KR102028614B1 - Synthesis of Ni-loaded Porous Organic Polymers and its Application to Heterogeneous Catalyst for Ethylene Dimerization - Google Patents

Abstract

The present invention relates to a porous organic polymer loaded with nickel, a method for preparing the same, and a catalyst for ethylene dimerization reaction including the porous organic polymer and an ethylene dimerization reaction method using the same. It is synthesized by using a reaction. It is very easy to synthesize. It is composed of covalent bonds and has excellent thermal and mechanical stability. It can be used in many fields. It is a heterogeneous catalyst that enables the synthesis of long carbon chain compounds from short carbon chains. It can be used.

Description

Synthesis of Ni-loaded Porous Organic Polymers and its Application to Heterogeneous Catalyst for Ethylene Dimerization

The present invention relates to a porous organic polymer equipped with nickel, a method for preparing the same, and a catalyst for ethylene dimerization reaction including the porous organic polymer and an ethylene dimerization method using the same.

Porous materials with large internal surface areas can often offer advantages over non-porous materials. Recently, gas storage (L.-B. Sun et al., Chem . Soc . Rev. 2015, 44, 5092-5147; R. Grunker et al., Chem . Commun . 2014, 50, 3450-3452; S. Shylesh et al., Angew . Chem ., Int . Ed . 2010, 49, 3428-3459; OK Farha et al., Nat. Chem. 2010, 2, 944-948; H. Furukawa et al., Science 2010, 329, 424-428; LJ Murray et al., Chem . Soc . Rev. 2009, 38, 1294-1314), chemical separation (M. Stalzer et al., Catal . Lett . 2015, 145, 3-14; TM McDonald et al., Nature 2015, 519, 303-308; H. Fei et al., J. Am. Chem . Soc . 2014, 136, 4965-4973; J. Lee et al., Chem . Soc . Rev. 2009, 38, 1450-1459), chemical sensing (HGT Nguyen et al., Cryst. Growth Des . 2013, 13, 3528-3534; LE Kreno et al., Chem . Rev. 2012, 112, 1105-1125) and Catalysis (EM Miner et al., Nat. Commun . 2016, 7, 10942; D. Yang et al., J. Am. Chem . Soc . 2015, 137, 7391-7396; J. Lee et al., Chem .. Soc Rev. 2009, 38, 1450-1459) such a material (e.g., metal-organic framework material (MOF) in a wide range of applications, including porous organic polymers (POP) and shared organic skeleton body (COF) ) Is growing in interest. They are applied to heterogeneous catalysis based on the fact that they have some potential advantages over homologous analogs.

Although homogeneous catalysts provide high selectivity or require relatively low activation energies (D. Astruc et al., Angew . Chem ., Int . Ed . 2005, 44, 7852-7872), products and catalysts are Low stability or difficulty in separation can be difficult (L. Yin et al., J. Chem . Rev. 2007, 107, 133-173). Therefore, important studies have focused on the development of "heterogenized" versions of homogeneous catalysts to overcome these limitations (L.-B. Sun et al., Chem . Soc. Rev. 2015, 44 , 5092-5147; R. Grunker et al, Chem Commun 2014, 50, 3450-3452;..... M. Stalzer et al, Catal Lett. 2015, 145, 3-14; P. McMorn et al., J. Chem . Soc . Rev. 2004, 33, 108-122). Well defined porous solids are promising supports for immobilizing transition metal-based molecular catalysts (HGT Nguyen et al., Cryst. Growth Des . 2013, 13, 3528-3534; LE Kreno et al., Chem . Rev. 2012 , 112, 1105-1125; EM Miner et al., Nat. Commun . 2016, 7, 10942; HGT Nguyen et al., ACS Catal . 2014, 4, 2496-2500). Unfortunately, these heterogeneous catalysts have low chemical stability (W. Zhou et al., Chem . Phys. Lett . 2010, 499 , 103-107; In D. Saha et al., J. Phys. Chem . Lett . 2009, 1, 73-78), often showing low conversion rates and turnover numbers (TON) (KK Tanabe et al., Angew. Chem., Int. Ed . 2010, 49, 9730-9733).

Porous materials, such as zeolites, have excellent stability of the material, but are very difficult to synthesize, resulting in poor access to the material. In addition, the pore size is very small, there are many restrictions on the use. In addition, while porous materials such as MOF show excellent crystallinity, thermal stability is considerably reduced, and since the metal and the organic compound are formed by coordination bonds, they have low stability against strong polar solvents such as water. Therefore, there is a high demand for a porous material that is easy to synthesize and has high stability.

Because promising materials are usually composed of strong covalent bonds, such as carbon-carbon, carbon-nitrogen, and / or carbon-oxygen bonds, POPs may include catalyst-related ligands that are bound directly to structures with high chemical stability. Is a promising substance. In addition to high stability, POPs with high accessible surface areas can be synthesized to incorporate a wide range of chemical functions at high loads. As a result, POPs with well-defined pores are very attractive heterogeneous supports in a variety of applications, although they are amorphous materials that cannot be characterized through X-ray crystallographic studies (J. Weber et al., Langmuir 2010, 26). , 15650-15656; X. Wang et al., Applied Surface Science , 2017, 420, 496-503; P. Kaur et al., ACS Catal ., 2011, 1, 819-835).

Accordingly, the present inventors have made efforts to develop a porous material having high stability and a catalyst using the same, as a result of easy synthesis, and synthesized a Ni-loaded POP through a click-reaction and high in ethylene dimerization. By confirming that the catalyst activity was exhibited, the present invention was completed.

An object of the present invention is to provide a porous organic polymer, characterized in that represented by the following formula (1):

[Formula 1]

.

.

Another object of the present invention is to provide a porous organic polymer characterized in that the nickel is mounted on the porous organic polymer, represented by the following formula (2):

[Formula 2]

.

.

Still another object of the present invention is to provide a catalyst for ethylene dimerization reaction containing the porous organic polymer.

Another object of the invention is (a) tetra (4-azophenyl) methane and 5,5'-diethynyl-2,2'-bipyridine (5,5'-diethynul -2,2'-bipyridine) to provide a method for producing a porous organic polymer comprising the step of producing a porous organic polymer by a click reaction.

Another object of the present invention is to provide a method for ethylene dimerization using the catalyst.

In order to solve the above problems, the present invention provides a porous organic polymer, characterized in that represented by the following formula (1):

[Formula 1]

.

.

The present invention also provides a porous organic polymer characterized in that the nickel is mounted on the porous organic polymer, represented by the following formula (2):

[Formula 2]

.

.

The present invention also provides a catalyst for ethylene dimerization reaction comprising the porous organic polymer.

The present invention also relates to (a) tetra (4-azophenyl) methane and 5,5'-diethynyl-2,2'-bipyridine (5,5'-diethynyl-2 , 2'-bipyridine) by providing a method of producing a porous organic polymer comprising the step of combining the porous organic polymer by a click reaction.

The present invention also provides a process for the ethylene dimerization reaction using the catalyst.

The porous organic polymer according to the present invention is synthesized by using a click reaction and is very easy to synthesize, and is composed of covalent bonds, and thus has excellent thermal and mechanical stability, and thus can be utilized in many fields. It can be utilized as a heterogeneous catalyst that enables synthesis.

FIG. 1 shows the preparation of tetra (4-azidophenyl) methane and 5'5-diethynyl-2,2'-bipyridine of Example 1-2.
Figure 2 shows the manufacturing process of POP and Ni-containing POP of Example 2-1.
Figure 3 shows the manufacturing process of POP-1 and Ni (II) -POP-1 of Example 2-1.
4 shows FTIR spectra of POP-1 and the like of Example 2-2.
5 shows FTIR spectra of POP-1, Ni (II) -POP-1, and the like of Example 2-2.
FIG. 6 shows a ¹³ C CPMAS NMR spectrum of POP-1 of Example 2-2. FIG.
7 shows a catalyst circuit of the ethylene dimerization reaction of Ni (II) -POP-1 in Example 3. FIG.
8 shows the results of EDX analysis of Ni (II) -POP-1 in Example 2-2.
9 shows N ₂ adsorption (indicated by filled circles) and desorption (indicated by empty circles) isotherms such as POP-1 and Ni (II) -POP-1 in Example 2-2.
Figure 10 shows the results confirmed by the TGA analysis of the thermal properties of POP-1, Ni (II) -POP-1 and the like of Example 2.
FIG. 11 shows a catalyst circuit of the isomerization reaction of the ethylene dimerization reaction of Example 3. FIG.
12 is an SEM image of Ni (II) -POP-1 recovered after (a) POP-1, (b) Ni (II) -POP-1 and (c) catalysis of Example 3. FIG.
FIG. 13 is an SEM image of Ni (II) -POP-1 recovered after (a) once, (b) twice, (c) three times, and (d) four times the catalytic reaction of Example 3. FIG.
FIG. 14 is a DSC analysis result of ethylene polymer (PE) generated after catalytic reaction using Ni (II) -POP-1 of Example 3. FIG.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

In one aspect, the present invention relates to a porous organic polymer represented by the following Chemical Formula 1:

[Formula 1]

.

.

In another aspect, the present invention relates to a porous organic polymer having nickel on the porous organic polymer and represented by the following Chemical Formula 2:

[Formula 2]

.

.

In an embodiment of the present invention, as shown in Scheme 1, a mixed solution of tetra (4-azophenyl) methane and 5,5'-diethynyl-2,2'-bipyridine dissolved in DMF is heated, and copper sulfate And sodium ascorbate in turn, and after heating, the cooled and precipitated solid particles were separated, washed sequentially with water, methanol and THF, and the obtained brown solid was put in water, stirred and separated, and then vacuumed. Drying under, the brown solid polymer POP-1 was synthesized:

Scheme 1

.

.

In the present invention, the porous organic polymer (POP-1) of the general formula (1) is a porous polymer formed by covalent bonds through two organic connectors through a click reaction, has a pore of ~ 10nm, is a material having a large hole inside . POP-1 has a bispyridine group inside and has a functional group capable of introducing various transition metals, and various reactions such as oxidation reaction, hydrogenation reaction and polymerization reaction can be performed depending on the type of transition metal introduced. It can be used as a catalyst which can be promoted. POP-1 is capable of introducing various transition metals because bispyridine groups are included in the organic linkage and are not particularly limited.

In another embodiment of the present invention, after dissolving nickel chloride in DMF as shown in Scheme 2, after heating and cooling the mixture to which the POP-1 is added, the polymer particles are separated by a centrifuge, and then using DMF. After washing three times and washing three times with acetone, and dried under vacuum to synthesize a brown polymer Ni (II) -POP-1:

Scheme 2

.

.

In the present invention, the nickel-containing porous organic polymer represented by Chemical Formula 2 (Ni (II) -POP-1) is a polymer synthesized by reacting nickel chloride with POP-1 and has pores of ˜10 nm. Carda is a substance that has a pupil. Depending on the nature of nickel introduced by coordinating nickel chloride, which is a kind of transition metal, to the bispyridine group of POP-1 in coordination bond, it can be utilized as a catalyst for promoting the dimerization reaction of ethylene, and as a heterogeneous catalyst. The recovery rate of the catalyst can be increased as compared to the homogeneous catalyst, and thus it is widely applicable to various industrial fields using a polymerization reaction including an ethylene dimerization reaction. Ni (II) -POP-1 is a catalyst with good turnover and little effect on catalyst activity by reuse. The ethylene is not particularly limited, but preferably ethylene.

In another aspect, the present invention relates to a catalyst for ethylene dimerization reaction containing the porous organic polymer.

In another aspect of the present invention, (a) tetra (4-azophenyl) methane and 5,5'-diethynyl-2,2'-bipyridine (5,5'- Diethynul-2,2'-bipyridine) relates to a method for producing a porous organic polymer comprising the step of producing a porous organic polymer by combining in a click reaction.

In the present invention, (b) may include the step of preparing a nickel-based porous organic polymer by adding nickel chloride (NiCl ₂ ) to the porous organic polymer prepared in step (a).

As used herein, the term 'click reaction' is also referred to as a click chemistry reaction, and forms an intermolecular bond in high yield not only with a low molecule but also with a polymer by high reactivity, and generally to form a large molecule. It is a fast and irreversible reaction that binds small molecules.

In the present invention, the porous organic polymer prepared in step (a) may be represented by the formula (1), the nickel-based porous organic polymer prepared in step (b) is represented by the formula (2) It may be characterized by being displayed.

In the present invention, step (a) or step (b) may be characterized by using a dimethylformamide (dimethylformamide, DMF) solvent.

In another aspect, the present invention relates to a ethylene dimerization reaction method using the catalyst.

In the present invention, preferably, the ethylene dimerization reaction may be performed at a temperature of -40 to 20 ° C. If the temperature is less than -40 ℃ yield is not very low as 0.069 (μmol _{total product} / g _catalyst ) is not preferable, if the temperature exceeds 20 ℃ it is not preferable because the catalytic activity is reduced by the production of many polymers.

In the present invention, the ethylene dimerization reaction may be preferably performed at a pressure of 5 to 20 bar. If the pressure is less than 5 bar, the yield is very low, and if it exceeds 20 bar, the formation of the polymer is large and the yield is low, which is not preferable.

EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as being limited by these examples. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Example  1: General Experiment Method

1-1: Analysis Method

¹ H-NMR spectra were recorded with a Varian AS400 (399.937 MHz for ¹ H and 100.573 MHz for ¹³ C) and a Bruker 500 MHz Ascend spectrometer. ¹ H chemical shifts refer to proton resonances from proton residues in deuterated solvents, and ¹³ C chemical shifts record a downfield in ppm related to carbon resonances of deuterated solvents. Solid-phase MAS-NMR experiments were performed on a Bruker AVANCE II + 400 MHz NMR system at KBSI Seoul West Center (Korea). The rotation speed was 12 kHZ. Spectra were obtained using a ¹ H- ¹³ C CP contact time of ² ms and a recycle delay of 3 seconds between scans. ¹³ C NMR chemical shifts were corrected using tetramethylsilane (TMS) at 0 ppm. Fourier-transform infrared (FTIR) spectroscopy was performed on an ALPHA FT-IR Spectrometer (Bruker Optics) equipped with a single-reflective diamond ATR accessory for all samples. The frequency is expressed in inverse centimeters (cm-1).

Thermogravimetric analysis was performed using a Scinco TGA N-1000 instrument at an elevated rate of 10 ° C./min under N 2 flow (50 mL / min). Thermal properties were studied under a nitrogen atmosphere with TA Instruments DSC Q20 and measurements were performed at a heating (cooling) scan rate of 10 (-10) ° C./min. N ₂ adsorption and desorption isotherms were measured at 77 K using Micromeritics Tristar II equipment (Micromeritics Instrument Corporation, USA) and BELSORP-mini II equipment (MicrotracBEL Corp., Japan). The DEF pore size distribution was obtained from the resulting desorbed branches of the isotherm. Prior to each experiment, samples were activated at 80 ° C. for 3 hours under high vacuum on BELSORP Prep II (MicrotracBEL Corp., Japan) or critical point drying on SAMDRI-PVT-3D (Tousimis, USA). About 50-80 mg of sample Was used for each measurement. All gas using an Agilent Technologies 6890N Network GC system (Agilent Technologies, Inc., Santa Clara, CA, USA) equipped with a FID detector and an HP-5 capillary column (50 m X 320 μm X 0.17 μm film thickness) Chromatographic (GC) analysis was performed. All samples were prepared by brominating low-boiling ethylene in a pre-cooled solution (dry ice / acetone bath). Intrinsic activity for butenes (ratio between the amount of butenes formed and the Ni content of the catalyst) was evaluated based on the ratio of the peak area of the brominated butene product.

GC-MS analysis was performed with GC 7890B combined with MSD 5977A (Agilent) using a DB-624 capillary column (30 m × 250 μm; film thickness, 0.25 μm) at Kookmin University (Seoul, Korea). Scanning electron microscope (SEM) images were collected using a JSM-7001F (JEOL, Japan) microscope. Samples were activated and coated with Pt using Sputter Coater 108 Auto (Cressington, Watford, UK) prior to imaging. Nickel content was measured using inductively coupled plasma-atomic emission spectroscopy (ICP-AES, iCAP 7600, Thermo Scientific) compared to ICP standard solutions.

POP-1-supported Ni (II) catalyst (approx. 1 mg) was added 0.75 mL of sulfuric acid (ACS reagent, 95-98%, Sigma-Aldrich) and 0.25 mL of 30 wt% H ₂ O ₂ (aqueous, Sigma- Aldrich) and dissolved in the microwave using initiator + (Biotage) at 150 ° C. for 5 minutes. Ni (II) -POP-1 was characterized by scanning electron microscopy-energy injection spectroscopy at the KBSI Seoul Center. SEM / EDX experiments were performed using a Hitachi SU-70 SEM equipped with a silicon drift EDX detector (50 mm ² , Horiba, Japan). The acceleration beam voltage was fixed at 15 kV.

1-2: Preparation and Preparation of Experimental Materials

All reagents and solvents were purchased from commercial sources and used without further purification unless otherwise indicated. All reactions and operations were performed under air atmosphere unless otherwise indicated. The distilled solvent used in the inert-air reaction was dried according to standard procedures (D. D. Perrin and W. L. Armarego, Purification of Laboratory Chemicals, 3rd edn., 1988, Pergamon, Oxford). All flash column chromatography was performed using silica gel 60 (230-400 mesh, Merck, Germany) using the wet-packing method, and TLC was precoated silica gel plate (0.25 mm thick, 60 F254, Merck, Germany). ) Was observed under UV ultraviolet light. All deuterated solvents were purchased from Cambridge Isotope Laboratories and Aldrich.

1-2-1: Tetraphenylmethane (L1, Fig. 1)

In a round-bottom flask, chlorotriphenylmethane (20.0 g) and aniline (17.6 mL) were heated at 190 ° C. for 15 minutes with vigorous stirring. After the reaction mixture cooled to room temperature, the resulting solid was triturated. Then an aqueous HCl (2M, 80 mL) solution and methanol (120 mL) were added and the mixture was heated again at 80 ° C. for 30 minutes. After cooling to room temperature, the resulting solid was filtered, washed with water (250 mL) and dried in vacuo overnight. The dried solid was further ground and suspended in DMF and then cooled to -15 ° C. At this temperature, sulfuric acid (96%, 22 mL) and isoamyl nitrite (16 mL) were added slowly and the suspension was stirred for 1 hour. Hypophosphoric acid (50%, 60 mL) was then added dropwise. After the addition was complete, the reaction mixture was heated at 70 ° C. until gas evolution ceased. The solid was then filtered off and subsequently washed with DMF, water and ethanol. This washing procedure was repeated twice. Recrystallization in DMF to give a brown powder gave pure tetraphenylmethane (L1, 15.5 g, 67%). ¹ H NMR (500 MHz, CDCl ₃ ) δ = 7.20-7.29 (m, 20H ) (X. Wang et al., Catal . Sci. Technol. , 2015, 5, 2585-2589).

1-2-2: Tetra -(4- Nitrophenyl ) -Methane (L2, Figure 1)

L1 (2 g) was added to 10 mL fuming nitric acid (96%) and stirred at -10 ° C with vigorous stirring. To this mixture was slowly added 3.3 mL of acetic anhydride and 6.6 mL of glacial acetic acid and stirred for ˜15 minutes. Finally, the reaction mixture was diluted with 32 mL of glacial acetic acid and the resulting yellow solid was filtered on a glass frit, washed with acetic acid, methanol, cooled THF and dried under dynamic vacuum to give a yellow crystalline solid L2 (1.6). g, 51.2%). ¹ H NMR (400 MHz, DMSO-d6): δ (ppm) 8.23 (d, 8H, J = 8.60 Hz), 7.61 (d, 8H, J = 8.60 Hz), ¹³ C NMR (100 MHz, DMSO-d6 ): δ (ppm) 151.1, 146.1, 131.5, 123.8 (P. Ganesan et al., J. Am. Chem . Soc . , 2005, 127, 14530-14531).

1-2-3: Tetrakis (4-aminophenyl) methane (L3, Figure 1)

In a two-necked round-bottom flask, L2 (0.5 g) and Pd / C (10%, 0.01 g) were suspended in degassed methanol (20 mL) under nitrogen. The reaction mixture was degassed five times and filled with hydrogen. The resulting reaction mixture was stirred vigorously at room temperature for 48 hours under hydrogen atmosphere. The resulting mixture was then filtered through glass frit, washed with methanol and THF and then evaporated to give pure L3 as a pale yellow solid (0.94 g, 96%). ¹ H NMR (400 MHz, DMSO-d6): δ (ppm) 6.67 (d, 8H, J = 8.60 Hz), 6.38 (d, 8H, J = 8.60 Hz), 4.85 (s, 8H), ¹³ C NMR (100 MHz, DMSO-d6): δ (ppm) 145.7, 135.9, 131.1, 112.6, 61.1 (O. Plietzsch et al., Org . Biomol . Chem. , 2009, 7, 4734-4743).

1-2- 4: 5 , 5'- Dibromo -2,2'- Bipyridine (L4, Fig. 1)

To a 2,2'-bipyridine (10 g) solution in methanol (75 mL), acetyl bromide (12 mL) was added dropwise with vigorous stirring at 0 ° C. using a disposable plastic syringe. After complete addition, the cooling bath was removed and the reaction mixture was stirred for an additional 30 minutes at room temperature. After removal of volatiles using a rotary evaporator, the residue was dried under high vacuum for 4 hours. The dried solid (3.2 g) was placed in a mortar and pestle, and 3.3 mL bromine was added slowly. The tip of the needle was allowed to dig out the dried solid. Occasionally, the mixture was mixed and ground using a mortar and spoon. After addition, the reaction mixture was triturated until a uniform orange powder was obtained and the resulting mixture was transferred to a 20 mL vial. The vial was then transferred to a stainless steel bomb to seal the steel bomb. The steel bomb was placed in an oven at 185 ° C. for 72 hours. After cooling to room temperature, the bombs were opened and the resulting reaction mixture was placed in a mortar and carefully ground. After the glass pieces were removed with forceps, the reaction mixture was ground until fine powder was obtained. The crude product was transferred to a large Erlenmeyer flask and 2M NaOH solution (120 mL), EDTA tetrasodium salt (6 g), Na ₂ SO ₃ (6 g) and CH ₂ Cl ₂ (60 mL) were added. The reaction mixture was stirred for 2 hours at room temperature, then the organic phase was separated and extracted from the aqueous solution phase five times with CH ₂ Cl ₂ . Combine organics and dry Na ₂ SO ₄ Dried over phase. After recrystallization from CH ₂ Cl ₂ , white solid L4 was obtained (1.3 g, 39%). ¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.70 (d, 2H, J = 2.0 Hz), 8.28 (d, 2H, J = 8.6 Hz), 7.94 (dd, 2H, J = 8.6 Hz, J = 2.3 Hz) (DM D'Souza et al., Nat. Protoc . 2012, 7, 2022-2028).

1-2- 5: 5 , 5'- Trimethylsilylacetylene -2,2'- Bipyridine (L5, Fig. 1)

In a two-neck round-bottom flask, L4 (0.5 g), PdCl ₂ (PPh ₃ ) ₂ (0.11 g) and CuI (0.05 g) were suspended in THF (33.5 mL) and NEt ₃ (12.5 mL). The solution was then bubbled N ₂ for 5 minutes. Trimethylsilylacetylene (0.65 mL) was added to the resulting mixture and then stirred at 60 ° C. overnight under nitrogen. After cooling, the reaction mixture was filtered, concentrated at reduced pressure, the residue was dissolved in CH ₂ Cl ₂ , extracted with an aqueous saturated solution of NH ₄ Cl followed by brine and then dried over anhydrous MgSO ₄ . After filtration, the solvent was removed under reduced pressure and purified by column chromatography (CH ₂ Cl ₂ : Hex, 1: 2 v / v) to give L5 as a pale yellow solid (0.55 g, 95.6%). ¹ H NMR (400 MHz, CDCl 3): δ (ppm) 8.72 (s, 2H), 8.36 (d, J = 8.2 Hz, 2H), 7.86 (dd, J = 8.2, 2.1 Hz, 2H), 0.28 (s , 18H), ¹³ C NMR (125 MHz, CDCl ₃ ): δ (ppm) 154.1, 152.0, 139.8, 120.5, 120.3, 101.7, 99.4, -0.2 (JF Ayme et al., Nat. Chem. 2012, 4, 15-20).

1-2-6: Tetra (4-azidophenyl) methane (1, Fig. 1 And 2)

L3 (0.4 g) was dissolved in 2N aqueous HCl (21 mL) in a 500-mL round-bottom flask and cooled to 0 ° C. A solution of NaNO ₂ (0.45 g) in H 2 O (2 mL) was then added dropwise to the cooled reaction flask with vigorous stirring. The reaction mixture was kept at 0 ° C. for 30 minutes before neutralizing with CaCO ₃ (0.65 g). To the mixture was then added a solution of NaN ₃ (0.5 g) in H 2 O (2 mL). The resulting mixture was stirred for additional 20 minutes at 0 ° C. and then filtered. The obtained solid was washed with excess H ₂ O and dried under dynamic vacuum to give 1 as a white solid (0.5 g, 95%). ¹ H NMR (400 MHz, CDCl 3): δ (ppm) 7.13 (d, 8H, J = 8.60 Hz), 6.93 (d, 8H, J = 8.60 Hz), ¹³ C NMR (125 MHz, CDCl ₃ ): δ (ppm) 142.8, 138.1, 132.0, 118.4, 63.2 (P. Pandey et al., J. Mater. Chem . , 2011, 21, 1700-1703).

1-2- 7: 5'5 - Dietinyl -2,2'- Bipyridine (2, FIGS. 1 and 2)

L5 (0.10 g) was dissolved in methanol and THF mixture (1: 1, 5 mL) and powder K ₂ CO ₃ (0.04 g) was added. The mixture was stirred at rt for 3 h and the solution was filtered and concentrated under reduced pressure. The residue was dissolved in CH ₂ Cl ₂ and extracted with brine. The organic fractions were treated with activated charcoal, dried over anhydrous MgSO ₄ and the solvent was removed under reduced pressure. After column chromatography (CH ₂ Cl ₂ : Hex, 1: 2 v / v), pure 2 was obtained as a beige solid (0.05 g, 89%). ¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 8.76 (d, J = 1.8 Hz, 2H), 8.38 (d, J = 8.2 Hz, 2H), 7.89 (dd, J = 8.2, 2.1 Hz, 2H), 3.31 (s, 2H), ¹³ C NMR (125 MHz, CDCl ₃ ): δ (ppm) 154.4, 152.2, 140.0, 120.5, 119.4, 81.6, 80.5 (JF Ayme et al., Nat. Chem . 2012 , 4, 15-20).

Example  2: Preparation of porous organic polymer (POP) and metallization method of porous organic polymer

2-1: Manufacturing of POP and POP Metallization  Way

Tetra (4-azidophenyl) methane (1 in Example 1) and 5,5'-diethynyl-2,2'-bipyridine (2 in Example 1) were in distilled DMF under N ₂ atmosphere. Binding via click reaction yielded POP-1. NiCl ₂ in distilled DMF Subsequent reaction with solution gave Ni (II) -POP-1 (FIG. 3).

2-1-1: Preparation of POP-1

Example 1 1 (200 mg), Example 1 2 (168.6 mg) and DMF (82.4 mL, 1: 1 alkyne to azide functional group ratio, to prepare a 0.02 M azide functional group solution) Was added to a 250-mL flask equipped with a magnetic stir bar and reflux condenser. The resulting mixture was then heated to 60 ° C. to make a clear solution. Then CuSO ₄ .5H ₂ O (41.2 mg, 0.1 equivalent per acetylene functional group) and sodium ascorbate (32.7 mg, 0.1 equivalent per acetylene functional group) were then added. The reaction mixture was heated at 100 ° C. for 24 hours. After cooling, the reaction mixture was filtered through a fine fritted funnel and washed successively with water (2 X 50 mL), methanol (2 X 50 mL), and THF (2 X 50 mL). The resulting brown solid was shaken in water (10 mL) for 5 hours at room temperature before filtering with a fine fritted funnel. After drying under vacuum, POP-1, a yellow to brown solid, was prepared (357 mg, 91% yield) (P. Pandey et al., J. Mater. Chem . , 2011, 21, 1700-1703).

2-1-2: POP Metallization

NiCl ₂ · 6H ₂ O (400 mg) was dissolved in distilled DMF (26 mL) and the POP powder of Example 2-1-1 (0.35 g) was added. The mixture was placed in an 80 ° C. oven for 24 hours. After cooling to room temperature, the mixture was centrifuged. The liquid was decanted and the remaining solid washed three times with fresh DMF. The solid was soaked in acetone overnight and then washed twice with acetone. After drying, a Ni (II) containing POP was prepared (˜60%), a yellow to brown solid (D. Feng et al., J. Am. Chem . Soc . 2013, 135, 17105-17110).

2-1-3: Ni Preparation of (II) -POP-3

Example 1 1 (200 mg), (5,5'-diethynyl-2,2'-bipyridyl) nickel (II) chloride (3, 272 mg in Figure 2) and DMF (82.4 mL, 1: At an alkyne to azide functional group ratio of 1, to prepare a 0.02 M azide functional solution) was added to a 250-mL flask equipped with a magnetic stir bar and a reflux condenser. The resulting mixture was then heated to 100 ° C. to make a clear solution. Then CuSO ₄ .5H ₂ O (41.12 mg, 0.2 equivalents per acetylene functional group) and sodium ascorbate (32.64 mg, 0.2 equivalents per acetylene functional group) were then added. The reaction mixture was heated at 130 ° C. for 24 hours before stopping. After cooling to room temperature, the reaction mixture was filtered through a fine fritted funnel and washed successively with water (2 X 50 mL), methanol (2 X 50 mL), and THF (2 X 50 mL). The resulting brown solid was shaken in water (10 mL) for 5 hours at room temperature before filtering with a fine fritted funnel. After drying under vacuum, a brown solid, Ni (II) -POP-3, was prepared (60 mg, 12%).

2-1-4: Ni (bpy) Cl ₂ of  Produce

NiCl ₂ · 6H ₂ O (1 g) and 2,2′-dipyridyl (0.5 g) were each dissolved in 34 mL of hot anhydrous ethanol under nitrogen. Both solutions were mixed and refluxed for 4.5 h. After cooling, the resulting precipitate was filtered off, washed with cold ethanol and dried under vacuum. Pure Ni (bpy) Cl ₂ was prepared as a light green powder (0.11 g, 12%). Anal. Calcd for Ni (bpy) Cl ₂ + H ₂ O (NiC ₁₀ H ₁₀ N ₂ Cl ₂ O): C, 39.54; H, 3. 32; N, 9.22. Found: C, 40.06; H, 3. 28; N, 9.20 (DG Yakhvarov et al., Russ. Chem . Bull. 2007, 56, 935-942; B. Brewer et al., J. Chem . Cryst. 2003, 33, 651-662).

2-2: manufactured POP and Ni  -Containing POP analysis results

Infrared (IR) and solid nuclear magnetic resonance (NMR) spectrum analysis of POP-1 clearly showed evidence of triazole formation. Azide and terminal alkyn stretch at 2114 and 3251 cm −1 parent tetra (4-azidophenyl) methane in the infrared spectra of POP-1 (FIG. 4) and Ni (II) -POP-1 (FIG. 5), respectively. It was strongly reduced compared to the (1) and 5,5'-diethynyl-2,2'-bipyridine (2) materials, indicating complete formation of triazole. In the ¹³ C-CPMAS NMR spectrum of POP-1, the peaks at 145 and 154 ppm clearly show the formation of triazole rings (FIG. 6) (P. Pandey et al., J. Mater. Chem . 2011, 21 , 1700-1703). Brunauer-Emmett-Teller (BET) analysis of POP-1 shows an average pore size of 11.6 nm and a surface area of 595 m 2 / g (FIG. 7).

Inductively coupled plasma atomic emission spectroscopy (ICP-AES) analysis of decomposed Ni (II) -POP-1 showed a Ni content of 5.0 wt%, which yielded a Ni content of 5.65 wt%. It was further confirmed by indicating energy dispersive X-ray spectroscopy (EDX) analysis (FIG. 8). BET analysis of Ni (II) -POP-1 showed an average pore size of 16.9 nm and a slight decrease in surface area (375 m ² / g) (FIG. 92), presumably the mass by metallization with NiCl ₂ . This may be due to the addition of (Table 1).

TABLE 1

Interestingly, when the polymer (POP-2) and its metalized analogs (Ni (II) -POP-2) were prepared in air, the separation yield of POP-2 drastically decreased to 61%. Although analysis by IR showed evidence of triazole formation in the same way as POP-1 (FIG. 5), N2 isotherm measurements were 320 m ² / g for POP-2, Ni (II) -POP-2 In the case of 220 m2 / g showed a relatively low BET surface area (Fig. 9 and Table 1). This decrease in yield and surface area is probably due to the decomposition of ascorbic acid in the polymerization process under an air atmosphere (KN Prasad et al., Proc . Natn . Acad . Sci . , USA 1979, 76, 829-832). As a control, a nickel-metalized material, Ni (II) -POP-3, using [5,5'-diethynyl-2,2'-bipyridyl] nickel dichloride (3) in position 2 Was prepared in very low yield (12%) and the calculated surface area was further reduced (85 m ² / g, FIG. 9 and Table 1). Lack of solubility of 3 and its oligomeric intermediates in DMF are believed to be responsible for this result.

Thermogravimetric analysis under nitrogen of a series of POPs shows that the polymers are thermally stable up to 300 ° C., while a small amount of continuous weight loss at low temperatures expands the range of thermal energy at which the polymer chains collapse. It is due to the deterioration of the irregular structure of (Fig. 10) (A. Dani et al., J. Mater. Chem . A. 2017, 5, 372-383).

Example  3: ethylene Dimerization  reaction

3-1: ethylene Dimerization  General process for reaction

In an Ar-filled glove box, Ni (II) -POP-1 (8.5 mg, 7.2 μmol Ni) was added anhydrous heptane (15 mL) and Et ₂ AlCl (1M solution in 0.5 mL hexane, note: pyrophoric liquid). Mix in a 45-mL pressure vessel (Parr Instruments Series 4714) fitted to a pressure gauge and filled with a magnetic stir bar. The pressure vessel was closed and taken out of the glove box. The reaction mixture was stirred for 10 minutes and sonicated for 10 minutes. The pressure reactor was then connected to a T-joint assembly with an ethylene gas tank and a Schlenk line. The reaction mixture was then stirred at 20 ° C. for 1 hour under constant ethylene pressure. After completion, the reactor was shut off from the ethylene source, quickly cooled in a dry ice / acetone bath (-78 ° C.) and the pressurized ethylene was released. The reactor was opened in a cold bath and aliquots (1.0 mL) of the reaction mixture were transferred to 4-mL vials located inside a dry ice / acetone bath. Excess bromine (0.5 mL, 10 mmol) was added to the sample and the vial was capped, shaken and warmed to room temperature. The resulting brown solution was washed with concentrated aqueous solution of Na ₂ S ₂ O ₃ until dry, dried over Na ₂ SO ₄ and analyzed by GC-FID (ST Madrahimov et al., ACS Catal . 2015 , 5, 6713-6718).

3-2: ethylene Dimerization  Reaction result

As in Example 3-1, the solution-phase ethylene dimerization reaction was performed with suspended Ni (II) -POP-1 at 20 ° C. with ethylene pressure in 20 bar heptanes (Table 2).

TABLE 2

Result of Ethylene Dimerization of Ni (II) -POP-1 ^a

[ ^a reaction condition: 8.5 mg of catalyst (7.2 μmol Ni), 0.5 mL of Et ₂ AlCl (1M in hexane), 15 mL of heptane, reaction time: 1 hour; ^b Due to the detection limits of GC-FID and GC-Mass, ethylene longer than C10 could not be recorded; ^c Formation of an insoluble white polymer coating coated around the Ni (II) -POP-1 particles was observed and this polymer was found to be polyethylene (PE) by DSC analysis; ^d The amount of product formed was calculated by GC-FID and GC-Mass analysis of the reaction mixture after in-situ bromination with dodecane as internal standard. Ethylene (ethylene less than the detection limit of GC, which cannot be detected by GC-FID) or a small amount of insoluble polymer coating formed around POP particles was not included in the calculation; ^e Intrinsic activity was calculated based on the ratio between the Ni content of each product and catalyst formed. The amount of butenes further converted to longer chain alkenes was not included in the IA calculations; ^The standard error for the ^f IA data was calculated by five replicate measurements on the Ni (II) -POP-1 catalyst; ^g selectivity is considered to be ethylene selectivity based on ethylene consumed for C4, C6, C8 and C10. Ethylene (ethylene less than the detection limit of GC, which cannot be detected by GC-FID) or a small amount of insoluble polymer coating formed around POP particles was not included in the calculation; ^h Items 9-11 include a series of "reuse" experiments in which the catalyst is recovered after each experiment and is strongly washed to remove the polymer coating formed around the catalyst with dichloromethane (DCM) and toluene. Finally, the catalyst is immersed in EtOH and activated under supercritical CO ₂ drying conditions before being put into a glove box for the next catalyst circuit; ^{i The} standard error for the IA data in items 9-11 was calculated by making three replicate measurements; ^j Reaction conditions: 1 hour (item 12), 2 hours (item 13). The standard error for the IA data of items 12 and 13 was calculated from three replicate measurements.]

70 eq. Et ₂ AlCl (based on Ni content) was added to all reactions to produce enzymatically activated nickel-hydrido species (FIG. 7) (D. Roy et al., Org . Biomol . Chem. 2010, 8, 1040-1051; A. Berkefeld et al., J. Am Chem . Soc . 2009, 131, 1565-1574). Since the products are very volatile, in-situ bromination was performed to stabilize the product by introducing bromine into the reactor after completion of the reaction and before GC-FID analysis.

When POP-1 alone was used as a control, no enzymatic activity for ethylene dimerization was observed, indicating that no background reaction would occur without the presence of the (bpy) Ni (II) Cl ₂ moiety. Based on these results, Ni (II) -POP-1, which has a larger surface area among a series of Ni (II) -POPs, was used exclusively for further studies on enzymatic activity on ethylene dimerization. When the reaction was performed at room temperature and 20 bar of ethylene pressure in heptane, the intrinsic activity (IA) for butenes of 800 ± 79 mol _Product / mol _Ni h (J. Canivet et al., J. Am. Chem . Soc . , 2013, 135, 4195-4198; K.-M. Song et al., Catal . Lett . , 2009, 131, 566-573; M Gonzalez et al., Faraday Discuss , 2017) and 54% Very high enzymatic activity was observed with butene (C4) selectivity of (Table 2, item 1). By reducing the substrate pressure to 15 bar, a significant decrease in both IA and C4 selectivity was observed (Table 2, item 2), and this trend of reduction of IA and C4 selectivity continued to substrate pressure of 5 bar (Table 2). , Items 3 and 4). Interestingly, when the reaction was performed at 0 ° C., the C4 selectivity was significantly increased while the IA value was slightly decreased (Table 2, items 5-8). Based on these results, enzyme activity was investigated at low reaction temperature and low concentration of ethylene. The C2 pressure was reduced from 20 to 5 bar at 0 ° C., leading to a sharp increase in C4 selectivity to 74%, while IA decreased to 299 mol _Product / mol _Ni h (Table 2, item 8).

Enzymatic activity increased with increasing reaction temperature, while selectivity increased with decreasing reaction temperature. In addition, it was confirmed that α-C4 selectivity to β-C4 increased rapidly as the reaction temperature and substrate concentration decreased (FIG. 11). When the reaction was carried out under a C2 pressure of 5 bar at 0 ° C., 83% of the C4 product was α-C4 (Table 2, item 8).

Initial attempts to test the reusability of Ni (II) -POP-1 under the same conditions as at item 1 (20 ° C., 20 bar of ethylene in heptane) have been successful due to the formation of a large amount of white insoluble polymer around the POP particles. I couldn't. Scanning electron microscopy (SEM) images of the recovered catalyst showed complete diffusion of the Ni (II) -POP-1 catalyst by web-like polymers (FIGS. 12 and 13). The differential scanning calorimeter (DSC) pattern of the solid material obtained after the reaction indicates that the majority is polyethylene (PE). The wide melting range (115-131 ° C.) shows PE with a high polydispersity index (FIG. 14). However, using the light conditions of item 8 (0 ° C., 5 bar of ethylene in heptane), in the SEM image of the post-catalyst material, the Ni (II) -POP-1 solid catalyst was partially covered and connected with polyethylene-web. (Table 2, items 8 and 9), relatively small amount of polymer formation was observed (FIG. 13). As expected, activity on the catalyst continued for four cycles of the reuse test, but the calculated IA values decreased significantly after each run (Table 2, items 9-11). The decrease in enzymatic activity after the second and third cycles will be due to the increase in the polymer layer coating on the surface of the catalyst (Table 2, items 9 and 10, FIG. 13). This polymeric coating prevents ethylene from accessing the active site, resulting in a decrease in IA. SEM images of Ni (II) -POP-1 catalyst recovered after each reuse test show material with increased amounts of polymer range (FIG. 13).

As a control, (bpy) NiCl ₂ was prepared (DG Yakhvarov et al., Russ. Chem . Bull. 2007, 56, 935-942) and the same conditions as item 1 (20 ° C., 20 bar of ethylene in heptane, item 12 And 13), the enzymatic activity was tested. As expected, very low enzymatic activity was observed, with IA values of 86 ± 2 mol _Product / mol _Ni h for 1 hour reaction time and 33 ± 1 mol _Product / mol _Ni h for 2 hour reaction time. It shows that the molecular catalyst is deactivated after less than 1 hour under ethylene oligomerization conditions.

The specific parts of the present invention have been described in detail above, and it is apparent to those skilled in the art that such specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. something to do. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (12)

A porous organic polymer having a repeating unit represented by Formula 1 below:
[Formula 1]

.
The porous organic polymer of claim 1, wherein nickel is mounted on the porous organic polymer, and the repeating unit is represented by the following Chemical Formula 2:
[Formula 2]

.
Catalyst for ethylene dimerization reaction comprising the porous organic polymer of claim 1.
Method for producing a porous organic polymer comprising the following steps:
(a) tetra (4-azophenyl) methane and 5,5'-diethynyl-2,2'-bipyridine (5,5'-diethynyl-2,2'- bipyridine) is combined by a click reaction to prepare a porous organic polymer.
The method of claim 4, further comprising the following steps:
(b) adding nickel chloride (NiCl ₂ ) to the porous organic polymer prepared in step (a) to prepare a porous organic polymer loaded with nickel.
The method of claim 4, wherein the porous organic polymer prepared in step (a) is represented by the following Chemical Formula 1 as a repeating unit:
[Formula 1]

.
The method of claim 4, wherein the step (a) uses dimethylformamide (DMF) solvent.
The method of claim 5, wherein the nickel-containing porous organic polymer prepared in step (b) is represented by the following Chemical Formula 2:
[Formula 2]

.
The method of claim 5, wherein the step (b) uses a dimethylformamide (DMF) solvent.
Ethylene dimerization reaction method using the catalyst of claim 3.
The method for ethylene dimerization according to claim 10, wherein the reaction is carried out at a temperature of -40 to 20 ° C.
The method for ethylene dimerization according to claim 10, wherein the reaction is carried out at a pressure of 5 to 20 bar.

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