiment 69: Similarly the novel technique produces high molecular weight micron sized polypropylene within a range of 0.2 to 0.5 µm using the solvent of decalin at a temperature of -20°C, shear rate of 150 rad/s and in the nitrogen/ argon atmosphere.
Experiment 70: Similarly the novel technique produces high molecular weight micron sized polypropylene within a range of 0.2 to 0.9 µm using the solvent of 1-chloronaphthalene at a temperature of 20°C, shear rate of 175 rad/s and in the nitrogen/ argon atmosphere.
Experiment 71: Similarly the novel technique produces high molecular weight micron sized polypropylene within a range of 0.5 to 1.1 µm using the solvent of cyclohexane at a temperature of-10°C, shear rate of 175 rad/s and in the nitrogen/ argon atmosphere.
Experiment 72: Similarly the novel technique produces high molecular weight micron sized polypropylene within a range of 0.2 to 0.9 µm using the solvent of diphenyl ether at
a temperature of 30°C, shear rate of 150 rad/s and in the nitrogen/ argon atmosphere.
Experiment 73: Similarly the novel technique produces high molecular weight micron sized polypropylene within a range of 1.0 to 1.9 µm using the solvent of biphenyl at a temperature of 90°C, shear rate of 150 rad/s and in the nitrogen/ argon atmosphere.
Experiment 74: Similarly the novel technique produces high molecular weight micron sized polypropylene within a range of 0.2 to 1.7 µm using the solvent of isoamyl acetate at a temperature of -30°C, shear rate of 175 rad/s and in the nitrogen/ argon atmosphere.
Experiment 75: Similarly the novel technique produces high molecular weight micron sized polypropylene within a range of 0.8 to 2.2 µm using the solvent of isobutyl acetate at a temperature of -30°C, shear rate of 175 rad/s and in the nitrogen/ argon atmosphere.
Experiment 76: Similarly the novel technique produces high molecular weight micron sized polypropylene within a range of 0.2 to 1.5 µm using the solvent of phenyl ether at a temperature of 60°C, shear rate of 175 rad/s and in the nitrogen/ argon atmosphere.
Experiment 77: The particle size distribution of high molecular weight micron sized polypropylene increases from 0.17-0.47 µm to 0.45-1.55 urn when the experiment
is carried out at a temperature of 30°C and shear rate of 150 rad/s using xylene as solvent and in oxygen environment.
Experiment 78: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.3-0.8 µm to 0.6-1.1 urn when the experiment is carried out at a temperature of 0°C and shear rate of 175 rad/s using 1-octanol as solvent and in oxygen environment.
Experiment 79: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.2-1.0 µm to 0.7-1.9 µm when the experiment is carried out at a temperature of -10°C and shear rate of 150 rad/s using isoamyl alcohol as solvent and in oxygen environment.
Experiment 80: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.4-1.1 µm to 0.9 to 2.2 µm when the experiment is
carried out at a temperature of 25°C and shear rate of 175 rad/s using benzene as solvent and in oxygen environment.
Experiment 81: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.2-1.9 µm to 0.7 to 2.5 urn when the experiment is carried out at a temperature of 30°C and shear rate of 150 rad/s using cyclohexane as solvent and in oxygen environment.
Experiment 82: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.2-0.5 µm to 1.2-2.5 µm when the experiment is carried out at a temperature of -30°C and shear rate of 175 rad/s using toluene as solvent and in oxygen environment.
Experiment 83: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.2-0.7 µm to 1.0-2.1 µm when the experiment is carried out at a temperature of -20°C and shear rate of 150 rad/s using decalin as solvent and in oxygen environment.
Experiment 84: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.2-0.9 µm to 1.1-1.9 µm when the experiment is carried out at a temperature of 20°C and shear rate of 175 rad/s using 1-chloronaphthalene as solvent and in oxygen environment.
Experiment 85: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.5-1.1 µm to 1.6-2.9 µm when the experiment is carried out at a temperature of-10°C and shear rate of 175 rad/s using cyclohexane as solvent and in oxygen environment.
Experiment 86: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.2-0.9 µm to 1.0-1.9 µm when the experiment is carried out at a temperature of 30°C and shear rate of 150 rad/s using diphenyl ether as solvent and in oxygen environment.
Experiment 87: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 1.0-1.9 µm to 2.1-2.9 µm when the experiment is carried out at a temperature of 90°C and shear rate of 150 rad/s using biphenyl as solvent and in oxygen environment.
Experiment 88: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.2-1.7 urn to 0.5-1.6 µm when the experiment is carried out at a temperature of -30°C and shear rate of 175 rad/s using isoamyl acetate as solvent and in oxygen environment.
Experiment 89: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.8-2.2 urn to 1.9-3.1 µm when the experiment is carried out at a temperature of -30°C and shear rate of 175 rad/s using isobutyl acetate as solvent and in oxygen environment.
Experiment 90: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.2-1.5 µm to 0.9-1.8 µm when the experiment is carried out at a temperature of 60°C and shear rate of 175 rad/s using phenyl ether as solvent and in oxygen environment.
Experiment 91: The particle size distribution of high molecular weight micron sized polypropylene increases from 0.17-0.47 µm to the higher size, when the experiment is carried out at a temperature greater than 30°C and shear rate of less than and greater than 150 rad/s using xylene as solvent and in oxygen environment.
Experiment 92: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.3-0.8 µm to the higher size, when the experiment is carried out at a temperature greater than 0°C and shear rate of less than and greater than 175 rad/s using 1-octanol as solvent and in oxygen environment.
Experiment 93: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.2-1.0 µm to the higher size, when the experiment is carried out at a temperature greater than -10°C and shear rate of less than and greater than 150 rad/s using isoamyl alcohol as solvent and in oxygen environment.
Experiment 94: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.4-1.1 µm to the higher size, when the experiment is carried out at a temperature greater than 25°C and shear rate of less than and greater than 175 rad/s using benzene as solvent and in oxygen environment.
Experiment 95: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.2-1.9 µm to the higher size, when the experiment is carried out at a temperature greater than 30°C and shear rate of less than and greater than 150 rad/s using cyclohexane as solvent and in oxygen environment.
Experiment 96: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.2-0.5 µm to the higher size, when the experiment is

carried out at a temperature greater than -30°C and shear rate of less than and greater than 175 rad/s using toluene as solvent and in oxygen environment.
Experiment 97: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.2-0.7 urn to the higher size, when the experiment is carried out at a temperature greater than -20°C and shear rate of less than and greater than 150 rad/s using decalin as solvent and in oxygen environment.
Experiment 98: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.2-0.9 µm to the higher size, when the experiment is carried out at a temperature greater than 20°C and shear rate of less than and greater than 175 rad/s using 1-chloronaphthalene as solvent and in oxygen environment.
Experiment 99: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.5-1.1 µm to the higher size, when the experiment is carried out at a temperature greater than -10°C and shear rate of less than and greater than 175 rad/s using cyclohexane as solvent and in oxygen environment.
Experiment 100: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.2-0.9 µm to the higher size, when the experiment is carried out at a temperature greater than 30°C and shear rate of less than and greater than 175 rad/s using diphenyl ether as solvent and in oxygen environment
Experiment 101: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 1.0-1.9 µm to the higher size, when the experiment is carried out at a temperature greater than 90°C and shear rate of less than and greater than 150 rad/s using biphenyl as solvent and in oxygen environment.
Experiment 102: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.2-1.7 µm to the higher size, when the experiment is carried out at a temperature greater than -30°C and shear rate of less than and greater than 175 rad/s using isoamyl acetate as solvent and in oxygen environment.
Experiment 103: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.8-2.2 µm to the higher size, when the experiment is carried out at a temperature greater than -30°C and shear rate of less than and greater than 175 rad/s using isobutyl acetate as solvent and in oxygen environment.
Experiment 104: Again the particle size distribution of high molecular weight micron sized polypropylene increases from 0.2-1.5 urn to the higher size, when the experiment is carried out at a temperature greater than 60°C and shear rate of less than and greater than 175 rad/s using phenyl ether as solvent and in oxygen environment.
Experiment 105: It was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of 1,2,4-trichloro benzene in oxygen/argon/oxygen atmosphere.
Experiment 106: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of dodecanol in oxygen/argon/oxygen atmosphere.
Experiment 107: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of diphenylmethane in oxygen/argon/oxygen atmosphere.
Experiment 108: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of hexadecane in oxygen/argon/oxygen atmosphere.
Experiment 109: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of chloroform in oxygen/argon/oxygen atmosphere.
Experiment 110: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of decahydronaphthalene in oxygen/argon/oxygen atmosphere.
Experiment 111: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of diethyloxalate in oxygen/argon/oxygen atmosphere.
Experiment 112: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of dimethylphthalate in oxygen/argon/oxygen atmosphere.
Experiment 113: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of dioxane in oxygen/argon/oxygen atmosphere.
Experiment 114: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of ethyl acetate in oxygen/argon/oxygen atmosphere.
Experiment 115: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of ethyl benzene in oxygen/argon/oxygen atmosphere.
Experiment 116: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of methyl chloride in oxygen/argon/oxygen atmosphere.
Experiment 117: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of 1-nitopropane in oxygen/argon/oxygen atmosphere.
Experiment 118: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of phosphorous trichloride in oxygen/argon/oxygen atmosphere.
Experiment 119: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of tetrahydofuran in oxygen/argon/oxygen atmosphere.
Experiment 120: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of tributyl phosphate in oxygen/argon/oxygen atmosphere.
Experiment 121: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of acrylonitrile in oxygen/argon/oxygen atmosphere.
Experiment 122: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of chlorobenzene in oxygen/argon/oxygen atmosphere.
Experiment 123: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of acetic acid in oxygen/argon/oxygen atmosphere.
Experiment 124: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of carbon tetrachloride in oxygen/argon/oxygen atmosphere.
Experiment 125: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of acetophenone in oxygen/argon/oxygen atmosphere.
Experiment 126: Similarly it was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of paraffin liquid in oxygen/argon/oxygen atmosphere.
Experiment 127: The novel technique produces high molecular weight micron sized polystyrene within a range of 0.17 to 0.51 urn using the solvent of dimethyl siloxane at a temperature of 30°C, shear rate of 175 rad/s and environment of nitrogen/argon.
Experiment 128: The novel technique produces 9% high molecular weight polystyrene having a diameter of less than 1 µm using the solvent of dimethyl siloxane at a temperature of 30°C, shear rate of 175 rad/s and environment of nitrogen/argon.
Experiment 129: The novel technique produces 37% high molecular weight polystyrene having a diameter within the range of 1 to 9 µm using the solvent of dimethyl siloxane at a temperature of 30°C, shear rate of 175 rad/s and environment of nitrogen/argon.
Experiment 130: Again it is also worth to mention here this technique produces micron sized polystyrene with a yield of 100% using the solvent of dimethyl siloxane at a temperature of 30°C, shear rate of 175 rad/s and environment of nitrogen/argon.
Experiment 131: Similarly the novel technique produces high molecular weight micron sized polystyrene within a range of 0.5 to 1.2 µm using the solvent of benzene at a temperature of 10°C, shear rate of 150 rad/s and environment of nitrogen/argon.
Experiment 132: Similarly the novel technique produces high molecular weight micron sized polystyrene within a range of 0.2 to 0.5 µm using the solvent of carbon disulfide at a temperature of -30°C, shear rate of 150 rad/s and environment of nitrogen/argon.
Experiment 133: Similarly the novel technique produces high molecular weight micron sized polystyrene within a range of 0.6 to 2.5 µm using the solvent of chloroform at a temperature of-20°C, shear rate of 175 rad/s and environment of nitrogen/argon.
Experiment 134: Similarly the novel technique produces high molecular weight micron sized polystyrene within a range of 0.9 to 1.5 µm using the solvent of cyclohexane at a temperature of -10°C, shear rate of 175 rad/s and environment of nitrogen/argon.
Experiment 135: Similarly the novel technique produces high molecular weight micron sized polystyrene within a range of 0.8 to 1.5 µm using the solvent of decahydronaphthalene at a temperature of -10°C, shear rate of 175 rad/s and environment of nitrogen/argon.
Experiment 136: Similarly the novel technique produces high molecular weight micron sized polystyrene within a range of 0.5 to 1.1 µm using the solvent of diethyloxalate at a temperature of -20°C, shear rate of 150 rad/s and environment of nitrogen/argon.
Experiment 137: Similarly the novel technique produces high molecular weight micron sized polystyrene within a range of 0.3 to 1.9 urn using the solvent of dimethylphthalate at a temperature of 20°C, shear rate of 175 rad/s and environment
of nitrogen/argon.
Experiment 138: Similarly the novel technique produces high molecular weight micron sized polystyrene within a range of 0.3 to 0.9 µm using the solvent of dioxane at a temperature of 30°C, shear rate of 150 rad/s and environment of nitrogen/argon.
Experiment 139: Similarly the novel technique produces high molecular weight micron sized polystyrene within a range of 0.3 to 0.6 µm using the solvent of ethyl acetate at a temperature of -30°C, shear rate of 150 rad/s and environment of nitrogen/argon.
Experiment 140: Similarly the novel technique produces high molecular weight micron sized polystyrene within a range of 0.3 to 1.6 urn using the solvent of ethyl benzene at a temperature of -30°C, shear rate of 175 rad/s and environment of nitrogen/argon.
Experiment 141: Similarly the novel technique produces high molecular weight micron sized polystyrene within a range of 0.6 to 1.6 µm using the solvent of methyl chloride at a temperature of -20°C, shear rate of 150 rad/s and environment of nitrogen/argon.
Experiment 142: Similarly the novel technique produces high molecular weight micron sized polystyrene within a range of 0.2 to 0.9 urn using the solvent of 1-nitropropane at a temperature of -30°C, shear rate of 175 rad/s and environment of nitrogen/argon.
Experiment 143: Similarly the novel technique produces high molecular weight micron sized polystyrene within a range of 0.3 to 0.6 µm using the solvent of phosphorous trichloride at a temperature of -30°C, shear rate of 150 rad/s and environment of nitrogen/argon.
Experiment 144: Similarly the novel technique produces high molecular weight micron sized polystyrene within a range of 0.6 to 2.6 µm using the solvent of tetrahydrofuran at a temperature of -30°C, shear rate of 150 rad/s and environment of nitrogen/argon.
Experiment 145: Similarly the novel technique produces high molecular weight micron sized polystyrene within a range of 0.9 to 2.6 µm using the solvent of tributyl
phosphate at a temperature of -10°C, shear rate of 175 rad/s and environment of nitrogen/argon.
Experiment 146: The particle size distribution of high molecular weight micron sized polystyrene increases from 0.17-0.51 to 0.3-1.01 µm using the solvent of dimethyl siloxane at a temperature of 30°C and shear rate of 175 rad/s using dimethyl siloxane as a solvent and in oxygen environment.
Experiment 147: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.5-1.2 to 0.9-1.5 µm using the solvent of benzene at a temperature of 10°C and shear rate of 150 rad/s using benzene as a solvent and in oxygen environment.
Experiment 148: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.2-0.5 to 0.6-1.1 µm using the solvent of carbon disulfide at a temperature of -30°C and shear rate of 150 rad/s using carbon disulfide as a solvent and in oxygen environment.
Experiment 149: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.6-2.5 to 0.7-2.7 µm using the solvent of chloroform at a temperature of -20°C and shear rate of 175 rad/s using chloroform as a solvent and in oxygen environment.
Experiment 150: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.9-1.5 to 1.4-1.9 µm using the solvent of cyclohexane at a temperature of -10°C and shear rate of 175 rad/s using cyclohexane as a solvent and in oxygen environment.
Experiment 151: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.8-1.5 to 1.1-2.1 µm using the solvent of decahydronaphthalene at a temperature of -10°C and shear rate of 175 rad/s using decahydronaphthalene as a solvent and in oxygen environment.
Experiment 152: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.5-1.1 to 0.9-2.1 µm using the solvent of diethyloxalate at a temperature of -20°C and shear rate of 150 rad/s using diethyloxalate as a solvent and in oxygen environment.
Experiment 153: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.3-1.9 to 0.6-2.1 µm using the solvent of
dimethylphthalate at a temperature of 20°C and shear rate of 175 rad/s using dimethylphthalate as a solvent and in oxygen environment.
Experiment 154: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.3-0.9 to 0.7-1.5 urn using the solvent of dioxane at a temperature of 30°C and shear rate of 150 rad/s using dioxane as a solvent and in oxygen environment.
Experiment 155: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.3-0.6 to 0.5-1.1 µm using the solvent of ethyl acetate at a temperature of-30°C and shear rate of 150 rad/s using ethyl acetate as a solvent and in oxygen environment.
Experiment 156: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.3-1.6 to 0.7-2.1 µm using the solvent of ethyl benzene at a temperature of-30°C, shear rate of 175 rad/s using ethyl benzene as a solvent and in oxygen environment.
Experiment 157: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.6-1.6 to 1.3-2.1 µm using the solvent of methyl chloride at a temperature of -20°C and shear rate of 150 rad/s using methyl chloride as a solvent and in oxygen environment.
Experiment 158: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.2-0.9 to 0.5-2.9 µm using the solvent of 1-nitropropane at a temperature of -30°C and shear rate of 175 rad/s using 1-nitropropane as a solvent and in oxygen environment.
Experiment 159: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.3-0.6 to 0.7-1.2 µm using the solvent of phosphorous trichloride at a temperature of-30°C and shear rate of 150 rad/s using phosphorous trichloride as a solvent and in oxygen environment.
Experiment 160: Similarly the novel technique produces high molecular weight micron sized polystyrene increases from 0.6-2.6 to 0.9-3.1 µm using the solvent of tetrahydrofuran at a temperature of -30°C and shear rate of 150 rad/s using tetrahydrofuran as a solvent and in oxygen environment.
Experiment 161: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.9-2.6 to 2.1-4.1 µm using the solvent of tributyl
phosphate at a temperature of -10°C and shear rate of 175 rad/s using tributyl phosphate as a solvent and in oxygen environment.
Experiment 162: The particle size distribution of high molecular weight micron sized polystyrene increases from 0.17-0.51 to the higher size, when the experiment is carried out at a temperature of 30°C and shear rate of less than and greater than 175 rad/s using dimethyl siloxane as a solvent and in oxygen environment.
Experiment 163: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.5-1.2 to the higher size, when the experiment is carried out at a temperature of 10°C and shear rate of less than and greater than 150 rad/s using benzene as a solvent and in oxygen environment.
Experiment 164: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.2-0.5 to the higher size, when the experiment is carried out at a temperature of -30°C and shear rate of less than and greater than 150 rad/s using carbon disulfide as a solvent and in oxygen environment.
Experiment 165: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.6-2.5 to the higher size, when the experiment is carried out at a temperature of-20°C and shear rate of less than and greater than 175 rad/s using chloroform as a solvent and in oxygen environment.
Experiment 166: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.9-1.5 to the higher size, when the experiment is carried out at a temperature of-10°C and shear rate of less than and greater than 175 rad/s using cyclohexane as a solvent and in oxygen environment.
Experiment 167: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.8-1.5 to the higher size, when the experiment is carried out at a temperature of -10°C and shear rate of less than and greater than 175 rad/s using decahydronaphthalene as a solvent and in oxygen environment.
Experiment 168: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.5-1.1 to the higher size, when the experiment is carried out at a temperature of -20°C and shear rate of less than and greater than 150 rad/s using diethyloxalate as a solvent and in oxygen environment.
Experiment 169: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.3-1.9 to the higher size, when the experiment is
carried out at a temperature of 20°C and shear rate of less than and greater than 175 rad/s using dimethylphthalate as a solvent and in oxygen environment.
Experiment 170: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.3-0.9 to the higher size, when the experiment is carried out at a temperature of 30°C and shear rate of less than and greater than 150 rad/s using dioxane as a solvent and in oxygen environment.
Experiment 171: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.3-0.6 to the higher size, when the experiment is carried out at a temperature of-30°C and shear rate of less than and greater than 150 rad/s using ethyl acetate as a solvent and in oxygen environment.
Experiment 172: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.3-1.6 to the higher size, when the experiment is carried out at a temperature of -30°C, shear rate of less than and greater than 175 rad/s using ethyl benzene as a solvent and in oxygen environment.
Experiment 173: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.6-1.6 to the higher size, when the experiment is carried out at a temperature of -20°C and shear rate of less than and greater than 150 rad/s using methyl chloride as a solvent and in oxygen environment.
Experiment 174: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.2-0.9 to the higher size, when the experiment is carried out at a temperature of-30°C and shear rate of less than and greater than 175 rad/s using 1-nitropropane as a solvent and in oxygen environment.
Experiment 175: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.3-0.6 to the higher size, when the experiment is carried out at a temperature of-30°C and shear rate of less than and greater than 150 rad/s using phosphorous trichloride as a solvent and in oxygen environment.
Experiment 176: Similarly the novel technique produces high molecular weight micron sized polystyrene increases from 0.6-2.6 to the higher size, when the experiment is carried out at a temperature of-30°C and shear rate of less than and greater than 150 rad/s using tetrahydrofuran as a solvent and in oxygen environment.
Experiment 177: Similarly the particle size distribution of high molecular weight micron sized polystyrene increases from 0.9-2.6 to the higher size, when the experiment is
carried out at a temperature of -10°C and shear rate of less than and greater than 175 rad/s using tributyl phosphate as a solvent and in oxygen environment.
Experiment 178: It was not possible to synthesis micron sized polypropylene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of xylene in oxygen/argon/oxygen atmosphere.
Experiment 179: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of 1,2,4-trichloro benzene in oxygen/argon/oxygen atmosphere.
Experiment 180: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of decalin in oxygen/argon/oxygen atmosphere.
Experiment 181: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of 1-chloronaphthalene in oxygen/argon/oxygen atmosphere.
Experiment 182: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of biphenyl in oxygen/argon/oxygen atmosphere.
Experiment 183: It was not possible to synthesis micron sized polystyrene over the range ot temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of dodecanol in oxygen/argon/oxygen atmosphere.
Experiment 184: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of diphenylmethane in oxygen/argon/oxygen atmosphere.
Experiment 185: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of diphenyl ether in oxygen/argon/oxygen atmosphere.
Experiment 186: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of hexadecane in oxygen/argon/oxygen atmosphere.
Experiment 187: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of 1-octanol in oxygen/argon/oxygen atmosphere.
Experiment 188: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of isoamyl alcohol in oxygen/argon/oxygen atmosphere.
Experiment 189: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of phenyl ether in oxygen/argon/oxygen atmosphere.
Experiment 190: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of acrylonitrile in oxygen/argon/oxygen atmosphere.
Experiment 191: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of chlorobenzene in oxygen/argon/oxygen atmosphere.
Experiment 192: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of acetic acid in oxygen/argon/oxygen atmosphere.
Experiment 193: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of n-butanol in oxygen/argon/oxygen atmosphere.
Experiment 194: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of isobutanol in oxygen/argon/oxygen atmosphere.
Experiment 195: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of methanol in oxygen/argon/oxygen atmosphere.
Experiment 196: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of acetophenone in oxygen/argon/oxygen atmosphere.
Experiment 197: It was not possible to synthesis micron sized polystyrene over the range of temperatures from -30 to +150°C and shear rates of 0.2 to 200 rad/s using the solvent of paraffin liquid in oxygen/argon/oxygen atmosphere.
Experiment 198: The BET surface area reveals the minimµm surface area of high molecular weight micron sized polyethylene is 16.2 m2/gm when the experiment is carried out using the solvent of xylene at a temperature of 30°C, shear rate of 175 rad/s and in the nitrogen/ argon atmosphere.
Experiment 199: The BET surface area reveals the minimµm surface area of high molecular weight micron sized polypropylene is 16.2 m /gm using the solvent of xylene at a temperature of 30°C and shear rate of 150 rad/s.
Experiment 200: The BET surface area reveals the minimµm surface area of high molecular weight micron sized polystyrene is 17.7 m2/gm using the solvent of using the solvent of dimethyl siloxane at a temperature of 30°C and shear rate of 175 rad/s.
Experiment 201: The micro graph obtained from scanning electron microscopy shows that the high molecular weight micron sized polyethylene is spherical in nature.
Experiment 202: The micro graph obtained from scanning electron microscopy shows that the high molecular weight micron sized polypropylene is spherical in nature.
Experiment 203: The micro graph obtained from scanning electron microscopy shows that the high molecular weight micron sized polystyrene is spherical in nature.
Experiment 204: There is no difference in chemical structure between the commercial high density polyethylene and high molecular weight micron sized polyethylene supported by infrared spectroscopy analysis.
Experiment 205: There is no difference in chemical structure between the commercial low density polyethylene and high molecular weight micron sized polyethylene supported by infrared spectroscopy analysis.
Experiment 206: There is no difference in chemical structure between the commercial polypropylene and high molecular weight micron sized polypropylene supported by infrared spectroscopy analysis.
Experiment 207: There is no difference in chemical structure between the commercial polystyrene and high molecular weight micron sized polystyrene supported by infrared spectroscopy analysis.
Experiment 208: The high molecular weight micron sized polyethylene is more crystalline in nature with respect to commercial low density polyethylene supported by the peak observed at 22° (20) through X-ray diffraction studies.
Experiment 209: The high molecular weight micron sized polyethylene is more crystalline in nature with respect to commercial high density polyethylene supported by the peak observed at 22° (20) through X-ray diffraction studies.
Experiment 210: The high molecular weight micron sized polyethylene is more crystalline in nature with respect to commercial low density polyethylene supported by the peak observed at 24° (20) through X-ray diffraction studies.
Experiment 211: The high molecular weight micron sized polyethylene is more crystalline in nature with respect to commercial high density polyethylene supported by the peak observed at 24° (20) through X-ray diffraction studies.
Experiment 212: The high molecular weight micron sized polypropylene is more crystalline in nature with respect to commercial polypropylene supported by the peak observed at 16.8° (29) through X-ray diffraction studies.
Experiment 213: The high molecular weight micron sized polypropylene is more crystalline in nature with respect to commercial polypropylene supported by the peak observed at 18.6° (20) through X-ray diffraction studies.
Experiment 214: The high molecular weight micron sized polypropylene is more crystalline in nature with respect to commercial polypropylene supported by the peak observed at 21.8° (20) through X-ray diffraction studies.
Experiment 215: The high molecular weight micron sized polystyrene is more crystalline in nature with respect to commercial polystyrene supported by the peak observed at 16.7° (20) through X-ray diffraction studies.
Experiment 216: The storage modulus increases from commercial high density polyethylene to the high molecular weight micron sized polyethylene over the range of temperatures from 35 to 125°C and frequency of 1 Hz.
Experiment 217: The storage modulus increases from commercial high density polyethylene to the high molecular weight micron sized polyethylene over the range of temperatures from 35 to 125°C and frequency of 2 Hz.
Experiment 218: The storage modulus increases from commercial high density polyethylene to the high molecular weight micron sized polyethylene over the range of temperatures from 35 to 125°C and frequency of 5 Hz.
Experiment 219: The storage modulus increases from commercial high density polyethylene to the high molecular weight micron sized polyethylene over the range of temperatures from 35 to 125°C and frequency of 10 Hz.
Experiment 220: The storage modulus increases from commercial polypropylene to the high
molecular weight micron sized polypropylene over the range of temperatures from
40 to 170°C and frequency of 1 Hz. Experiment 221: The storage modulus increases from commercial polypropylene to the high
molecular weight micron sized polypropylene over the range of temperatures from
40 to 170°C and frequency of 2 Hz.
Experiment 222: The storage modulus increases from commercial polypropylene to the high molecular weight micron sized polypropylene over the range of temperatures from 40 to 170°C and frequency of 5 Hz.
Experiment 223: The storage modulus increases from commercial polypropylene to the high molecular weight micron sized polypropylene over the range of temperatures from 40 to 170°C and frequency of 10 Hz.
Experiment 224: The storage modulus increases from commercial polystyrene to the high molecular weight micron sized polystyrene over the range of temperatures from 30 to 120°C and frequency of 1 Hz.
Experiment 225: The storage modulus increases from commercial polystyrene to the high molecular weight micron sized polystyrene over the range of temperatures from 30 to 120°C and frequency of 2 Hz.
Experiment 226: The storage modulus increases from commercial polystyrene to the high molecular weight micron sized polystyrene over the range of temperatures from 30 to 120°C and frequency of 5 Hz.
Experiment 227: The storage modulus increases from commercial polystyrene to the high molecular weight micron sized polystyrene over the range of temperatures from 30 to 120°C and frequency of 10 Hz.
Experiment 228: The loss modulus decreases from commercial high density polyethylene to the high molecular weight micron sized polyethylene over the range of temperatures from 40 to 170°C and frequency of 1 Hz.
Experiment 229: The loss modulus decreases from commercial high density polyethylene to the high molecular weight micron sized polyethylene over the range of temperatures from 35 to 125°C and frequency of 2 Hz.
Experiment 230: The loss modulus decreases from commercial high density polyethylene to the high molecular weight micron sized polyethylene over the range of temperatures from 35 to 125°C and frequency of 5 Hz.
Experiment 231: The loss modulus decreases from commercial high density polyethylene to the high molecular weight micron sized polyethylene over the range of temperatures from 35 to 125°C and frequency of 10 Hz.
Experiment 232: The loss modulus decreases from commercial polypropylene to the high molecular weight micron sized polypropylene over the range of temperatures from 40 to 170°C and frequency of 1 Hz.
Experiment 233: The loss modulus decreases from commercial polypropylene to the high molecular weight micron sized polypropylene over the range of temperatures from 40 to 170°C and frequency of 2 Hz.
Experiment 234: The loss modulus decreases from commercial polypropylene to the high molecular weight micron sized polypropylene over the range of temperatures from 40 to 170°C and frequency of 5 Hz.
Experiment 235: The loss modulus decreases from commercial polypropylene to the high molecular weight micron sized polypropylene over the range of temperatures from 40 to 170°C and frequency of 10 Hz.
Experiment 236: The loss modulus decreases from commercial polystyrene to the high molecular weight micron sized polystyrene over the range of temperatures from 30 to 120°C and frequency of 1 Hz before the glass transition temperature.
Experiment 237: The loss modulus decreases from commercial polystyrene to the high molecular weight micron sized polystyrene over the range of temperatures from 30 to 120°C and frequency of 2 Hz before the glass transition temperature.
Experiment 238: The loss modulus decreases from commercial polystyrene to the high molecular weight micron sized polystyrene over the range of temperatures from 30 to 120°C and frequency of 5 Hz before the glass transition temperature.
Experiment 239: The loss modulus decreases from commercial polystyrene to the high molecular weight micron sized polystyrene over the range of temperatures from 30 to 120°C and frequency of 10 Hz before the glass transition temperature.
Experiment 240: But the loss modulus increases from commercial polystyrene to the high molecular weight micron sized polystyrene over the range of temperatures from 30 to 120°C and frequency of 1 Hz after the glass transition temperature.
Experiment 241: Similarly the loss modulus increases from commercial polystyrene to the high molecular weight micron sized polystyrene over the range of temperatures from 30 to 120°C and frequency of 2 Hz after the glass transition temperature.
Experiment 242: Similarly the loss modulus increases from commercial polystyrene to the high molecular weight micron sized polystyrene over the range of temperatures from 30 to 120°C and frequency of 5 Hz after the glass transition temperature.
Experiment 243: Similarly the loss modulus increases from commercial polystyrene to the high molecular weight micron sized polystyrene over the range of temperatures from 30 to 120°C and frequency of 10 Hz after the glass transition temperature.
Experiment 244: The loss tangent decreases from commercial polystyrene to the high molecular weight micron sized polystyrene over the range of temperatures from 30 to 120°C and frequency of 1 Hz before the glass transition temperature.
Experiment 245: The loss tangent decreases from commercial polystyrene to the high molecular weight micron sized polystyrene over the range of temperatures from 30 to 120°C and frequency of 2 Hz before the glass transition temperature.
Experiment 246: The loss tangent decreases from commercial polystyrene to the high molecular weight micron sized polystyrene over the range of temperatures from 30 to 120°C and frequency of 5 Hz before the glass transition temperature.
Experiment 247: The loss tangent decreases from commercial polystyrene to the high molecular weight micron sized polystyrene over the range of temperatures from 30 to 120°C and frequency of 10 Hz before the glass transition temperature.
Experiment 248: The loss tangent decreases from commercial high density polyethylene to the high molecular weight micron sized polyethylene over the range of temperatures from 35 to 125°C and frequency of 1 Hz.
Experiment 249: The loss tangent decreases from commercial high density polyethylene to the high molecular weight micron sized polyethylene over the range of temperatures from 35 to 125°C and frequency of 2 Hz.
Experiment 250: The loss tangent decreases from commercial high density polyethylene to the high molecular weight micron sized polyethylene over the range of temperatures from 35 to 125°C and frequency of 5 Hz.
Experiment 251: The loss tangent decreases from commercial high density polyethylene to the high molecular weight micron sized polyethylene over the range of temperatures from 35 to 125°C and frequency of 10 Hz.
Experiment 252: The loss tangent decreases from commercial polypropylene to the high molecular weight micron sized polypropylene over the range of temperatures from 40 to 170°C and frequency of 1 Hz.
Experiment 253: The loss tangent decreases from commercial polypropylene to the high molecular weight micron sized polypropylene over the range of temperatures from 40 to 170°C and frequency of 2 Hz.
Experiment 254: The loss tangent decreases from commercial polypropylene to the high molecular weight micron sized polypropylene over the range of temperatures from 40 to 170°C and frequency of 5 Hz.
Experiment 255: The loss tangent decreases from commercial polypropylene to the high molecular weight micron sized polypropylene over the range of temperatures from 40 to 170°C and frequency of 10 Hz.
Experiment 256: The commercial high density polyethylene starts to degrade at 250°C whereas the high molecular weight micron sized polyethylene starts to degrade at 243°C in the nitrogen atmosphere.
Experiment 257: Both high molecular weight micron sized polyethylene and commercial high density polyethylene show multiple step degradation. These multi steps degradation temperature for commercial high density polyethylene are 370, 395 and
427°C, whereas for high molecular weight micron sized polyethylene are 327, 423, 454 and 485°C.
Experiment 258: The commercial polypropylene starts to degrade at 256°C whereas the high molecular weight micron sized polypropylene starts to degrade at 228°C.
Experiment 259: The maximµm rate of degradation for commercial polypropylene and high molecular weight micron sized polypropylene are at temperature of 280 and 244°C respectively.
Experiment 260: The commercial polystyrene starts to degrade at 300°C whereas the high molecular weight micron sized polystyrene starts to degrade at 288°C.
Experiment 261: But the maximµm rate of degradation for commercial polystyrene and high molecular weight micron sized polystyrene are 325 and 343°C respectively.
MAIN ADVANTAGES OF THE INVENTION:
1: This is the first time in the world we have prepared high molecular weight micron
sized polyethylene, polypropylene and polystyrene and going to report in the literature.
2: The size of the high molecular weight micron sized polyethylene is in between
0.05 to 70 µm in diameter. It is not possible to obtain this high molecular weight micron sized size using any other techniques used for other materials like polystyrene, PVC, PVA etc. For polypropylene the size of the high molecular weight micron sized is within the range of 0.17 to 40 µm, where as in case of high molecular weight micron sized polystyrene it is within the range of 0.17 to 47 µm.
3: The material performance, i.e storage modulus is high compared to the
commercial polyethylene. Same observation is also observed for the high molecular weight micron sized polypropylene and polystyrene.
4: The loss modulus and loss tangent are low with respect to commercial
polyethylene. Same observation is also observed for the high molecular weight micron sized polypropylene and polystyrene.
5: The high molecular weight micron sized polyethylene has higher thermal stability
compared to the commercial polyethylene. Same observation is also observed for the high molecular weight micron sized polypropylene and polystyrene.
6: Hope this technique could be used to prepare other high molecular weight micron
sized polymers including liquid crystal polymers.
7: The high molecular weight micron sized polyethylene could be used to form
plastic articles into intricate shapes with precise dimensions.
8: The high molecular weight micron sized polyethylene will allow production of
polymer alloys, self-reinforced plastic and elastomeric composites having a combination of desirable properties that can be exploited in nµmerous engineering applications.
The high molecular weight micron sized size polymer will allow intimate mixing of the polymer powders with other particles at micrometer length scales not possible with current polymer powders.
10: Another reason of this invention is 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.
A further expected outcome of this invention is its versatility that can be easily configured to produce high molecular weight micron sized polymers with diameters as low as 0.01 micron.
12: This high molecular weight micron sized polyethylene could be used in other
applications within 5 to 15 years. These are reduce waste and improved energy efficiency; 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.
13. a) Industry
A. Reduce waste and improved energy efficiency: Nanoscale materials for Lithiµm
batteries (used in mobile phones), cathodes (aerogel or zerogel V2O5) can
substantially increase capacity, cell life and charge/discharge rates.
B. Materials science and nano designed materials: The use of nanostrutures in alloys
and nanoparticles in composite materials protective and smart coatings (optical fibers, sun-protection products, biocompatible materials), "intelligent" and "conductive" polymers.
C. Catalysis: Biocatalyst for food, fuel for polymer, pharmaceuticals, environmental
protection enzymes (metallic and non-metallic nanoparticles, organometallic
complex molecules (dendrimers) for photo-catalysis, sensors, etc.).
D. Chemical nanotechnology: High definition flat optical displays, molecular machines
and assemblers, molecular and organic photovoltaic cells, diagnostoc laboratory on a
chip/biochips, surfactants and colloids for food and health, drug-carrying
nanoparticles.
E. Adhesives and coatings: Novel microstructures and surface effect polymers and
ceramics, new pigments, paints and textiles.
F. Chemistry in electronics and optics: Use of nanoscale chemistry (e.g., self
assembling systems) to make organic electronic semiconductors and other electronic
and optical components at the smallest possible scale (20 gigabytes on 3.5 inch
diskette, 25 m transistors/cm2 on a chip). Cheap computing power for all
applications.
G. Development of mechanical, optical and atomic scale machine: Capable of
precision operations at the nanoscale, essential for reliable production and quality
control of nanoscale materials.
b) Society:
A. Environmentally benign composite structures: The ability to incorporate nanoscale
inclusions in composites has the potential to produce materials with improved
properties and tailored to specific applications such as improved filter systems. This
can produce systems with increased environmental robustness, resulting in longer
service life and reduced overall system costs and replacement needs and reduced
environmental impact It also can produce lighter, smaller structures, resulting in
systems with reduced energy consumption.
B. Waste remediation: Nanostructured materials have an increasingly important role in
the remediation of wastes. This can take many forms, from using Titaniµmdioxide
(known in the pre-nano era as white pigments e.g. applied in toothpaste)
nanoparticles to oxidize organic wastes and biological contaminants (this is currently
being tested in hospital operating rooms and elsewhere) to employing nanoscale
scavengers to capture heavy metals in contaminated waste sites. An example of a
recent development is: the use of UV-illuminated nanoscale titanium dioxide to clean
atmospheric contaminants, including hazardous organic chemicals, cells and viruses.
C. Energy conversion: Use of energy indirectly or as electricity and as fuel for
transportation is responsible for an enormous impact on the environment. Nanoscale
systems offer the potential for renewable energy conversion systems with much less
waste production; when this potential coupled with improved batteries, the impact on
the environment could be enormous.
D. Investigation on the toxicity of nanomaterials: Given the enhanced bioavailability
of nanomaterials, comparative toxicity studies to explore possible differences
between normal- and nanomaterials should be undertaken.




WE CLAIM
1. A process for preparing micron sized high molecular weight polymer, having particle size in the range of 0.05 urn to 70 urn and improved mechanical and processing characteristics including high surface to volume ratio, from millimeter sized high molecular weight polymer, said process comprising the steps of:
a) mixing catalysts namely titatinium chloride and trimethyl aluminium in a amount in the range of 0.5gm to 10 gm in a solvent of amount 500cc to 1500cc, maintaining at a temperature in the range of -30°C to 45°C in inert atmosphere, stirring the same for a predetermined time period to obtain a solution,
b) mixing the solution of step (a), with millimeter sized high molecular weight polymer in a amount of 10 gm to 500 gm at a pressure in the range of 0.1 to 2.0 MPa and at a temperature in the range of -30°C to 100°C, to obtain a mixture comprises monomer residue or traces thereof,
c) heating the mixture of step (b) for removing monomer residues and traces thereof,
d) treating the mixture with solvent in a ratio 1:1 to 1: 0.1 such as mentioned herein and acidifying with traces of HC1 so as to decompose and to dissolve the catalyst in a solution,
e) heating the solution of step (d) up to 100°C to form a clear solution,
f) cooling the clear solution and stirring the same at a shear rate in the range of 0.2 to 200 rad/s for a predetermined time to obtain a precipitate,
g) filtering the precipitate and drying the same in order to get the micron sized high molecular weight polymer.
2. A process as experimented in claim 1 wherein in step (a) and (d), the solvent is selected from the group comprising from 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, tetrahydofuran, tributyl phosphate, acrylonitrile, chlorobenzene, acetic acid, n-
butanol, isobutanol, carbon tetrachloride, dimethyl siloxane, methanol, acetophenone, paraffin liquid and water.
3. A process as claimed in claim 1 wherein in step (a) the ratio of catalysts titatinium chloride and trimethyl aluminium is in the range of 0.5gm to 7gm.
4. A process as claimed in claim 1 wherein in step (a), the time period is in the range of 0.5 to 10 hours.
5. A process as claimed in claim 1 wherein in step (b), the monomer residues and traces are unreacted catalyst such as titanium chloride and tri methyl aluminum.
6. A process as claimed in claim 1 wherein in step (c), the mixture is being heated up to 170°C.
7. A process as claimed in claim 1 wherein in step (f), the time period is in the range of 0.5 to 10 hours.
8. A process as claimed in claim 1 wherein in step (f), the clear solution is being cooled up to 25°C.
9. A process as claimed in claim 1, wherein the molecular weight of millimeter sized polymer is in the range of 1, 00, 000 to 1, 50, 000 (Viscosity average molecular weight).
10. A process as claimed in claim 1, wherein the millimeter sized high molecular weight polymer are homopolymer or copolymer.
11. A process as claimed in claim 9, wherein the homopolymer and copolymer are selected from the group comprising polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), polyvinylchloride (PVC), polymethyl methacrylate (PMMA), polyamide (PA), acrylonitrile butadiene styrene (ABS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyoxymethylene (POM), polyphenylene ether (PPE), polysulfone (PSF), polyphenylene oxide (PPO), polyamide-imide (PAI), liquid crystal polymer (LCP), poly ether ether ketone (PEEK).
12. A process as claimed in claim 10, wherein the millimeter sized high molecular weight polymer are selected from polypropylene / polyethylene / polystyrene.
13. A process as claimed in claim 1, wherein high molecular weight micron sized polyethylene is prepared in the range 0.17 to 50 µm in diameter.
14. A process as claimed in claim 1 wherein in step (g), the micron sized high molecular weight polypropylene is prepared in the range 0.17 to 40 µm in diameter.
15. A process as claimed in claim 1 wherein in step (g), the micron sized high molecular weight polystyrene is prepared in the range 0.17 to 47 µm in diameter.
16. A process as claimed in claim 1 wherein in step (g), the micron sized high molecular weight polyethylene is prepared in the range 0.17 to 50 µm in diameter.
17. A process as claimed in claim 14, wherein the micron sized high molecular weight polypropylene having minimum BET surface area is 16.2 m2/gm in presence of xylene at a temperature of 30°C and shear rate of 150 rad/s.
18. A process as claimed in claim 15, wherein the micron sized high molecular weight polystyrene having minimum BET surface area is 17.7 m /gm in presence of solvent of dimethyl siloxane at a temperature of 30°C and shear rate of 175 rad/s.
19. A process as claimed in claim 16, wherein the micron sized high molecular weight polyethylene having minimum BET surface area is 16.2 m /gm in presence of xylene, at a temperature of 30°C, shear rate of 175 rad/s and in the nitrogen/ argon atmosphere.
20. A process as claimed in claim 1, wherein the micron sized high molecular weight polyethylene / polypropylene / polystyrene are spherical in nature.
21. A process as claimed in claim 1, wherein loss modulus and loss tangent of high molecular weight polyethylene / polypropylene / polystyrene are low as compare to commercial available polyethylene / polypropylene / polystyrene.
22. A process as claimed in claim 1, wherein the micron sized high molecular weight polyethylene / polypropylene / polystyrene having crystallinity in the range of 40 to 60 %.
23. A process as claimed in claim 1, wherein the glass transition temperature of high molecular weight micron sized polyethylene / polypropylene / polystyrene increase in the range of 5 to 25°C as compare to commercial polyethylene / polypropylene / polystyrene.
24. A process as claimed in claim 1, wherein the thermal stability of high molecular weight micron sized polyethylene / polypropylene / polystyrene increase in the range of 10 to 30°C as compared to commercial polyethylene / polypropylene / polystyrene.
25. The micron sized high molecular weight polymer having particle size in the range of 0.5 to 70 µis produced by the process as claimed in Claim 1 to 23.
26. A process for preparing micron sized high molecular weight polymer, having particle size in the range of 0.05 µm to 70 µm and improved mechanical and processing characteristics including high surface to volume ratio, from millimeter sized high molecular weight polymer, substantially as herein described with reference to the accompanying drawings and examples.
27. The micron sized high molecular weight polymer having particle size in the range of
0.5 to 70µm, substantially as herein described with reference to the accompanying
drawings and examples.

Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=zuHJgZe4vpwb1YgtbFa2Xg==&loc=+mN2fYxnTC4l0fUd8W4CAA==


Patent Number 268253
Indian Patent Application Number 2503/DEL/2004
PG Journal Number 35/2015
Publication Date 28-Aug-2015
Grant Date 24-Aug-2015
Date of Filing 16-Dec-2004
Name of Patentee INDIAN INSTITUTE OF TECHNOLOGY
Applicant Address DEPARTMENT OF MECHANICAL ENGINEERING, KANPUR- 208 016, INDIA
Inventors:
# Inventor's Name Inventor's Address
1 DR. KAMAL K. KAR INDIAN INSTITUTE OF TECHNOLOGY, KANPUR 208 016, INDIA
2 MR. PRADIP PAIK INDIAN INSTITUTE OF TECHNOLOGY, KANPUR 208 016, INDIA
PCT International Classification Number C08L23/16
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA