Solvent-linked porous covalent organic polymers and method of preparing the same
11535701 · 2022-12-27
Assignee
Inventors
Cpc classification
C08G61/02
CHEMISTRY; METALLURGY
B01J20/262
PERFORMING OPERATIONS; TRANSPORTING
C08G2261/3424
CHEMISTRY; METALLURGY
C08G2261/314
CHEMISTRY; METALLURGY
B01J20/28054
PERFORMING OPERATIONS; TRANSPORTING
International classification
C08G61/02
CHEMISTRY; METALLURGY
B01J20/26
PERFORMING OPERATIONS; TRANSPORTING
Abstract
Solvent-linked porous covalent organic polymers (COPs) and a method of preparing the same are described. The porous covalent organic polymers are linked by a solvent and are thus suitable for the transportation and storage of natural gas. A method of preparing the porous covalent organic polymers by conducting alkylation polymerization between an aromatic monomer and a chlorine-based solvent in the presence of a Lewis acid catalyst is described. Porous stretchable covalent organic polymers having pores with various sizes can be synthesized simply and quickly at room temperature and atmospheric pressure without a heating or purification step. The covalent organic polymers have very high natural gas storage capacity due to the flexible porous network structure thereof and thus are suitable for storage and transportation of natural gas and useful as a natural gas adsorbent.
Claims
1. A flexible porous covalent organic polymer represented by Formula 1, 2 or 3, which has a specific surface area of 10 to 2,500 m.sup.2/g and pore size of more than 0 and 40 nm or less and is present as a combination of microporous, mesoporous and microporous structures: ##STR00014## wherein n is an integer of 10 to 100,000 and ##STR00015## is the position where monomer repeats; ##STR00016## wherein n is an integer of 10 to 100,000 and ##STR00017## is the position where monomer repeats; and ##STR00018## wherein n is an integer of 10 to 100,000 and ##STR00019## is the position where monomer repeats.
2. A method of preparing a porous covalent organic polymer comprising preparing the porous covalent organic polymer represented by Formula 1, 2 or 3 by adding an aromatic monomer and a chlorinated solvent in presence of a Lewis acid catalyst and performing a Friedel-Crafts alkylation polymerization reaction: ##STR00020## wherein n is an integer of 10 to 100,000 and ##STR00021## is the position where monomer repeats; ##STR00022## wherein n is an integer of 10 to 100,000 and ##STR00023## is the position where monomer repeats; and ##STR00024## wherein n is an integer of 10 to 100,000 and ##STR00025## is the position where monomer repeats.
3. The method of preparing a porous covalent organic polymer of claim 2, wherein the chlorinated solvent is added in an amount of 500 to 20,000 parts by weight with respect to 100 parts by weight of the aromatic monomer.
4. The method of preparing a porous covalent organic polymer of claim 2, wherein the Lewis acid catalyst is aluminum chloride (AlCl.sub.3).
5. The method of preparing a porous covalent organic polymer of claim 2, wherein the aromatic monomer is one or more selected from the group consisting of benzene, toluene, xylene, mesitylene, phenol, aniline, pyridine, 1,2-dichlorobenzene, triphenylamine, triphenylphosphine, naphthalene, biphenyl, triphenylmethane, tetraphenylmethane, tetraphenyladamantane, diphenyl ether, triphenylbenzene, triphenylmethane and diphenylamine.
6. The method of preparing a porous covalent organic polymer of claim 2, wherein the chlorinated solvent is dichloromethane, chloroform or 1,2- dichloroethane.
7. The method of preparing a porous covalent organic polymer of claim 2, wherein the chlorinated solvent is a linker connecting the aromatic monomers.
8. The method of preparing a porous covalent organic polymer of claim 2, wherein the reaction is carried out in presence of inert gas at −25 to 125° C. for 24 to 72 hours.
9. The method of preparing a porous covalent organic polymer of claim 2, wherein the reaction is one-pot polymerization.
10. A natural gas adsorbent comprising the porous covalent organic polymer of claim 1.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.
(2) The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
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BEST MODE FOR CARRYING OUT THE INVENTION
(16) Unless defined otherwise, all technical and scientific terms used herein have the same meanings as appreciated by those skilled in the field to which the present invention pertains. In general, the nomenclature used herein is well-known in the art and is ordinarily used.
(17) In the present invention, the covalent organic polymer having a solvent as a linker, which is synthesized through Friedel-Crafts alkylation polymerization using an aromatic monomer and an excess of a chlorinated solvent in the presence of a Lewis acid catalyst such as aluminum chloride (AlCl.sub.3), has a high storage capacity due to the flexible porous network structure thereof, and is thus considered suitable for the transportation and storage of natural gas, and can be prepared in a simple and fast manner since it requires neither heating nor purification steps at room temperature and atmospheric pressure, and facilitates reduced production costs and industrial mass production since readily available and inexpensive raw materials are used for the preparation thereof.
(18) Therefore, in one aspect, the present invention is directed to a porous covalent organic polymer represented by the following Formula 1, 2 or 3:
(19) ##STR00007##
wherein n is an integer of 10 to 100,000;
(20) ##STR00008##
wherein n is an integer of 10 to 100,000; and
(21) ##STR00009##
wherein n is an integer of 10 to 100,000.
(22) In Formula 1, the repeating unit of Formula 1 is bonded to each
(23) ##STR00010##
to produce a polymer having a number of repeating units of 10 to 100,000.
(24) In Formula 2, the repeating unit of Formula 2 is bonded to each
(25) ##STR00011##
to produce a polymer having a number of repeating units of 10 to 100,000.
(26) In Formula 3, the repeating unit of Formula 3 is bonded to each
(27) ##STR00012##
to produce a polymer having a number of repeating units of 10 to 100,000.
(28) Therefore, in another aspect, the present invention is directed to a method of preparing a porous covalent organic polymer including conducting a Friedel-Crafts alkylation polymerization reaction using an aromatic monomer and a chlorinated solvent in the presence of a Lewis acid catalyst to prepare the porous covalent organic polymer represented by Formula 1, 2 or 3.
(29) In the present invention, the porous covalent organic polymer may have a specific surface area of 10 to 2,500 m.sup.2/g, preferably 15 to 1,700 m.sup.2/g.
(30) In the present invention, the porous covalent organic polymer may be present as a combination of microporous, mesoporous and macroporous structures.
(31) In the preparation method of the present invention, the chlorinated solvent may be added in an amount of 500 to 20,000 parts by weight with respect to 100 parts by weight of the aromatic monomer.
(32) Within the above content range of the chlorinated solvent, there is an effect in which the solvent-linked polymer is formed.
(33) The Lewis acid catalyst may be aluminum chloride (AlCl.sub.3), but any substance may be used without limitation as long as it can serve as a Lewis acid catalyst causing the Friedel-Crafts alkylation reaction between the aromatic monomer and the chlorinated solvent.
(34) In the present invention, the Lewis acid catalyst may include one or more selected from the group consisting of aromatic benzene, toluene, xylene, mesitylene, phenol, aniline, pyridine, 1,2-dichlorobenzene, triphenylamine, triphenylphosphine, naphthalene, biphenyl, triphenylmethane, tetraphenylmethane, tetraphenyladamantane, diphenyl ether, triphenylbenzene, triphenylmethane and diphenylamine, but is not limited thereto.
(35) In the present invention, the chlorinated solvent may be dichloromethane, chloroform or 1,2-dichloroethane, but is not limited thereto. In the present invention, the excess of chlorinated solvent can serve as both a linker for linking the aromatic monomers, and a solvent. The excess linker formed a network structure, and a highly reactive intermediate formed by the reaction between the aromatic monomer and the chlorinated solvent provides a higher-molecular-weight network polymer than a multi-substituted aromatic compound through self-polymerization.
(36) According to a specific embodiment of the present invention, organic compounds that can be used as aromatic monomers (1-15), chlorinated solvents (17-19) and Lewis acid catalysts (16) used to synthesize the covalent organic polymer are shown in
(37) The reaction scheme of the covalent organic polymer according to a specific embodiment of the present invention is as follows. The porous covalent organic polymer has a network structure and is formed through self-polymerization of highly reactive intermediates.
(38) ##STR00013##
(39) In the present invention, the reaction may be carried out in the presence of inert gas at −25 to 125° C. for 24 to 72 hours.
(40) In the present invention, the reaction may be one-pot polymerization. In the present invention, the term “one-pot polymerization” refers to a synthetic operation in which, when a target compound is synthesized through a reaction process including two or more steps, addition and reaction of reactants in a subsequent step are successively conducted in a single reactor, thereby obtaining the target compound without isolating or purifying the product (intermediate product) obtained during each step in the reaction process. In general, this method is capable of avoiding substance loss due to isolation and purification of the intermediate product and thus providing improved overall yield compared to a method including isolating and purifying each intermediate and then conducting a subsequent step, as long as the byproducts do not interfere with the reaction of the subsequent step.
(41) The present invention identified that the porous covalent organic polymer has pores with various sizes, elasticity and much higher storage capacity than the target set by the US Department of Energy (DOE), and the flexible porous network structure of the polymer is thus ideal for use in ANG systems.
(42) In another aspect, the present invention is directed to a natural gas adsorbent including the porous covalent organic polymer.
(43) In the present invention, the prepared covalent organic polymer exhibits an ultra-high surface area which can have a nonporous structure or a highly porous structure, and a BET surface area in the range from 10 to 2,500 m.sup.2/g which can have a combination of microporous, mesoporous and macroporous structures.
(44) Materials having adsorption capability at pressures of 5 bar or less cannot be used in ANG technologies. The flexible porous network structure is low porous or non-porous at low pressures, but is highly porous and has high adsorption capacity at high pressures. Unlike rigid porous materials, the flexible polymer according to the present invention is highly reusable.
(45) In a specific embodiment of the present invention, in order to analyze the ranges of the specific surface areas of the synthesized COPs 124 to 152, the Brunauer-Emett-Teller (BET) surface area was measured. The result showed that the BET surface area has a wide range from 2.5 to 1,655 m.sup.2/g (Table 1).
(46) TABLE-US-00001 TABLE 1 Solvent Monomer DCM CHCl.sub.3 DCE Benzene COP-124 COP-131 COP-150 30 m.sup.2/g 120 m.sup.2/g Toluene COP-132 COP-144 Xylene COP-133 (mixture) Diphenyl ether COP-139 Diphenyl amine COP-141 COP-151 Triphenylamine COP-142 632 m.sup.2/g 1,2- COP-143 dichlorobenzene Naphthalene COP-127 COP-134 COP-145 17 m.sup.2/g 724 m.sup.2/g Biphenyl COP-128 COP-135 COP-146 30 m.sup.2/g 710 m.sup.2/g Triphenylmethane COP-125 COP-136 COP-147 75.5 m.sup.2/g Tetraphenylmethane COP-126 COP-137 COP-148 48 m.sup.2/g 2.5 m.sup.2/g Tetraphenyladamantane COP-129 COP-138 COP-152 531 m.sup.2/g 408 m.sup.2/g 523 m.sup.2/g 1,3,5- COP-130 COP-140 COP-149 Triphenylbenzene 1665 m.sup.2/g 1216 m.sup.2/g 479 m.sup.2/g
(47) In a specific embodiment of the present invention, the result of analysis of the pore size distribution of the synthesized COPs 124 to 152 showed that the pore size was variously distributed in a wide range of 0 to 40 nm (
(48) Hereinafter, the present invention will be described in more detail with reference to examples. However, it will be obvious to those skilled in the art that these examples are provided only for illustration of the present invention and should not be construed as limiting the scope of the present invention.
EXAMPLE
Synthesis Example 1
Synthesis of COP-124
(49) 3.0 g of AlCl.sub.3 and a magnetic stirring bar were added to a 30 mL glass vial, and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 1 ml of a benzene solution in 20 ml of dichloromethane was injected into the vial, and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 2
Synthesis of COP-125
(50) 1.64 g of A1C1.sub.3, 1.00 g of triphenylmethane and a magnetic stirring bar were added to a 30 mL glass vial, and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 20 ml of dried dichloromethane was injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 3
Synthesis of COP-126
(51) 0.84 g of AlCl.sub.3, 0.50 g of triphenylmethane and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 10 ml of dried dichloromethane was injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 4
Synthesis of COP-127
(52) 3.12 g of AlCl.sub.3, 1.00 g of naphthalene and a magnetic stirring bar were added to a 30 mL glass vial, and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 20 ml of dried dichloromethane was injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 5
Synthesis of COP-128
(53) 2.60 g of AlCl.sub.3, 1.00 g of biphenyl and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 20 ml of dried dichloromethane was injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 6
Synthesis of COP-129
(54) 0.60 g of AlCl.sub.3, 0.50 g of tetraphenyladamantane and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 10 ml of dried dichloromethane was injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 7
Synthesis of COP-130
(55) 1.31 g of AlCl.sub.3, 1.00 g of 1,3,5-triphenylbenzene and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 20 ml of dried dichloromethane was injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 8
Synthesis of COP-131
(56) 3.00 g of AlCl.sub.3 and a magnetic stirring bar were added to a 30 mL glass vial, and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 1.00 mL of benzene and 20 mL of chloroform were injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 9
Synthesis of COP-132
(57) 2.52 g of AlCl.sub.3 and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 1.00 mL of toluene and 20 mL of dried chloroform were injected into the vial, and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 10
Synthesis of COP-133
(58) 2.20 g of AlCl.sub.3 and a magnetic stirring bar were added to a 30 mL glass vial, and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 1.00 mL of xylene and 20 mL of dried chloroform were injected into the vial, and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 11
Synthesis of COP-134
(59) 3.12 g of AlCl.sub.3, 1.00 g of naphthalene and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 20 ml of dried chloroform was injected into the vial, and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 12
Synthesis of COP-135
(60) 2.60 g of AlCl.sub.3, 1.00 g of biphenyl and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 20 ml of dried chloroform was injected into the vial, and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 13
Synthesis of COP-136
(61) 1.64 g of AlCl.sub.3, 1.00 g of triphenylmethane and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 20 ml of dried chloroform was injected into the vial, and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 14
Synthesis of COP-137
(62) 0.84 g of AlCl.sub.3, 0.50 g of tetraphenylmethane and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 10 ml of dried chloroform was injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 15
Synthesis of COP-138
(63) 0.60 g of AlCl.sub.3, 0.50 g of tetraphenyladamantane and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 10 ml of dried chloroform was injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 16
Synthesis of COP-139
(64) 2.90 g of AlCl.sub.3 and a magnetic stirring bar were added to a 30 mL glass vial, and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 1.00 mL of diphenyl ether and 20 ml of dried chloroform were injected into the vial, and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 17
Synthesis of COP-140
(65) 1.31 g of AlCl.sub.3, 1.00 g of 1,3,5-triphenylbenzene and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa.
(66) In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 20 ml of dried chloroform was injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 18
Synthesis of COP-141
(67) 3.15 g of AlCl.sub.3 and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 1.00 mL of diphenyl amine and 20 ml of dried chloroform were injected into the vial, and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 19
Synthesis of COP-142
(68) 2.20 g of AlCl.sub.3, 1.00 g of triphenylamine and a magnetic stirring bar were added to a 30 mL glass vial, and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 20 ml of dried chloroform was injected into the vial, and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 20
Synthesis of COP-143
(69) 1.40 g of AlCl.sub.3 and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 1.00 ml of 1,2-dichlorobenzene and 20 ml of dried chloroform were injected into the vial, and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 21
Synthesis of COP-144
(70) 2.52 g of AlCl.sub.3 and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 1.00 ml of toluene and 20 ml of dried 1,2-dichloroethane were injected into the vial, and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 22
Synthesis of COP-145
(71) 3.12 g of AlCl.sub.3, 1.00 g of naphthalene and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 20 ml of dried 1,2-dichloroethane was injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 23
Synthesis of COP-146
(72) 2.60 g of AlCl.sub.3, 1.00 g of biphenyl and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 20 ml of dried 1,2-dichloroethane was injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 24
Synthesis of COP-147
(73) 1.64 g of AlCl.sub.3, 1.00 g of triphenylmethane and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 20 ml of dried 1,2-dichloroethane was injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 25
Synthesis of COP-148
(74) 0.84 g of AlCl.sub.3, 0.50 g of triphenylmethane and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 10 ml of dried 1,2-dichloroethane was injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 26
Synthesis of COP-149
(75) 1.31 g of AlCl.sub.3, 1.00 g of 1,3,5-triphenylbenzene and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 20 ml of dried 1,2-dichloroethane was injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 27
Synthesis of COP-150
(76) 150 g of anhydrous AlCl.sub.3 was added to a 2 L beaker containing 50 ml of a benzene solution in 1L of 1,2-dichloroethane and the resulting mixture was stirred outdoors at room temperature for 40 minutes. After stirring for 40 minutes, stirring could not be conducted any further due to the formation of aggregates around the magnetic stirring bar (note: the experiment should be performed under a suitable fume hood due to the formation of HCl gas). After 18 hours, the reaction mixture was slowly quenched by the addition of a methanol ice mixture (1 L) to break up the formed aggregates (note: the water should be slowly added since the reaction between AlCl.sub.3 and methanol/water is very exothermic). After quenching, the solid was filtered, dried and ground into small particles. The product was washed twice with 1.0 L of water at 80° C. for 4 hours. The product was then stirred at 60° C. for 6 hours and washed four times with 1.0 L of ethanol. The product was then stirred at 60° C. for 6 hours and washed twice with 1.0 L of CHCl.sub.3. Finally, the solid was stirred at room temperature for 6 hours and washed with 1.0 L of dichloromethane. The solid was then dried in a vacuum at 120° C. to obtain 82 g of a yellow powder.
Synthesis Example 28
Synthesis of COP-151
(77) 3.15 g of AlCl.sub.3 and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 1.00 ml of diphenylamine and 20 ml of dried 1,2-dichloroethane were injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Synthesis Example 29
Synthesis of COP-152
(78) 0.60 g of AlCl.sub.3, 0.50 g of tetraphenyladamantane and a magnetic stirring bar were added to a 30 mL glass vial and the glass vial was then tightly sealed with a rubber septa. In order to maintain an inert medium, N.sub.2 gas was made to flow into the vial. 10 ml of dried 1,2-dichloroethane was injected into the vial and the resulting mixture was stirred for 48 hours in an N.sub.2 atmosphere (note: HCl may increase the vial pressure). After 48 hours, methanol was slowly added to quench the reaction mixture (note: the reaction between AlCl.sub.3 and methanol is highly exothermic), the solids were filtered, and the residue was washed with methanol and chloroform (10 mL each) and extracted with a mixture of 100 ml of chloroform and 100 ml of methanol using a Soxhlet extractor for 24 hours. After washing, the product was dried in a vacuum at 120° C. for 12 hours.
Example 1
Characterization of Synthesized COP
1. Structural Analysis Using Fourier-Transform Infrared Spectrum Representative structures (one of COPs linked with dichloromethane, one of
(79) COPs linked with chloroform and one of COPs linked with 1,2-dichloromethane) from each of chlorinated solvents were selected and subjected to Fourier-transform infrared spectroscopy.
(80) All structures have adsorptivity. As shown in
2. Structure Analysis Using NMR
(81) Representative structures (one of COPs linked with dichloromethane, one of COPs linked with chloroform and one of COPs linked with 1,2-dichloromethane) from each of chlorinated solvents were selected and subjected to NMR.
(82) As shown in
3. Analysis of Surface Area, Pore Size and Pore Size Volume of COPs (124-130) Linked with Dichloromethane
(83) The COPs (124-130) were degassed in a vacuum at 120° C. for 6 hours, and the surface area was measured using Argon adsorption isotherms at 87 K. The pore size distribution was calculated using a nonlocal density functional theory (NLDFT) method and a slit pore model. The results are shown in Table 2 and in
(84) TABLE-US-00002 TABLE 2 V.sub.tot (ml/g) Total List of Solvent SA.sub.BET SA.sub.Lang pore COPs Monomer linker (m.sup.2/g) (m.sup.2/g) volume COP- Benzene DCM 30 41 0.17 124 COP- Triphenylmethane DCM 75.5 92 0.45 125 COP- Tetraphenylmethane DCM 48 60 0.055 126 COP- Naphthalene DCM 17 23 0.048 127 COP- Biphenyl DCM 616 754 0.41 128 COP- Tetraphenyladamantane DCM 531 605 0.19 129 COP- 1,3,5- DCM 1665 2033 0.11 130 triphenylbenzene
4. Analysis of Surface Area, Pore Size and Pore Size Volume of COPs (131-143) linked with chloroform
(85) The COPs (131-143) were degassed in a vacuum at 120° C. for 6 hours and the surface area was measured using Argon adsorption isotherms at 87 K. The pore size distribution was calculated using a nonlocal density functional theory (NLDFT) method and a slit pore model. The results are shown in Table 3 and in
(86) TABLE-US-00003 TABLE 3 V.sub.tot (ml/g) Total List of Solvent SA.sub.BET SA.sub.Lang pore COPs Monomer linker (m.sup.2/g) (m.sup.2/g) volume COP- Benzene CHCl.sub.3 0 0 0 131 COP- Toluene CHCl.sub.3 0 0 0 132 COP- Xylene CHCl.sub.3 0 0 0 133 COP- Naphthalene CHCl.sub.3 724 822 0.35 134 COP- Biphenyl CHCl.sub.3 710 813 0.35 135 COP- Triphenylmethane CHCl.sub.3 0 0 0 136 COP- Tetraphenylmethane CHCl.sub.3 0 0 0 137 COP- Tetraphenyladamantane CHCl.sub.3 408 467 0.32 138 COP- Diphenylether CHCl.sub.3 0 0 0 139 COP- 1,3,5- CHCl.sub.3 1216 1302 0.57 140 triphenylbenzene COP- Diphenylamine CHCl.sub.3 0 0 0 141 COP- Triphenylamine CHCl.sub.3 632 715 0.33 142 COP- Dichlorobenzene CHCl.sub.3 0 0 0 143
5. Analysis of Surface Area, Pore Size And Pore Size Volume of COPs (144-152) Linked with 1,2-Dichloroethane
(87) The COPs (144-152) were degassed in a vacuum at 120° C. for 6 hours and the surface area was measured using Argon adsorption isotherms at 87 K. The pore size distribution was calculated using a nonlocal density functional theory (NLDFT) method and a slit pore model. The results are shown in Table 4 below and shown in
(88) TABLE-US-00004 TABLE 4 V.sub.tot (ml/g) Total List of Solvent SA.sub.BET SA.sub.Lang pore COPs Monomer linker (m.sup.2/g) (m.sup.2/g) volume COP- Toluene DCE 0 0 0 144 COP- Naphthalene DCE 0 0 0 145 COP- Biphenyl DCE 0 0 0 146 COP- Triphenylmethane DCE 0 0 0 147 COP- Tetraphenylmethane DCE 2.5 — 0.0032 148 COP- 1,3,5- DCE 479 571 0.36 149 Triphenylbenzene COP- Benzene DCE 120 158 0.061 150 COP- Diphenylamine DCE 0 0 0 151 COP- Tetraphenyladamantane DCE 523 600 0.47 152
6. Analysis of Methane Adsorption of COP-148 and COP-150
(89) As shown in
(90) COP-150 had a gravimetric working capacity (at 5 to 100 bar) at 273K of 0.625 g/g, which corresponds to 98% of the total capacity (0.64 g/g) (
(91) COP-148 had a gravimetric operating capacity (5 to 80 bar) at 273 K of 0.762 g/g, which corresponds to 96% of the total capacity (0.79 g/g) (
(92) The high-pressure methane adsorption isotherms of COP-150 and COP-148, respectively (
(93) This demonstrates that the covalent organic polymer of the present invention is suitable for the transportation and storage of natural gas.
(94) Although specific configurations of the present invention have been described in detail, those skilled in the art will appreciate that this description is provided to set forth preferred embodiments for illustrative purposes and should not be construed as limiting the scope of the present invention. Therefore, the substantial scope of the present invention is defined by the accompanying claims and equivalents thereto.
INDUSTRIAL APPLICABILITY
(95) The porous covalent organic polymer according to the present invention can be utilized in a variety of applications as an adsorbent of natural gas because it is suitable for transporting and storing natural gas due to elasticity (flexibility) and very high storage capacity. In addition, the method of preparing a porous covalent organic polymer is capable of preparing a porous covalent organic polymer at room temperature and atmospheric pressure through simple and fast one-pot polymerization without the necessity for a heating or purification step. The method is carried out using Lewis acid catalysts, aromatic monomers and chlorinated solvents, which are readily available and inexpensive, thus facilitating reduced production costs and industrial mass production.