MODIFIED POROUS HYPERCROSSLINKED POLYMERS FOR CO2 CAPTURE AND CONVERSION

Abstract

The present disclosure describes a process for making a hyperporous material for capture and conversion of carbon dioxide. The process comprises the steps a first self-polymerisation of benzyl halides via Friedel-Crafts reaction. In the second step the obtained hypercrosslinked polymer is further coupled with an amine or heterocyclic compound having at least one nitrogen ring atom. The invention also relates to the material obtained to the process and its use in catalytic reactions, for instance the conversion of epoxides to carbonates. Salt-modified porous hypercrosslinked polymers obtained according to the invention show a high BET surface (BET surface area up to 926 m.sup.2/g) combined with strong CO.sub.2 capture capacities (14.5 wt %). The nitrogen compound functionalized hypercrosslinked polymer catalyst shows improved conversion rates compared to known functionalized polystyrene materials and an excellent recyclability. A new type of imidazolium salt modified polymers shows especially high capture and conversion abilities. Carbonates can be produced in high yields according to the inventive used of the obtained polymers.

Claims

1. A process for making a hypercrosslinked, porous polymer material comprising the steps of: (a) a self-polymerisation of benzyl halides via Friedel-Crafts reaction, and (b) coupling of an amine or heterocyclic compound having at least one nitrogen ring atom to the obtained polymer.

2. The process of claim 1, wherein the heterocyclic compound in step (b) is an optionally substituted heterocyclic compound having 5 or 6 ring atoms and 1 to 3 hetero atoms in the optionally benzofused ring and is coupled to the polymer to form a salt.

3. The process of claim 2, wherein the heterocyclic compound is an optionally benzofused, optionally heteroaromatic fused and optionally C.sub.1-C.sub.4-alkyl, halogen, cyano or nitro substituted pyrrole, pyrrolidine, pyrroline, piperidine, imidazole, imidazoline, imidazolidine, tetrazole, triazole, pyrazole, pyrazoline, pyrazolidine, oxazole, isoxazole, thiazole, morpholine, thiomorpholine, piperazine or isothiazole.

4. The process of claim 1, wherein the heterocyclic compound is an optionally 1-substituted imidazole.

5. The process of claim 1, wherein the benzyl halide is selected from a compound of the formula (I), (II), (III) or mixtures of compounds of these compounds ##STR00019## wherein X is a hydroxyl group (OH) or halogen, and at least one X is halogen; R is independently selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.3-alkyl or halgeno-C.sub.1-C.sub.3-alkyl; m is 1, 2, 3 or 4; n is 1, 2, or 3; p is 0, 1 or 2.

6. The process of claim 5, wherein the benzyl halide is a compound of formula (I), m is 1, n is 2 and p is 0.

7. The process of claim 5, wherein one X stands for chlorine and others stand for chlorine or a hydroxyl group.

8. The process of claim 1, wherein in step (a) a strong Lewis acid is used.

9. The process of claim 8, wherein the Lewis acid is selected from ferric halides.

10. The process of claim 1, wherein the Friedel-Crafts reaction in step (a) is performed at elevated temperatures, in an anhydrous organic solvent in the presence of a strong Lewis acid, and the coupling step (b) is performed in an inert organic solvent at elevated temperatures.

11. The process of claim 10, wherein the polymerization product of step (a) is separated off and purified before use in step (b).

12. The hypercrosslinked polymer material obtainable in the process of claim 1.

13. The hypercrosslinked polymer material of claim 12, having a BET surface area of about 500 to 1500 m.sup.2/g, calculated in a relative pressure range of P/P.sub.0=0.01 to 1.

14. The hypercrosslinked polymer material of claim 12, having pores of a pore size of about 0.1 to 50 nm.

15. The hypercrosslinked polymer material of claim 14, predominantly having micropores of a pore size of about 0.1 to 2 nm.

16. Use of the material according to claim 12 as a catalyst for conversion reactions in the presence of a gas.

17. The use of claim 16, wherein the coupled amine or heterocyclic compound supports the conversion reaction.

18. The use of claim 16, wherein the conversion reaction comprises the steps of: (a) carbon dioxide capture; and (b) carbon dioxide conversion.

19. The use of claim 18 wherein an epoxide group of a substrate compound is converted to a carbonate group.

20. The use of claim 16, wherein the catalyst is recycled for further use after the conversion reaction.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0072] The accompanying drawings illustrate a disclosed embodiment or serve to explain the principles of the disclosed embodiment. It is to be understood, however, that the drawings are designed for purposes of illustration only, and not as a definition of the limits of the invention.

[0073] FIG. 1 refers to the various synthesis schemes of supported imidazolium salts and the typical structure of POM-IM.

[0074] FIG. 2 refers to a solid-13C NMR spectrum for POM1-IM

[0075] FIG. 3 refers to an FT-IR spectrum for POM1-IM

[0076] FIG. 4 refers to an the thermogram of POM1-IM by TGA

[0077] FIG. 5 refers to the N.sub.2 adsorption and desorption isotherms for the obtained porous organic polymers POM1 and POM1-IM at 77 K.

[0078] FIG. 6 refers to a pore size distribution for POM3-IM calculated using NLDFT

[0079] FIG. 7 refers to a TEM image of POM1-IM.

[0080] FIG. 8 refers to the obtainable yield using recycled catalyst (reaction conditions: PO (1.43 mmol), POM3-IM (5 mmol % based on the imidazolium salt), Ethanol (2 ml), CO.sub.2 pressure (1 MPa), Temperature (120 C.), Time (4 h).

EXAMPLES

[0081] Non-limiting examples of the invention and a comparative example will be further described in greater detail by reference to specific Examples, which should not be construed as in any way limiting the scope of the invention.

Materials and Methods

[0082] The 1-methylimidazole, 1,4-bis (chloromethyl) benzene, 1,2-bis (chloromethyl) benzene and iron chloride were provided by Sigma-Aldrich. The chloromethyl polystyrene was purchased from Fluka, and the epoxides were purchased from the VWR international. GC-MS were measured on SHIMADZU-QP2010. GC analyses were performed on an Agilent GC-6890 using a flame ionization detector. NMR spectra were recorded on a Bruker 400. N.sub.2 sorption analysis and CO.sub.2 sorption analysis were performed on a Micromeritics Tristar 3000 (77 and 273 K, respectively). TEM experiments were conducted on a FEI Tecnai G2 F20 electron microscope (200 kV). TGA was performed on a Perkin-Elmer Pyris-1 thermogravimetric analyzer. Elemental analysis (CHNS) was performed on an Elementarvario MICRO cube. FT-IR experiments were performed on a Perkin Elmer Spectrum 100. Solid-13C NMR experiments were conducted at a Bruker Avance 400 (DRX400) with CP/MAS.

[0083] The calculations were carried out by performing DFT by use of the B3PW91 functional with the 6-31++G (d, p) basis set as implemented in Gaussian 03 program package. The solvent effect uses the Conductor Polarizable Continuum Model (CPCM) in each case. Vibrational frequency calculations, from which the zero-point energies were derived, have been performed for each optimized structure at the same level to identify the natures of all the stationary points. All the bond lengths are in angstroms (). Structures were generated using CYLview (CYLview, 1.0b; C. Y. Legault, Universite de Sherbrooke, 2009 (http://www.cylview.org).

[0084] The CO.sub.2 experiments were performed on a Belsorp-mimi II at 273 and 298 K. Before each measurement, the samples were heated at 150 C. in vacuum for 24 h. TGA gas capture experiments were conducted on a on a Perkin-Elmer Pyris-1 thermogravimetric analyzer. Porous carbons (5 mg) were subjected to the following gas capture and cycling experiment at 25 C.: CO.sub.2 (99.8%) gas flow at 20 mL min.sup.1 for 30 min, followed by N.sub.2 (99.9995%) gas flow at 20 mL min.sup.1 for 45 min. Changes in weight were recorded by using TGA. Prior to the cyclic treatment, the sample was first purged under N.sub.2 gas flow at 200 C. for 60 min, followed by cooling to room temperature. Change in buoyancy effects arising from the switching of gases was recorded by using an empty sample pan, and the buoyancy effects were corrected for in the TGA results. For the adsorption kinetics analysis, the porous carbon was first purged under Ar gas flow (20 mL min.sup.1) at 200 C. for 60 min, followed by cooling to room temperature. The gas was then switched from Ar to CO.sub.2 or N.sub.2 (20 mL min.sup.1). The selectivity of CO.sub.2 over N.sub.2 is calculated by the saturated absorption according to reported work by Fuertes (M. Sevilla and A. B. Fuertes, Energy Environ. Sci., 2011, 4, 1765).

Example 1: Synthesis of the Hyperporous Functonalized Polymer

[0085] The benzyl halide-functionalized organic polymers were synthesized according to methods generally known from C. D. Wood, B. Tan, A. Trewin, H. Niu, D. Bradshaw, M. J. Rosseinsky, Y. Z. Khimyak, N. L. Campbell, R. Kirk, E. Stockel and A. I. Cooper, Chem. Mater., 2007, 19, 2034 and C. F. Martin, E. Stockel, R. Clowes, D. J. Adams, A. I. Cooper, J. J. Pis, F. Rubiera, C. Pevida, J. Mater. Chem., 2011, 21, 5475. Typically, iron (III) chloride (120 mmol) was added to a solution of benzyl halide compound (60 mmol) in anhydrous dichloroethane (80 ml). The resulting mixture was heated at 80 C. for 24 h. When the reaction was completed, the solid product was centrifuged and washed with methanol (320 mL). The product was further purified by Soxhlet extraction in methanol for 20 h and dried in vacuum at 60 C. for 24 h. The polymers were obtained in quantitative yields. The content of chloride or bromide in the obtained polymers was determined by elemental analysis (Table 1). The polymers were further reacted with N-methylimidazole (molar ratio of Cl:N-methylimidazole=1:2) in 20 ml toluene at 80 C. for 24 h, the resultant supported imidazolium salts were washed with methanol (320 ml) and dried in vacuum at 60 C. for 24 h. From elemental analysis results, the modification was not completed for most of samples.

TABLE-US-00001 TABLE 1 C H Cl Br POM (wt %) (wt %) (wt %) (wt %) POM1 74.53 4.56 24.13 / POM2 74.71 4.42 10.70 / POM3 76.81 4.76 5.61 / POM4 71.43 3.92 / 6.8 POM5 71.91 4.35 / 1.5 POM6 87.42 5.05 <0.5 /

[0086] Table 1 refers to the elemental analysis results for POM16.

Synthesis Imidazolium Salt

[0087] A mixture of benzyl chloride (12 mmol), 1-methylimidazole (10 mmol) and toluene (10 mL) was heated at 80 C. for 24 h in a 25 mL flask with vigorous stirring. After cooled down to room temperature, the solid residue washed with benzene (35 mL) and ethyl acetate (35 mL). Then, the solid was dried under vacuum at 60 C. for 12 h and the imidazolium salt was obtained.

Comparative Example: Synthesis of Polystyrene Resin Supported Imidazolium Salt

[0088] Polystyrene (PS) resin supported imidazolium salt was made according to a method generally known from J. Sun, W. G. Cheng, W. Fan, Y. H. Wang, Z. Y. Meng, and S. J. Zhang, Catal. Today, 2009, 148, 361-367). A mixture of chloromethyl polystyrene (1.0 g, 5.5 mmol Cl content), 1-methylimidazole (16.5 mmol) and toluene (10 mL) was heated at 80 C. for 24 h in a 25 mL flask with vigorous stirring. After cooled down to room temperature, the solid residue was collected by filtration and washed with methanol (35 mL). Then, the solid was dried under vacuum at 60 C. for 12 h and polystyrene resin supported imidazolium salt was obtained. The loading of imidazolium salt attached on the PS was 3.6 mmol/g determined by nitrogen content from elementary analysis.

Example 2: CO.SUB.2 .Capture

[0089] Imidazolium salt-modified porous hypercrosslinked polymers were subjected to the following gas capture and cycling experiment at 25 C.: CO.sub.2 (99.8%) gas flow at 20 ml/min for 30 min, followed by N.sub.2 (99.9995%) gas flow at 20 ml/min for 45 min. Changes in weight were recorded by TGA. Prior to the cyclic treatment, the sample was first purged under N.sub.2 gas flow at 100 C. for 60 min, followed by cooling to room temperature. Change in buoyancy effects arising from the switching of gases was recorded by using an empty sample pan, and the buoyancy effects were corrected.

[0090] For the adsorption kinetics analysis of CO.sub.2 and N.sub.2, the porous supported imidazolium salt was first purged under Ar gas flow (20 ml/min) at 100 C. for 60 min, followed by cooling to room temperature. The gas was then switched from Ar to CO.sub.2 or N.sub.2 (20 ml/min).

Example 3: CO.SUB.2 .Conversion

[0091] CO.sub.2 conversion reactions were conducted in a 50 ml stainless steel reactor equipped with a magnetic stirrer and automatic temperature control system. Typically, an appropriate volume of CO.sub.2 (1.0 MPa) was added to a mixture of propylene oxide (PO) (0.1 ml), ethanol (2 ml), porous supported imidazolium salt (5 mmol % based on contents of the imidazolium salt) in the reactor at room temperature. The temperature was then raised to 120 C. After the reaction was preceded for 4 h, the reactor was cooled to 0 C. in an ice water bath, and the remaining CO.sub.2 was slowly removed.

[0092] The product was then analysed by GC and NMR. The porous supported imidazolium salts could be easily separated by centrifugation, and used in the next run without further purification.

Results Using the Material and Methods of the Examples

[0093] The synthetic approach to imidazolium-modified porous hypercrosslinked polymers of the examples is shown in FIG. 1. The monomers were directly self-polymerized via Friedel-Crafts reactions. The resultant polymers with remaining benzyl chloride (or benzyl bromide) groups were further reacted with N-methylimidazole. All the polymers were produced as insoluble dark brown solids in yields over 90% on a typical scale of 10 g per batch. The materials were characterized by 13C NMR (solid-state), FT-IR and elemental analysis. The resolved resonance around 129 ppm and 134 ppm was found and is assumed to correspond to the aromatic carbons of the benzene ring and imidazole ring (FIG. 2). A signal around 35 ppm was assumed to the methylene carbon formed via Friedel-Crafts reaction. In FT-IR spectra, the presence of imidazolium salts was confirmed by strong absorption bands around 1600 cm.sup.1 (FIG. 3). The nitrogen content of porous materials from bis-substituted monomers was determined by elemental analysis to be about 1.8 to 2.8 wt % (imidazolium loading 0.6 to 1.0 mmol/g, Table 2).

TABLE-US-00002 TABLE 2 C H N Degree of halogen POM (wt %) (wt %) (wt %) substitution (%) POM1-IM 74.36 4.85 2.01 11% POM2-1M 75.41 4.69 2.01 23% POM3-IM 72.11 5.06 2.84 63% POM4-IM 68.04 4.44 1.85 78% POM5-IM 80.74 5.13 1.19 >99% POM6-IM 71.89 4.63 <0.50 POM3-IM.sup.a 72.22 5.04 2.82 .sup.aAfter six runs

[0094] Table 2 refers to Elemental analysis results for POM16-IM.

[0095] Polymers synthesized from mono-substituted monomers gave much lower nitrogen loading, especially for POM6-IM. Thermal gravimetric analysis (TGA) shows that all porous organic materials (POM16 and POM16-IM) have excellent thermal stability (FIG. 4, POM1-IM as example).

[0096] The porosities of the original porous polymers (POM) and imidazolium salt functionalized porous polymers (POM-IM) were evaluated by N.sub.2 adsorption-desorption isotherms (FIG. 5).

[0097] The micro pore size distributions of these materials are predominantly around 1.4 nm (FIG. 6, POM3-IM as an example). However, also meso- and macrostructures (>2.0 nm) were observed based on related isotherms curves. The transmission electron microscopy (TEM) image of POM1-IM also demonstrated a uniform micro pore (FIG. 7). The textural properties of the first-step polymers (POM16) and imidazolium modified polymers are shown in the Table 3. The BET surface areas for the imidazolium modified porous polymers are in the range of 99 and 926 m.sup.2/g. The total pore volume and the micro pore volume are as high as 1.06 cm.sup.3/g and 0.17 cm.sup.3/g, respectively. The BET surface area and pore volume of the imidazolium-modified polymers are similar or lower than the respective original polymers (POM16-IM vs POM16). In addition, the porosity of the materials from bis-substituted precursors (POM 1-4) is much larger than those from mono-substituted precursors (POM 5-6), as bis-substituted precursors could form more crosslinks during the reaction. As for the choice of halide, benzyl chloride resulted in better porous materials than corresponding benzyl bromide (POM 5 vs 6).

TABLE-US-00003 TABLE 3 S.sub.BET.sup.a/ S.sub.micro.sup.b/ V.sub.total.sup.b V.sub.micro/ CO.sub.2 uptake.sup.c/wt % Polymers m.sup.2/g m.sup.2/g cm.sup.3/g cm.sup.3/g (273K) POM1 1089 390 1.31 0.17 13.8 POM2 1047 486 0.82 0.22 13.0 POM3 1088 563 0.71 0.26 16.4 POM4 752 418 0.54 0.19 12.4 POM5 81 0 0.75 0 3.8 POM6 664 297 0.45 0.13 9.5 POM1-IM 926 373 1.06 0.17 13.9 POM2-IM 653 335 0.51 0.15 14.5 POM3-IM 575 334 0.39 0.15 14.2 POM4-IM 632 375 0.48 0.17 10.6 POM5-IM 50 0 0.12 0 5.7 POM6-IM 659 278 0.45 0.12 5.5 POM3-IM.sup.d 530 320 0.32 0.12 14.2

[0098] Table 3 refers to the physical properties for the porous organic materials (.sup.aThe BET surface area was calculated in a relative pressure range P/P0=0.01-1. .sup.bThe micropore surface area Sm, and micropore volume V.sub.micro were estimated from the t-plot method. .sup.cMeasured at 273 k and 1 bar. .sup.dafter six runs.)

[0099] According to the examples it has been found that materials derived from bis-substituted benzenes exhibited better CO.sub.2 capture capacity (10.614.5 wt % by BET at 273 K and 1 bar and 4.64.8 wt % by TGA at 298 K and 1 bar). The CO.sub.2 capture capacity of different polymers is closely correlated with micro pore volumes and load of imidazolium salts. In general, the introduction of functional groups decreased its porosity of the material (such as BET surface area and pore volume), as well as CO.sub.2 capture capacity. For imidazolium-modified polymers (POM1, 2, 4, 5-IM), their porosities are indeed decreased. Surprisingly, their CO.sub.2 capture capacities were kept in the same range or slightly increased (Table 3). On the contrary, the CO.sub.2 capacities of POM3-IM and POM6-IM were lower than that of POM3 and POM6 possibly because of the significant decrease in BET surface area and pore volume in these two cases. POM3 has highest CO.sub.2 capture capacity due to its high micro pore volume and the presence of hydroxyl group. Polymers derived from mono-substituted monomers (benzyl chloride and benzyl bromide) have a bit lower CO.sub.2 capture capacities. The heat of absorption for POM13-IM is 25.6, 31.1 and 31.5 kJ/mol, respectively. But, these materials have fast adsorption rate, over 97% of CO.sub.2 was adsorbed within 8 min. The CO.sub.2 and N.sub.2 selectivity of these materials is as high as 13 at the equilibrium conditions. The CO.sub.2 adsorption of these materials is fully reversible. The polymer made according to the inventive process is stable in hot water. No polymer degrading was observed and the CO.sub.2 capture capacity of polymer kept the same after hot water treatment (80 C., 18 h). Although the CO.sub.2 capture capacity of current materials is not the highest as comparing to other knitted polymer, this imidazolium modified porous polymer provides an excellent opportunity to look for the synergistic effect of CO.sub.2 capture and conversion.

[0100] In addition, polymers are more hydrophilic after being modified by imidazolium salts, which is also beneficial for CO.sub.2 conversion. The catalytic activities of the synthesized porous hypercrosslinked polymer-supported imidazolium salts were tested for the conversion of CO.sub.2 and propylene oxide (PO) into propylene carbonate (PC). Surprisingly, these materials (POM-IM) demonstrated much higher activities than the conventional PS supported materials under the same reaction conditions (entry 1 vs 7, Table 4). The catalytic activities of POM1-IM and POM3-IM were even higher than the homogeneous imidazolium catalyst (entry 1 vs 8). This may be attributed to the synergistic effect of the micro pore structure and the catalytic centres which are located in the pore structure. The polymers could capture and concentrate CO.sub.2, which results in a 20 higher CO.sub.2 concentration near catalytic centres and makes the catalytic reaction more efficient. To prove this, reactions under low CO.sub.2 pressure (0.2 MPa vis 1 MPa) were carried out. As shown in Table 4, POM3-IM retained more than half of its original catalytic activity at low CO.sub.2 pressure (42% yield vis 78% 25 yield), while PS-IM and homogeneous BMIC almost lost all their catalytic activities (entries 9-11). 42% yield of POM3-IM catalyst at 0.2 MPa is higher than PS-IM (30%) and close to BMIC catalysts (49%) under 1 MPa. The total pore volume of POM3-IM is 0.39 cm.sup.3. It can capture more than 0.5 wt % (5 mg/g) of CO.sub.2 at 120 C. under 0.1 MPa. 5 mg of CO.sub.2 will occupy more than 3 cm.sup.3 volume (vis 0.39 cm.sup.3 total pore volume) at 120 C. under 0.1 MPa. This could explain the high activity of POM3-IM and further confirmed that the micro pore structure does play an important role in imidazolium salt catalysed CO.sub.2 transformation. In addition, the catalytic activity of polymers was generally corresponded to their BET surface area and halide loading. No activity was observed for POM6-IM due to the low contents of imidazolium salts (entry 6).

TABLE-US-00004 TABLE 4 Entry Cat. PO conv..sup.b (%) PC yield.sup.b (%) 1 POM1-IM 59 58 2 POM2-IM 46 46 3 POM3-IM 78 78 4 POM4-IM 40 40 5 POM5-IM 38 38 6 POM6-11V1 Trace Trace 7.sup.c PS-IM 30 30 8.sup.d BMIC 49 49 9.sup.e POM3-IM 42 42 10.sup.e BMIC 6 6 11.sup.e PS-IM 5 5

[0101] Table 4 refers to the activities of supported imidazolium salts for the conversion of CO.sub.2 with propylene oxide into propylene carbonate.sup.a (.sup.aReaction conditions: PO (1.43 mmol), catalyst (5 mmol % based on the imidazolium salt), ethanol (2 ml), CO.sub.2 pressure (1 MPa), 120 C., 4 h. .sup.bYield and conversion were determined by GC using biphenyl as the internal standard. .sup.cPS=polystyrene resin. .sup.dBMIC=1-benzyl-3-methylimidazolium chloride. .sup.eCO.sub.2 pressure (0.2 MPa).)

[0102] Surprisingly, POM3-IM, which has hydroxyl functionality in its framework, demonstrated the highest activity among them for the conversion of CO.sub.2 with PO to propylene carbonate (entry 4 vs 1 and 2). It is believed that the high activity of this material is due to the hydrogen bond interactions between hydroxyl groups and reactants. Recycling experiments indicated that the POM-IM materials have excellent stability and recyclability. It was reused for six runs and no obvious loss in activity was observed (FIG. 8). FT-IR spectra of POM3-IM catalyst before and after the reaction did not show any notable difference which further supported the stability of the porous POM-IM materials. The stability of reused polymeric catalyst is further verified by N.sub.2 adsorption and elemental analysis, the surface area changed slightly from 575 to 530 cm.sup.2/g (Table 3), and the contents of nitrogen has no obvious decrease.

[0103] Quantum calculations were also carried out to investigate the reaction mechanism with 1-benzyl-3-methylimidazolium chloride as the model catalyst. The calculation was conducted by use of the B3PW91 functional with the 6-311++G (d, p) basis set as implemented in Gaussian 09 program package. The catalytic cycle was presumed to occur in three steps.

[0104] The first step is ring-opening through the attack of the nucleophile (Clfrom imidazolium salt) on epoxide, which was considered to be the most difficult step with the largest activation energy (E=21.25 kcal/mol). The second step was the insertion of CO.sub.2. The last step was the formation of cyclic carbonate with activation energy of 19.3 kcal/mol. This catalytic cycle involving C(2)-H of imidazolium salt activation process is exothermic with low activation barrier, which allows the reaction to be performed under mild condition. The reaction mechanism of POM3-IM with hydroxyl group was also studied using 1-benzyl-3-methylimidazolium chloride and benzyl alcohol as the model system. A double activation process with both C(2)-H of the imidazolium salt and hydroxyl group of benzyl alcohol may be proposed. This double activation process further decreased the activation energy, especially for the ring-opening step (18.35 vis 21.25 kcal/mol).

[0105] The epoxide substrate scope was screened using POM3-IM as the catalyst. As shown in Table 5, the catalytic system was found to be effective for a variety of terminal epoxides (entries 1-8). Furthermore, epoxides functionalized with alkene or long hydrophobic chain were also suitable substrates for this catalytic system (entries 5-8). Compared with other reported functionalized porous organic polymers the POM-IM is indeed very promising as a heterogeneous organocatalyst for two respects: the catalysts were synthesized in a simple and easily controllable way, and the reactions proceeded well under relatively mild condition.

TABLE-US-00005 TABLE 5 Time/ Conv./ Yield/ Entry Epoxide Product h %.sup.b %.sup.b 1 [00003] [00004] 8 94 92 2 [00005] [00006] 8 96 90 3 [00007] [00008] 12 90 89 4 [00009] [00010] 12 91 91 5 [00011] [00012] 12 76 73 6 [00013] [00014] 12 70 68 7 [00015] [00016] 30 98 93 8 [00017] [00018] 30 86 85

[0106] Table 5 refers to the substrate scope in the conversion reactions. (.sup.aReaction condition: Epoxide (1.43 mmol), POM3-IM (5 mmol % based on the imidazolium salt), ethanol (2 ml), CO.sub.2 pressure (1 MPa), Temperature (120 C.), every experiment was conducted in triplicate. .sup.bYield and conversion were determined by NMR.

INDUSTRIAL APPLICABILITY

[0107] The hypercrosslinked material made according to the process of the present disclosure may be useful in catalysis involving CO.sub.2 as gaseous reagents due to its high ability to capture CO.sub.2 and its ability to convert chemical compounds with the captured CO.sub.2. The process allows for the conversion of CO.sub.2 and epoxides to cyclic carbonates in high yields.

[0108] The materials obtained by the process according to the invention demonstrate high stability and reusability for both CO.sub.2 capture and conversion and may find use in industrial catalysis at larger scales.

[0109] Due to their capture abilities the hypercrosslinked material made according to the process of the invention may be useful in other applications in which a gas, ion, atom or molecule or needs to be captured. Such applications could include water treatment or heavy metal removal.

[0110] It will be apparent that various other modifications and adaptations of the invention will be apparent to the person skilled in the art after reading the foregoing disclosure without departing from the spirit and scope of the invention and it is intended that all such modifications and adaptations come within the scope of the appended claims.