DESC:CATALYTIC POLYHIPES AND PROCESS FOR INTENSIFICATION OF HETEROGENEOUS CATALYTIC REACTIONS THROUGH CONTINUOUS FLOW REACTORS.

FIELD OF THE INVENTION
[001] The present invention generally relates to the field of continuous flow chemistry and more particularly relates to a composition for heterogenous molecular catalyst support and a process for intensification of heterogeneous catalytic reactions by integration of heterogenous molecular catalyst with dynamically stirred continuous flow reactors.

OBJECT OF THE INVENTION
[002] The object of the present invention is to provide a safe, efficient, and economically viable scalable solution for heterogenous catalytic reactions and processes.
[003] Another object of the present invention is to design and synthesize a heterogeneous catalyst support.

BACKGROUND OF THE INVENTION
[004] With an era of continuous flow chemistry slowly but steadily overtaking the conventional batch synthesis due to many phenomenal revolutionary advantages it exhibits over the latter, some of the most challenging lab processes can now be more efficiently and safely dealt with. Commercially available heterogeneous catalysts for continuous flow processes by virtue of their sizes in nanoscales, have been traditionally put into use either as a stationary column (Fixed-Bed) that makes the process easier to handle or in a fluidized bed system that enables efficient mixing. Fixed-Bed systems have largely limited the productivity of continuous flow due to issues like leaching, bed-cracking, and saturation over time affecting the former. In the case of fluidized-bed reactors, engineering drawbacks and poor system-specificity remain major challenges. The use of existing conventional flow catalysts still poses a serious cause for concern due to their limited applicability. Heterogeneous molecular catalysts, which exhibit a highly accessible surface morphology with excellent mechanical strength in addition to high resistance to chemical degradation; are chosen as admirable candidates for the purpose.
[005] The catalyst market is populated predominantly by catalysts having small particle sizes, mostly based on gels or beads, due to their capability to provide a high surface area for effective reaction progress. However, such small particulate catalysts pose a variety of drawbacks if considered their long-term applications. Broadly speaking, such materials show high surface area only if employed in low particle sizes or by enabling them to have a porous morphology. However, both these conditions can lead to serious concerns when looked in the viewpoint of reaction scale-up or process intensification. Reactions that employ catalysts having very small particle sizes can lead to difficult separation of catalyst from the product post-reaction. Similarly, having too porous a nature of the catalyst can disrupt the capillary action during reaction progress thus leading to poor accessibility of internal surfaces, ultimately decreasing the catalytic efficiency. Till date, the most common use of such heterogeneous catalysts has been in the form of a fixed bed column through which reagents flow in and react inside the catalyst-filled column to yield the product as desired. However, there are a few issues encountered with this application as well. Firstly, the packed bed starts actively leaching with time, thus leading to a drastic decrease in the catalytic efficiency with use. Secondly, a packed-column reactor is prone to bed-cracking and saturation. Thus, poorer activity with every repeated use. On the other hand, there has been another reactor – the fluidized bed type – that allows the use of such particulate catalysts allowing reaction progress in a buoyant medium. Though this design of a reactor very efficiently overcomes the limitations of the former, there are a few shortcomings in this too. Different kinds of processes need different types of fluidization which makes designing of an application-specific fluidized bed reactor highly system-dependent, which is complex for both engineering and production. As a result of these factors, a reactor system which is easy and universal to use (like a packed or stationary bed column), as well as one that gives efficient mixing (like a fluidized bed reactor), is needed.
[006] As seen above, conventional heterogeneous catalysts owing to their limited application due to small particle sizes; continue to pose a question for long-term efficiency and application in scaled-up syntheses. Hence, new catalysts that possess the basic requirement of a large surface area facilitated by a highly accessible inter- and intra-particulate surface morphology; in addition to both larger size (but not in a manner that would compromise on the catalytic efficiency) and better mechanical strength (which is very rare in most conventional catalysts) are needed.

SUMMARY OF THE INVENTION

[007] This summary is provided to introduce a selection of concepts in a simplified format that are further described in the detailed description of the invention. This summary is not intended to identify key or essential inventive concepts of the claimed subject matter, nor it is intended for determining the scope of the claimed subject matter.
[008] An embodiment of the present invention discloses a process for intensification of heterogeneous catalytic reactions through continuous flow chemistry, the process comprises of synthesizing Polymerized High Internal Phase Emulsions (PolyHIPE) using at least two monomers, wherein the monomers react with each other to yield a PolyHIPE containing residual reactive moieties. The synthesized PolyHIPE is then modified into a heterogeneous functional catalytic material, wherein the modification is carried out by incorporating a catalyst, the modified PolyHIPE is then integrated with a dynamically stirred continuous flow reactor to enhance heterogeneous catalytic processes.
[009] Another embodiment of the present invention discloses a composition for intensification of heterogeneous catalytic reactions, the composition comprising of a synthesis of PolyHIPE through the Thiol-ene/yne mechanism of polymerization containing at least two monomers and a transition metal wherein the monomers are selected from thiol, alkenes and alkynes and wherein particle size of the catalyst is in the size range of 10-50 microns.

BRIEF DESCRIPTION OF THE DRAWINGS
[0001] Reference will be made to embodiments of the invention, examples of which may be illustrated in the accompanying figures. These figures are intended to be illustrative, not limiting. Although the invention is generally described in the context of these embodiments, it should be understood that it is not intended to limit the scope of the invention to these particular embodiments.
[0002] The objects, features, and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
[0010] Figure 1 illustrates the SEM Micrograph of a porous polymer foam materials; the molecular catalyst (PolyHIPE); the catalytic basket assembly; the agitating reactor block; the Agitated Cell Reactor (ACR).
[0011] Figure 2 illustrates the scale-up tool Coflore Agitated Cell Reactor (ACR), (2) The actual reactor block, (3) The typical agitation motion of the reactor block as well as agitator, (4) Different types of agitator cells (from left to right) Ceramic agitator, Hastelloy agitator, Spring agitator for two-phase mixtures, Basket agitator for handling catalysts.
[0012] Figure 3 illustrates the basket assembly (accessory along with ACR) for loading a catalyst.
[0013] Figure 4 illustrates stepwise flow of the work; Step 3 (left to right) the Agitated Cell Reactor block, ten catalyst basket agitators corresponding to one CSTR each, integration of the chemically modified functional polyHIPE into the catalytic basket agitator for performing scaled-up, high throughput, efficient and fast chemically processes.
[0014] Figure 5 illustrates a general protocol for Palladium (catalyst) immobilization onto the molecular polymer foam supports (PolyHIPE)
[0015] Figure 6 illustrates PolyHIPEs formed using the monomer combinations (1) TMPTMP and TVCH and (2) PETTMP and TVCH at (a) Low magnification showing the homogeneity in pore size and distribution; (b) High magnification showing the large porosity of the material.
[0016] Figure 7 illustrates experimental synthesis results of PolyHIPE materials presently obtained.
[0017] Figure 8 illustrates experimental synthesis results of PolyHIPE materials presently obtained.
[0018] Figure 9 is tabular representation of a detailed experimental chart of the various optimizations carried out.
[0019] Figure 10 is a chemical representation of the ‘Thiol ene / yne polymerization reaction.
[0020] Figure 11 illustrates PHP-Flow integration procedure.
[0021] Figure 12 illustrates Pd-PolyHIPEs (Palladium-immobilized PolyHIPE) formed using the monomer combinations (1) TMPTMP and TVCH; and (2) PETTMP and TVCH; in each of which (a) High magnification images showing the wide diversity in the size of pores and interconnecting voids in addition to a ‘ballooning’ effect; (b) Energy Dispersive X-ray Spectroscopy (EDX) mapping depicting the distribution of Sulphur and Palladium groups all around the material. (The prefix 2’ to all images indicate Step-2; the modification of PolyHIPE into functional heterogeneous catalysts through incorporation of Palladium metal).
[0022] It should be appreciated by those skilled in the art that any diagrams herein represent conceptual views of illustrative systems embodying the principles of the present invention.

DETAILED DESCRIPTION
[0003] For the purpose of promoting an understanding of the principles of the invention, reference will now be made to the embodiment illustrated in the drawings, and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended, such alterations and further modifications in the illustrated system, and such further applications of the principles of the invention as illustrated therein being contemplated as would normally occur to one skilled in the art to which the invention relates. It will be understood by those skilled in the art that the foregoing general description and the following detailed description are explanatory of the invention and are not intended to be restrictive thereof.
[0004] Reference throughout this specification to “an aspect”, “another aspect” or similar language means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrase “in an embodiment”, “in another embodiment” or “in an exemplary embodiment” and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment.
[0005] The terms "comprises", "comprising", or any other variations thereof, are intended to cover a non-exclusive inclusion, such that a process or method that comprises a list of steps does not include only those steps but may include other steps not expressly listed or inherent to such process or method.
[0023] An embodiment of the present invention discloses a process for intensification of heterogeneous catalytic reactions, the process comprises of synthesizing Polymerized High Internal Phase Emulsions (PolyHIPE) using at least two monomers, wherein the monomers react together to form a PolyHIPE containing residual reactive moieties. The synthesized PolyHIPE is then modified into a heterogeneous functional catalytic material, wherein the modification is carried out by incorporating a catalyst. The catalyst is a transition metal selected from Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Sn, Re, W, Pt. The modified PolyHIPE is then integrated with a dynamically stirred continuous flow reactor to enhance heterogeneous catalytic processes. The dynamically stirred continuous flow reactors may be selected from Agitated Cell Reactor (ACR) or Agitated Tube Reactor (ATR). Present invention further discloses a composition for intensification of heterogeneous catalytic reactions, the composition comprises at least two monomers and a catalyst wherein the monomers are selected from thiols, alkenes and alkynes and wherein particle size of the catalyst is in the range of 10-50 microns.
[0024] As shown in Figure 1, the catalyst basket assembly of the ACR reactor behaves as an ideal holder for the molecular catalysts whose integration splendidly exhibits the combined benefits; thus, enhancing the overall productivity by manifolds. The present invention focuses on the development of a series of PolyHIPEs exploring different combinations involving a variety of monomer backbones like thiols, cyclic and aliphatic alkenes and alkynes with an aim to screen the materials most conducive for providing catalytic excellence (in any kind of chemical, biochemical or biological process), chemical insusceptibility to widely used solvents and reaction conditions; as well as mechanical endurance towards force and attrition commonly encountered in processes involving high shear and high-pressure in industrial dynamically stirred continuous flow reactors like the ACR and ATR.
[0025] The present invention, discloses two aspects of the invention, one, the dynamically stirred continuous flow reactor tool that enables efficient mixing (leading to rapid and fast reaction-scales) and scalable production; another, the macromolecular polymeric heterogeneous catalyst PolyHIPE that is suited to the purpose in both ways; engineering-wise and catalytic efficiency-wise. How each of them acts complementarily to the purpose; is elaborated in detail below:
As shown in figure 2, The Agitated Cell Reactor (ACR) and the ATR (Agitated Tube Reactor), a scalable version of the former; used exclusively for industrial scale-up, are dynamically stirred continuous flow tools that offer benefits like ease of use and efficient mixing, these attributes make them suitable for the scale-up of vital organic processes without long-term stability issues (which are generally experienced in a stationary column reactor) or specific engineering requirements (demanded by a fluidized bed reactor). For instance, the ACR (as can be seen from Figure 2) has multiple inlets through which any number of reagents could be fed at the same time. The agitating plate carries the reagents through the channel of the reactor; reacting all its way up to the collection point; from where the product is collected after completion; all under high attrition. This agitation, which is tuneable according to process requirement, brings about a homogenous and efficient mixing of the reagents inside; whose temperature changes or fluctuations, especially if the process is exothermic or endothermic, could be monitored externally through thermocouple sensors. In addition, the zigzag motion of flow up to the outlet enhances the available surface area by a marked amount. Thus, ultimately enhancing the level of mixing efficiency. Therefore, it is evident that the mixing ability of a dynamically stirred continuous flow reactor is very high as compared to a fluidized bed. Since it has no specific pre-requisites for operation and handling; and is robust for repeated use with same productivity every time, the limitations provided by the stationary bed type reactor are also circumvented.
[0026] These dynamically stirred continuous flow reactors have an ability to handle solid suspensions up to 45% in concentration, immiscible fluids, and gas-liquid biphasic systems; which are otherwise extremely cumbersome to handle; with proven efficiency for reactions over a time scale as wide as 8 seconds to 8 hours. Moreover, they exhibit a mass transfer rate of a minimum of 2 orders magnitude better than that of conventional batch processes and are self-baffling due to the presence of agitator cells or tubes in addition to the overall dynamically stirred motion of the reactors. Fully automated, they are also capable of giving a very high throughput.
[0027] The link that connects effective scale-up through these dynamically stirred continuous flow reactors to high-efficiency heterogeneous molecular catalysts having a high surface area, larger bulk size and better mechanical strength is shown in Figure 3. Among the accessories that potentiate the efficiency of the dynamically stirred continuous flow reactor ACR, is a basket assembly that has a mesh size of around 20-30 microns; into which catalysts may be loaded. This loaded assembly then could be put into the reactor, which could then be allowed to react through the agitation it provides, up to completion. Such a system would be very easy to handle (like the stationary bed), load or unload catalysts from the basket; exhibit efficient mixing (like the fluidized bed reactor) and be scalable and one of high throughput.
[0028] The particle size of the catalyst should be greater 20-30 microns so that it can be contained in the basket and not leach out while agitation during the course of the reaction. It is at this juncture that molecular catalysts or macroporous polymer emulsions (PolyHIPEs) suit into the purpose admirably. The following features that these moieties possess make them remarkable candidates for use as heterogeneous catalysts in the ACR:
a) Firstly, PolyHIPEs have a unique highly porous morphology (as can be seen from Figure 5) which allow their surface to be easily and efficiently accessible; thus, making them excellent heterogeneous catalyst supports.
b) Secondly, though they can be designed to have different pore sizes, they are a unit or bulk material which can be easily contained inside the baskets; contrary to the individual loose particles used as particulate catalysts which will leach out from the basket.
c) PolyHIPEs have excellent mechanical strength too, by virtue of which they will be able to sustain the force or agitation that occurs during the course of the reaction in the ACR, unlike the individual catalyst particles that leach out vigorously under agitation.
[0029] Another exemplary embodiment of the invention discloses the process for intensification of heterogeneous catalytic processes via integration of PolyHIPE-immobilized catalysts with dynamically stirred continuous flow reactors. The process comprises of the following steps:
1) Synthesis of PolyHIPEs using different monomer combinations –
All PolyHIPEs using different monomer combinations based on varied structural chemistries have been explored (viz. 4 thiols and 7 unsaturated compounds; as shown in figure 6) via the Thiol ene/yne polymerization reaction chemistry (shown in figure 9). The experimental protocols carried out were as reported in the literature for Thiol ene/yne polymerization reactions.
The various monomers evaluated in the present invention are as follows (the monomers are actually taken (italics) are representative examples from the main class (roman or normal). It is possible that other monomers not considered in this work also produce results similar to obtained here. In principle, the monomers considered here are not limited to the monomers disclosed in the present invention and may extend in application to others too.
Abbreviation legends for the monomers used:
a) Thiols –
i. Aliphatic Di-thiol
? 2,2'-(Ethylenedioxy) diethanethiol [EDDT]
ii. Aliphatic Tri-thiol
? Trimethylolpropane tris(3-mercaptopropionate) [TMPTMP]
iii. Aliphatic Tetra-thiol
? Pentaerythritol tetrakis(3-mercaptopropionate) [PETTMP]
iv. Aromatic Di-Thiol
? 4,4'-Thiobisbenzenethiol [TBBT]
b) Olefins (Alkenes) –
i. Aliphatic allyl ether
? Trimethylolpropane diallyl ether [TMPDE]
ii. Aliphatic vinyl ether
? 1,4-Butanediol divinyl ether [BDDV]
iii. Aliphatic vinyl triene
? 1,2,4-Trivinyl cyclohexane [TVCH]
iv. Cyclic or aromatic di-olefins
? Dicyclopentadiene [DCPD]
? Bicyclo [2.2.1] hepta-2,5-diene (2,5-Norbornadiene) [NBD]
c) Alkynes –
i. Terminal alkyne
? 1,7-Octadiyne [ODY]
ii. Internal alkyne
? 3,9-Dodecadiyne [DDY]

PolyHIPEs materials may be synthesized using all the monomer chemistries (as listed above) in different combinations (as tabulated in figure 6). Out of all the 28 combinations explored, 11 PolyHIPE materials have been presently obtained; which were further subjected to characterization tests. The summarized result-chart of the PolyHIPE materials synthesized through these 28 combinations are shown in figure 7.
Example:
1. The stirrer assembly (with a paddle and shaft assembly) was set.
2. TMPTMP and TVCH both have 3 reactive moieties each; thiol groups and pi-bonds respectively. Hence, the amounts taken of both would be in 1:1 ratio. The individual monomers TMPTMP (3.294 ml; 3.986 g) and TVCH (1.941 ml; 1.623 g) were weighed separately into two 5 ml glass vials.
3. In a separate 20-ml glass vial, Surfactant Hypermer B246 (7 % of the organic phase; 0.609 g) was taken. Into it, the organic solvent 1,2-Dichloroethane (5.235 ml; 6.575 g) was added and shaken vigorously (on a vortex mixer) to ensure dissolution of the semisolid (gel-like) surfactant into the organic solvent).
4. The above mixture (surfactant-organic solvent) once completely homogeneous; was distributed in approximately half quantities into each monomer vial; and shaken manually to ensure good mixing between the monomer, surfactant and organic solvent.
5. Further, these individual mixtures were collectively added into an RBF, fixed onto the stirrer assembly and allowed to stir homogeneously at 350 rpm for a period of 10 mins. However, the RPM may be adjusted in the range of 150-5000.
6. The Photo-initiator Diphenyl (2,4,6-trimethyl benzoyl) phosphine oxide (0.733 ml; 0.821 g) was added all at once and rapidly (to minimize contact with external atmosphere or light) into the RBF; and further allowed to homogeneously mix for a period of 10 minutes. Further, the photo-initiator may also be selected from 2-hydroxy-2-methyl-1-phenylpropane1-one (Darocure 1173), 1- hydroxycyclohexylphenylketone (Irgacure 184).
7. In the meanwhile, the Syringe pump was set up with a Plastic HSW syringe with the required content of the aqueous phase (41.879 ml) at the desired flow rate (0.46 ml per minute); and incorporation of the water phase started.
8. Once the addition was complete, a post-emulsification time of 10 minutes was allowed for complete and homogeneous emulsification.
9. The emulsion was quickly poured into glass moulds and passed through the UV chamber (three times each side) at full (100 %) power to yield solid and firm PolyHIPE.
Characterization: -
Scanning Electron Microscopy (SEM):
In order to understand the morphology of the PolyHIPE materials formed, all the materials produced were characterized for estimation of pore size or pore dimensions via SEM imaging. The polyHIPEs formed through a monomer combination of PETMTP with TVCH and TMPTMP with TVCH were observed to be ideal; with uniform and homogeneous particle size morphology; suitable for catalytic applications. The average pore diameter of the materials was calculated to be in the range of 8-20 microns. Figure 5 shows the SEM micrograph of the PolyHIPEs obtained from the monomer combinations as shown in figure 7.
Mercury Porosimetry:
In order to understand the pore and void window dimensions like volume and surface area, the best materials obtained above were subjected to Mercury Intrusion Porosimetry test. According to this characterization, the TMPTMP with TVCH PolyHIPE showed a pore area of 1.955 m2/g; while the one involving PETTMP with TVCH showed a pore area of 4.974 m2/g.
Compression Testing:
This aim of this characterization test is to estimate the mechanical strength of the PolyHIPEs; and check whether the materials are sturdy and mechanically robust enough to undergo various mechanical stresses like attrition, strain, force, and pressure while inside the Agitated Cell Reactor.
Elman’s Colorimetric Assay:
The aim of this characterization test is to estimate the residual Thiol content in the materials. This is of special importance while chemically modifying the materials into catalysts.
2) Modification of PolyHIPEs into heterogeneous functional catalytic materials –
In the present invention palladium may be incorporated on the above-synthesized PolyHIPEs using the Polyol method; Furthermore, these PolyHIPE materials; by virtue of the residual reactive moieties in them, enable enough versatility for varied kinds and methods of functionalization using a varied range of chemical moieties. Further, they may be conveniently modified for enabling biochemical or biological processes thus suiting the purpose of biocatalysis.
Example:
1. Set up:
a. The PolyHIPE blocks were neatly cut into smaller discs using a 5-mm biopsy punch. Each disc was weighed before employing into the actual reaction.
b. A heating assembly (with a paddle and shaft assembly) was set.
2. Solution A was prepared by dispersing the metal precursor (selected from Sodium Tetrachloropalladate, potassium tetrachloropalladate, palladium chloride, palladium acetate, palladium nitrate) into the solvent-cum-reducing agent (Diethylene glycol) by stirring under heat at 60°C -80°C for a period of around 10-15 minutes; until a homogeneous dispersion was obtained. Further, the solvent-cum-reductant may also be selected from ethylene glycol, triethylene glycol, tetraethylene glycol.
3. Solution B was prepared by dissolving Polyvinyl Pyrrolidone into Diethylene glycol by stirring under heat at 140 °C for 10 minutes; until a homogeneous solution was obtained.
4. The above synthesized PolyHIPE discs were dropped carefully into the Solution B.
5. Further, solution A was rapidly added into Solution B; and allowed to undergo reaction for period of 3 hours. The completion of reaction was indicated by the change of the initial reddish-brown suspension to a dark black one at the end of 3 hours.
6. The mixture was cooled down to room temperature.
7. The formed Pd-PolyHIPE were decanted from the reaction mixture, washed with water repeatedly for a couple of times till visible traces of the black reaction mixture were washed away. Then, they were soaked in Acetone and / or Ethanol for a period of 2 days (so that the internal unreacted reagents and other solvents get washed away). The PolyHIPE were further air-dried overnight; and then vacuum-dried for 24 hours to completely rid them of any moisture or solvent content.

3) Integration of PolyHIPEs with the ACR catalytic baskets for performing efficient and scaled-up catalytic processes –
The integration of the heterogeneous high surface area, mechanically robust and chemically insusceptible catalytic PolyHIPEs with the dynamically stirred continuous flow scale-up tool ACR (Agitated Cell Reactor) or Agitated Tube Reactor (ATR) is highly beneficial for the fast and efficient process intensification of various chemical and biological catalytic processes. When considered on an industrial scale, this high-efficient, high-throughput, safe, fast, and scalable mode of synthesis will be of tremendous value for the generation of various industrially, pharmaceutically and biologically important intermediates and compounds.
Palladium-based cross-coupling reactions have had an immensely important role to play in the field of heterogeneous chemical catalysis. Suzuki, Suzuki-Miyaura, Heck, Stille, Sonogashira, Negishi coupling reactions are just a few to name a huge list of coupling reactions that are of tremendous value in chemical synthesis. In this invention, the Suzuki-Miyaura coupling is chosen as a demonstration for the catalytic efficiency of the synthesized Pd-PHPs (Palladium immobilized PolyHIPE).
For the Suzuki-Miyaura coupling reaction, an aryl halide was chosen to react with a Lewis acid in the presence of a base and phase transfer catalyst (optional) in a suitable solvent under optimized reaction parameters. For carrying out the process, the Agitated Cell Reactor (ACR) with the catalytic PolyHIPE (Pd-PHP)-loaded catalyst baskets were chosen, with suitable pumps, temperature controller and back pressure regulator as accessories.
Example:
1. Firstly, the ACR reactor block was loaded with the catalyst baskets; each containing a pre-weighed number of Pd-PHP discs.
2. A solution of the solvent with the base and TBAB was prepared and introduced into the reactor from one of the bottom inlets; under equilibration at the set temperature (50-150°C) and pressure conditions (0-20 bar).
3. Once the equilibration was done, an unsaturated compound (aryl halide) was passed through the second bottom inlet.
4. After allowing a few minutes further for attaining the flow steady state, Lewis acid was passed through the second inlet.
5. The reaction was allowed for an optimized amount of time; and the product collected through the uppermost cell (outlet point).
6. The product was purified and characterized by GC or HPLC.
[0030] An unsaturated compound can be selected from a list inclusive of but not limited to alkenyl (vinyl), aryl, or alkynyl organoborane (boronic acid or boronic ester, or aryl trifluoroborane). Lewis acid can be selected from a list that is inclusive of but not limited to halides and triflates. The base is selected from a list that is inclusive of but not limited to triethylamines, sodium acetate, potassium phosphate, sodium hydroxide, potassium carbonate. The solvent is selected from a list that is inclusive of but not limited to water, ethanol, toluene, N, N-dimethylacetamide, and so on, either neat or as a mixture with varied proportions. An optional phase transfer catalyst could be added for improving reaction efficiency; and it is selected from tetra-n-butylammonium bromide (TBAB), methyltrioctylammonium chloride, benzyltriethylammonium chloride, methyltricaprylammonium chloride, methyltributylammonium chloride, and organic phosphonium salts.
[0031] Although the present disclosure has been described in the context of certain aspects and embodiments, it will be understood by those skilled in the art that the present disclosure extends beyond the specific embodiments to alternative embodiments and/or uses of the disclosure and obvious implementations.

,CLAIMS:We claim:
1. A process for intensification of heterogeneous catalytic reactions, the process comprising:
synthesizing Polymerized High Internal Phase Emulsions (PolyHIPE) using at least two monomers, wherein the monomers react to yield the PolyHIPE containing residual reactive moieties;
modifying the PolyHIPE into a heterogeneous functional catalytic material, wherein the modification is carried out by incorporating a catalyst; and
integrating the modified PolyHIPEs with dynamically stirred continuous flow reactors to enhance heterogeneous catalytic processes.
2. The process as claimed in claim 1, wherein synthesizing PolyHIPE comprises steps of:
weighing and mixing at least one thiol monomer and at least one alkene/alkyne monomer in a specific ratio to obtain a blend;
dissolving a surfactant in an organic solvent separately to obtain a mixture;
adding the mixture to the blend to obtain a homogenous mixture;
stirring the homogenous mixture for a specific time at a predetermined rotations per minute;
adding a photoinitiator to the homogenous mixture under constant stirring;
incorporating an aqueous phase at a desired flow rate in the homogenous mixture blended with the photoinitiator to obtain a homogenous emulsion; and
curing the emulsion under Ultraviolet rays to obtain solid PolyHIPE.
3. The process as claimed in claim 2, wherein the surfactant is selected from Hypermer 2296, cationic (CTAB), anionic surfactants, modified clay (cosurfactants), block copolymers, polyglycerol polyricinoleate (PGPR)
4. The process as claimed in claim 2, wherein the RPM is in the range of 150-5000.
5. The process as claimed in claim 2, wherein the specific time is in the range of 5-60 minutes.
6. The process as claimed in claim 2, wherein the photoinitiator is Diphenyl (2,4,6-trimethyl benzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropane1-one (Darocure 1173), 1- hydroxycyclohexylphenylketone (Irgacure 184).
7. The process as claimed in claim 2, wherein the flow rate is in the range of 20-30 ml per hour.
8. The process as claimed in claim 1, wherein the catalyst particle size in the range of 10 to 50 microns.
9. The process as claimed in claim 1, wherein the catalyst is a transition metal.
10. The process as claimed in claim 1, wherein the transition metal is selected from Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Sn, Re, W, or Pt.
11. The process as claimed in claim 1, wherein the monomers are selected from thiols, alkenes, and alkynes.
12. The process as claimed in claim 11, wherein thiol monomers are selected from 2,2'-(Ethylenedioxy) diethanethiol [EDDT], Trimethylolpropane tris(3-mercaptopropionate) [TMPTMP], Pentaerythritol tetrakis(3-mercaptopropionate) [PETTMP] and 4,4'-Thiobisbenzenethiol [TBBT].
13. The process as claimed in claim 11, wherein the alkene monomers are Trimethylolpropane diallyl ether [TMPDE], 1,4-Butanediol divinyl ether [BDDV], 1,2,4-Trivinyl cyclohexane [TVCH], Dicyclopentadiene [DCPD] and Bicyclo [2.2.1] hepta-2,5-diene (2,5-Norbornadiene) [NBD].
14. The process as claimed in claim 11, wherein the alkyne monomers are selected from 1,7-Octadiyne (ODY) and 3,9-Dodecadiyne [DDY].
15. The process as claimed in claim 1, wherein the modification of PolyHIPE comprises steps of:
combining a metallic precursor and a solvent-cum-reductant to form a homogenous dispersion at an elevated temperature;
preparing a homogenous solution by mixing a dispersant with the solvent-cum-reductant by heating under stirring;
adding the dispersion to the homogenous solution under stirring at an elevated temperature to form a mixture;
allowing the mixture to react until the mixture becomes dark black from an initial reddish brown;
cooling the mixture to room temperature to obtain PolyHIPE discs;
purifying the PolyHIPE discs by multiple washing with organic solvent and water; and
drying the PolyHIPE discs to obtain pure catalyst loaded PolyHIPE.
16. The process as claimed in claim 15, wherein the metallic precursor is selected from sodium tetrachloropalladate, potassium tetrachloropalladate, palladium chloride, palladium acetate, palladium nitrate.
17. The process as claimed in claim 15, wherein the solvent-cum-reductant is selected from diethylene glycol, to ethylene glycol, triethylene glycol, tetraethylene glycol.
18. The process as claimed in claim 15, wherein the dispersant is Polyvinyl Pyrrolidone.
19. The process as claimed in claim 15, wherein the elevated temperature is in the range of 130°C to 150 °C.
20. The process as claimed in claim 15, wherein the PolyHIPE discs are dried under vacuum for at least 24 hours.
21. The process as claimed in claim 15, wherein the metallic precursor and solvent-cum-reductant are combined at a temperature in the range of 60°C to 80°C.
22. A composition for intensification of heterogeneous catalytic reactions, the composition comprising at least two monomers and a catalyst wherein the monomers are selected from thiols, alkenes, and alkynes, wherein the particle size of the catalyst is in the range of 10-50 microns.
23. The process as claimed in claim 1, wherein integrating the modified PolyHIPEs with dynamically stirred continuous flow reactors to enhance heterogeneous catalytic processes comprises steps of:
loading the ACR reactor block with catalyst baskets filled with pre-weighed number of Pd-PHP discs;
preparing and introducing a solution of a solvent with a base and phase transfer catalyst into the reactor from one of the bottom inlets under equilibration at set temperature and pressure conditions;
passing an unsaturated compound through the second bottom inlet after the completion of equilibration;
passing a Lewis acid through the second inlet after allowing to attain a steady flow;
allowing the reaction to occur; and
collecting the product through uppermost outlet.
24. The process as claimed in Claim 23, wherein the unsaturated compound is selected from alkenyl (vinyl), aryl, or alkynyl organoborane (boronic acid or boronic ester, or aryl trifluoroborane).
25. The process as claimed in claim 23, wherein the Lewis acid is selected from halides and triflates.
26. The process as claimed in Claim 23, wherein the base is selected from triethylamines, sodium acetate, potassium phosphate, sodium hydroxide, potassium carbonate.
27. The process as claimed in Claim 23, wherein the solvent is selected from water, ethanol, toluene, N, N-dimethylacetamide, either neat or as a mixture with varied proportions.
28. The process as claimed in Claim 23, wherein the phase transfer catalyst is selected from tetra-n-butylammonium bromide (TBAB), methyltrioctylammonium chloride, benzyltriethylammonium chloride, methyltricaprylammonium chloride, methyltributylammonium chloride, and organic phosphonium salts.
29. The process as claimed in Claim 23, wherein the temperature is in the range of 50°C -150°C.
30. The process as claimed in claim 23, wherein the pressure is in the range of 0 bar to 20 bar.