Title of Invention

A PROCESS FOR THE PREPARATION OF HIGHLY DISPERSED NANOCLAY

Abstract

This invention relates to a process for the preparation of highly dispersed nanoclay varying in d spacing from 22-24°A comprising, dissolving the intercalent and raw clay independently in solvent to form solution, mixing one of the solutions with soluble medium, pouring both these solutions simultaneously into an ion exchange column. to form homogenous solution, filtering the resultant modified clay through nylon filter, collecting and washing the resultant modified clay with hot water to remove soluble by-products formed during the reaction, freeze drying the collected matter to yield a modified orgnaoclay.

Full Text

FORM 2 THE PATENTS ACT, 1970 COMPLETE SPECIFICATION SECTION 10 TITLE "Process for Improved D-spacing of Nanoclay." APPLICANT North Maharashtra University, Umavi Nagar, Jalgaon. The following specification particularly describes the invention and the manner in which it is to be performed. -2-"Process for Improved D-spacing of Nanoclay." Field of Invention This invention relates to a process for Improved D-spacing of Nanoclay. Background of Invention Clay silicates like montomorillonite (MMT), hectonite, and bentonite have been used as reinforcing fillers for polymers because of their high aspect ratio. Out of these, the current preferred nano clay is montomorillonite. The crystal lattices consist of two-dimensional layers where a central octahedral sheet of either aluminum or magnesium is fused to two external silica of the tetrahedral sheet by their tips so that the oxygen ions of the octahedral sheet also belong to the tetrahedral sheet. The thickness of the layer is around 1 nm and the lateral dimension of these layer may vary from 300 angstroms to several microns or even larger, depending on the particular silicate. The layers are stacked by a weak dipole force and exhibit a net negative charge on the lamellar surface; the interlayer between the galleries are normally occupied by cations such as Na+ and Ca+. As the forces that hold the stacks together are relatively weak, the interaction of small molecules between the layers is easy. -3- Due to its hydrophobic nature, montomorillonite is not compatible with most of the polymers and must be chemically modified to make its surface more hydrophobic. Out of the different methods used, the most popular surface treatment uses organic ammonium cations, which can be exchanged with cations existing on clay surface. There are a few methods available for preparation of highly hydrophobic and dispersed clay. US Patent No. 7,081,491 describes a method for fabricating polybenzoxazole/clay nanocomposite materials. Similarly, US Patent 7,238,751 describes a method for preparation of multi¬layer nanoparticles and its applications. Patents WO2005095506, EP1801158, WO2005068365 all describe methods for preparation of nanoclays. However, in all processes existing so far, there are chances of agglomeration of the clay and hence the d-spacing may not be achieved. The lumps that are formed in the existing processes need to be crushed before use. The present invention therefore uses a method wherein metal cations of the interlayer can be exchanged with weak ammonium salt of short chains, thus producing treated clay with less ionic or polar surface. This modification of the surface of nano clay improves compatibilization between the surface of the nanoclay and the hydrophobic polymer matrix, and the chains of polymer thus penetrate more easily into -4-galleries due to increase in galleries spacing. The main advantage of the process described herein is that the modified nanoclay is obtained directly in powdered form. There is a significant reduction in the time required to carry out the entire process and there is no variation in the uniformity of the product. In spite of the wide use, commercial process holds many drawbacks. This technique usually requires very large amount of intercalent, and it is used rarely for improvement in d-spacing of nanoclay. This process produces nanoclay with improved d-spacing with a high purity and good yield at a very low cost. Compare to the prior art, there is need for developing a technique for improvement in d-spacing of nanoclay, wherein, the method could produces uniform improved d-spaced nanoclay. This technique provides surface modified nanoclay with a high purity and with good yield. The d-spacing obtained using this technique is approx 22-24 A0 Object of Invention The main object of this invention is to develop a process for uniform improved D-spacing in between two plates of nanoclay. -5-Other object is to develop a process to produce High purity and cheaper nanoclay with improved chemical affinity with well dispersion in polymer matrix. Another object is to develop a process for producing nanoclay with high volume with a low cost and reproducible quality. Yet another object is to provide a simple, economic and rapid process for the preparation of highly dispersed nanoclay. Further object is to develop a process for improved D spacing of Nanoclay wherein a good hydrophobic surface is available. Other object is also to develop a method for manufacturing chemically modified nanoclay wherein metal cations of the interlayer are exchanged with weak ammonicem salt of short chains, thus producing treated clay with less on or polar surface, there by improving compatibilization between the surface of the nanoclay and the hydrophobic polymer matrixcaesing chains of polymers to penetrate more easily into galleries due to increase in galleries spacing. Another object is also to produce nanoclay with good hydrophobic surface to be used as extenders for promoting hiding power of paints, -6- filters for composites and automotive surfaces, as flame retardant, filters for nano composites and as UV absorbent in weather resistant product. . Statement of Invention This invention relates to a process for the preparation of highly dispersed nanoclay varying in d spacing from 22-24°A comprising, Dissolving the intercalent and raw clay independently in solvent to form solution, Mixing one of the solutions with soluble medium, Pouring both these solutions simultaneously into an ion exchange column to form homogenous solution, Filtering the resultant modified clay through nylon filter, Collecting and washing the resultant modified clay with hot water to remove soluble by-products formed during the reaction, Freeze drying the collected matter to yield a modified orgnaoclay. Brief description of accompanying drawings Figure 1 describes the reactor design for nanoclay synthesis Figure 2 describes the XRD pattern of surface modified (1%) sodium-MMT Figure 3 describes the XRD pattern of surface modified (2%) sodium-MMT Detailed description of invention The present invention is therefore an attempt to remove the problems existing in the prior art and to develop an efficient process for production -7-of improved d-space nanoclay. The present invention involves a method for manufacturing chemically modified nanoclay wherein metal cations of the interlayer are exchanged with weak ammonium salt of short chains, thus producing treated clay with less ionic or polar surface, thereby improving compatibilization between the surface of the nanoclay and the hydrophobic polymer matrix causing the chains of polymer to penetrate more easily into galleries due to increase in galleries spacing. Particularly, the present invention involves a method for manufacturing .chemically modified nanoclay wherein metal cations of the interlayer are exchanged with weak ammonium salt of short chains, thus producing treated clay with less ionic or polar surface, thereby improving compatibilization between the surface of the nanoclay and the hydrophobic polymer matrix causing the chains of polymer to penetrate more easily into galleries due to increase in galleries spacing. In other form of the invention, the process involves a method for manufacturing nanoclay using salts of weak acids having short chains, the variables governing d-spacing in between two plates In yet another form of the invention, the process describes methods for manufacturing nanoclay, using salts of weak acids having long chain. In one more from of the invention, the intercalent comprises of ammonium -8. chloride, hexamethylene diamine, alkyl amine, dodecyl amine and octyl amine In yet another form of the invention, the raw nanoclay comprises of sodium montomorillonite In one another form of the invention, the cation exchange column comprises of cellulose In one more form of the anion exchange column comprises of tulsion-2, Dowex-I, amberlite, Zeolite, FF Ip. In other form of the invention, the process describes method of adding stoichiometric amounts of clay and interfacial agent into ion exchange column at specific flow rates In some other form of the invention, the process describes method for collecting the modified nanoclay In other form of the invention, the process describes method of washing the modified nanoclay. The present invention relates to a simple, surface modification, non viscous, rapid and improved process for preparation of highly hydrophobic and dispersed nanoclay having improved d-spacing, which in the range of 22-24 A0. This invention is economically viable and less time consuming than other commercial methods. -9-With respect to figure 1, tank (9) contains clay slurry and tank (10) contains the intercalent solution of long or short chain amines. Both these solutions are allowed to pass through the membrane (4). The purpose of this membrane is for supporting and uniform flushing. These solutions pass through the membrane onto the resin column (3) and are allowed to react for 10 to 15 minutes so that there is uniform ion exchange between the clay and intercalent. After this process is complete, the slurry is collected into collector (5). This solution is now passed through the nylon filter mesh (7) to remove all impurities and water and collected into tank (8) and freeze dried with help of vacuum pump (6) to yield the modified organoclay. Example-1 Approximately 5 gm Na-MMT is dispersed in H2O with vigorous stirring at concentration of 5 % and an aqueous suspension was achieved. To purify Na-MMT the aqueous suspension was kept at room temperature for 24 h and deposition was rejected. A stoichiometric amount of interfacial agent alkyl amine (C4H9 N+ CH2 CH2OH, 0.01 mol/100 gm) is mixed and transferred into a cation exchange column packed with cellulose. The time of flow of mixture is approximately 25 - 35 ml/min through a glass column having length of 35-40 cm. The entire slurry of surface modified clay is passed through nylon filter (Mesh size is 400|i) and collected into a receiver. -10-It was washed three times by flushing the column with hot distilled water. This collected matter was then freeze dried to yield a modified organoclay. Example-2 Approximately 5 gm Na-MMT is dispersed in H2O with vigorous stirring at concentration of 5 % and an aqueous suspension was achieved. To purify Na-MMT, the aqueous suspension was kept at room temperature for 24 h and deposition was rejected. A stoichiometric amount of interfacial agent of octadecyl amine (0.01 mol/100 gm) is mixed with concentrate HC1 (2.9 ml) and transferred into a cation exchange column packed with cellulose. The time of flow of mixture is approximately 25 - 35 ml/min through a glass column having length of 35-40 cm. The entire slurry of surface modified clay is passed through nylon filter (Mesh size is 400p.) and collected into a receiver. It was washed three times by flushing the column with hot distilled water. This collected matter was then freeze dried to yield a modified organoclay. Example-3 Approximately 5 gm Na-MMT is dispersed in H2O with vigorous stirring at concentration of 5 % and an aqueous suspension was achieved. To purify Na-MMT the aqueous suspension was kept at room temperature for 24 h and deposition was rejected. A stoichiometric amount of interfacial agent of -11- C2H5-NH2 (0.01 mol/100 gm) is mixed with concentrate HC1 (2.9 ml) and transferred into a cation exchange column packed with cellulose. The time of flow of mixture is approximately 25 - 35 ml/min through a glass column having length of 35-40 cm. The entire slurry of surface modified clay is passed through nylon filter (Mesh size is 400JJ) and collected into a receiver. It was washed three times by flushing the column with hot distilled water. This collected matter was then freeze dried to yield a modified organoclay. Exarnple-4 Approximately 5 gm Na-MMT is dispersed in H2O with vigorous stirring at concentration of 5 % and an aqueous suspension was achieved. To purify Na-MMT the aqueous suspension was kept at room temperature for 24 h and deposition was rejected. A stoichiometric amount of interfacial agent of ammonium chloride (0.01 mol/100 gm) is mixed with concentrate HC1 (2.9 ml) and transferred into a cation exchange column packed with cellulose. The time of flow of mixture is approximately 25 - 35 ml/min through a glass column having length of 35-40 cm. The entire slurry of surface modified clay is passed through nylon filter (Mesh size is 400(A) and collected into a receiver. It was washed three times by flushing the column with hot distilled water. This collected matter was then freeze dried to yield a modified organoclay. -12-Example-5 Approximately 5 gm Na-MMT is dispersed in H2O with vigorous stirring at concentration of 5 % and an aqueous suspension was achieved. To purify Na-MMT the aqueous suspension was kept at room temperature for 24 h and deposition was rejected. A stoichiometric amount of interfacial agent of Hexamethyl diamine (0.01 mol/100 gm) is mixed with concentrate HC1 (2.9 ml) and transferred into a cation exchange column packed with cellulose. The time of flow of mixture is approximately- 25 - 35 ml/min through a glass column having length of 35-40 cm. The entire slurry of surface modified clay is passed through nylon filter (Mesh size is 400(a) and collected into a receiver. It was washed three times by flushing the column with hot distilled water. This collected matter was then freeze dried to yield a modified organoclay. Example-6 Approximately 5 gm Na-MMT is dispersed in H2O with vigorous stirring at ■concentration of 5 % and an aqueous suspension was achieved. To purify Na-MMT the aqueous suspension was kept at room temperature for 24 h and deposition was rejected. A stoichiometric amount of interfacial agent of ammonium chloride (0.01 mol/100 gm) is mixed with concentrate HC1 (2.9 ml) and transferred into an anion exchange column packed with tulsion-2. The time of flow of mixture is approximately 25 - 35 ml/min through a -13- glass column having length of 35-40 cm. The entire slurry of surface modified clay is passed through nylon filter (Mesh size is 400|a) and collected into a receiver. It was washed three times by flushing the column with hot distilled water. This collected matter was then freeze dried to yield a modified organoclay. Example-7 Approximately 5 gm Na-MMT is dispersed in H2O with vigorous stirring at concentration of 5 % and an aqueous suspension was achieved. To purify Na-MMT the aqueous suspension was kept at room temperature for 24 h and deposition was rejected. A stoichiometric amount of interfacial agent of ammonium chloride (0.01 mol/100 gm) is mixed with concentrate HC1 (2.9 ml) transferred into an anion exchange column packed with Dowex-I. The time of flow of mixture is approximately 25 - 35 ml/min through a glass column having length of 35-40 cm. The entire slurry of surface modified clay is passed through nylon filter (Mesh size is 400JJ,) and collected into a receiver. It was washed three times by flushing the column with hot distilled water. This collected matter was then freeze dried to yield a modified organoclay. -14-Example-8 Approximately 5 gm Na-MMT is dispersed in H2O with vigorous stirring at concentration of 5 % and an aqueous suspension was achieved. To purify Na-MMT the aqueous suspension was kept at room temperature for 24 h and deposition was rejected. A stoichiometric amount of interfacial agent of ammonium chloride (0.01 mol/100 gm) is mixed with concentrate HC1 (2.9 ml) and transferred into an anion exchange column packed with amberlite. The time of flow of mixture is approximately 25 - 35 ml/min through a glass column having length of 35-40 cm. The entire slurry of surface modified clay is passed through nylon filter (Mesh size is 400|a) and collected into a receiver. It was washed three times by flushing the column with hot distilled water. This collected matter was then freeze dried to yield a modified organoclay. Example-9 Approximately 5 gm Na-MMT is dispersed in H2O with vigorous stirring at concentration of 5 % and an aqueous suspension was achieved. To purify Na-MMT the aqueous suspension was kept at room temperature for 24 h and deposition was rejected. A stoichiometric amount of interfacial agent of ammonium chloride (0.01 mol/100 gm) is mixed with concentrate HC1 (2.9 ml) and transferred into an anion exchange column packed with Zeolite FF IP. The time of flow of mixture is approximately 25 - 35 ml/min through a -15- giass column having length of 35-40 cm. The entire slurry of surface modified clay is passed ^ through nylon filter (Mesh size is 400|a) and collected into a receiver. It was washed three times by flushing the column with hot distilled water. This collected matter was then freeze dried to yield a modified organoclay. Example-10 Approximately 5 gm Na-MMT is dispersed in H2O with vigorous stirring at concentration of 5 % and an aqueous suspension was achieved. To purify Na-MMT the aqueous suspension was kept at room temperature for 24 h and deposition was rejected. A stoichiometric amount of interfacial agent of ammonium chloride (0.01 mol/100 gm) is mixed with concentrate HC1 {2.9 mi) and transferred into an anion exchange column packed with Dowex-I. The time of flow of mixture is approximately 25 - 35 ml/min through a glass column having length of 35-40 cm. The entire slurry of surface modified clay is passed through' nylon filter (Mesh size is 400p,) and collected into a receiver. It was washed three times by flushing the column with hot distilled water. This collected matter was then freeze dried to yield a modified organoclay. -16-The present invention is advantageously provides several area of applications, such as, paint, drug delivery, textiles, surface modification in rubbers, elastomers and thermoplastics. Surface modified nanoclay has been prepared for uses as a reference standard in the calibration of various instruments, in medical research and in medical diagnostic tests. -17- We claim 1. A process for the preparation of highly dispersed nanoclay varying in d spacing from-22-24°A comprising: - a. Dissolving the intercalent and raw clay independently in solvent to form solution b. Mixing one of the solutions with soluble medium c. Pouring both these solutions simultaneously into an ion exchange column to form homogenous solution d. Filtering the resultant modified clay through nylon filter e. Collecting and washing the resultant modified clay with hot water to remove soluble by-products formed during the reaction. f. Freeze drying the collected matter to yield a modified orgnaoclay. 2. A process for the preparation of highly dispersed nanoclay as claimed in claim 1 wherein, the intercalent comprises of ammonium chloride, hexamethylene diamine, alkyl amine, dodecyl amine and octyl amine. 3. A process for the preparation of highly dispersed nanoclay claimed in claim 1 wherein the raw nanoclay comprises of sodium montomorillonite. 4. A process for the preparation of highly dispersed nanoclay claimed in claim 1 wherein the cation exchange column comprises of cellulose. -18- 5. A process for the preparation of highly dispersed nanoclay claimed in claim 1 wherein the anion exchange column comprises of Dowex-I, Zeolite FF IP, tulsion-2, amberlite. 6. A process for the preparation of highly dispersed nanoclay claimed in claim 1 wherein the apparatus comprising a reactor equipped with high pressure fluid, flushing temperature sensor, resin, membrane for support and uniform flush slurry collector. 7. A process for the preparation of highly dispersed nanoclay as described and illustrated herein with help of example and drawings.

Documents:

526-MUM-2009-ABSTRACT(23-7-2012).pdf

526-mum-2009-abstract.doc

526-mum-2009-abstract.pdf

526-MUM-2009-CLAIMS(AMENDED)-(21-3-2014).pdf

526-MUM-2009-CLAIMS(AMENDED)-(23-7-2012).pdf

526-mum-2009-claims.doc

526-mum-2009-claims.pdf

526-MUM-2009-CORRESPONDENCE(20-10-2009).pdf

526-MUM-2009-CORRESPONDENCE(25-2-2014).pdf

526-MUM-2009-CORRESPONDENCE(26-6-2009).pdf

526-MUM-2009-CORRESPONDENCE(IPO)-(18-8-2009).pdf

526-mum-2009-correspondence.pdf

526-mum-2009-description(complete).doc

526-mum-2009-description(complete).pdf

526-mum-2009-drawing.pdf

526-MUM-2009-FORM 1(21-3-2014).pdf

526-MUM-2009-FORM 1(26-6-2009).pdf

526-MUM-2009-FORM 1(9-3-2009).pdf

526-mum-2009-form 1.pdf

526-MUM-2009-FORM 18(23-10-2009).pdf

526-MUM-2009-FORM 2(TITLE PAGE)-(21-3-2014).pdf

526-mum-2009-form 2(title page).pdf

526-mum-2009-form 2.doc

526-mum-2009-form 2.pdf

526-MUM-2009-POWER OF ATTORNEY(26-6-2009).pdf

526-MUM-2009-REPLY TO EXAMINATION REPORT(23-7-2012).pdf

526-MUM-2009-REPLY TO HEARING(21-3-2014).pdf

526-MUM-2009-SPECIFICATION(AMENDED)-(23-7-2012).pdf

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