KR20170072557A - Norbonene-based membranes with hydrogen selective permeability, and manufacturing method thereof - Google Patents
Norbonene-based membranes with hydrogen selective permeability, and manufacturing method thereof Download PDFInfo
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Abstract
The present invention relates to a hydrogen-permeable norbornene-based membrane comprising a polymer film produced by using a polynorbornene-based polymer satisfying the following formula (1) or (2) and a method for producing the same.
(Wherein Ar is a substituted or unsubstituted aryl group having two or more benzene rings, and n is a real number of 150 to 3200).
Description
The present invention relates to a hydrogen-permselective norbornene-based membrane with improved selective permeability of hydrogen gas and a method for producing the same.
Concerns about environmental pollution and depletion of fossil energy have increased interest in alternative energy, and expectations for hydrogen energy among various gas components are increasing.
Since hydrogen has a characteristic of spontaneous ignition or explosion when it is bonded with oxygen in the atmosphere, all safety measures must be taken to prevent leakage of hydrogen. If hydrogen is leaked, a hydrogen sensor system It is impossible to use a wide range of hydrogen without being equipped. The importance of a hydrogen safety sensor capable of detecting such hydrogen leakage is increasing.
In order to increase the hydrogen sensing efficiency and produce high purity hydrogen energy, a hydrogen separator for selectively passing hydrogen is required, and a pressure swing adsorption (PSA), a thermal swing adsorption (TSA), a getter Getter, cryogenic distillation, membrane, and the like can be used to purify hydrogen (Korean Patent Laid-Open Publication No. 10-2012-0060987). Among these, compression swing adsorption, getter, and cryogenic liquefaction distillation require low energy efficiency and complicated construction.
The hydrogen separation membrane using the compression swing adsorption is liable to be fragile due to temperature or external pressure, and thus has a problem of poor durability.
In the case of a palladium-based dense separator, a high degree of separation can be obtained, but the hydrogen permeation amount per unit area is low and the manufacturing process is complicated. In the case of using a metal support, there arises a problem of hydrogen embrittlement.
In the case of a metal thin film, there are drawbacks that the operating conditions are complicated due to hydrogen embrittlement at a high temperature and at a low temperature. In the case of a porous separator using a ceramic support, there are many difficulties in the process of systematization of the finished separator. For the multi-layered structure of the membrane, it is essential to construct the system through sealing and welding, but the technology development has not been completed so far.
Gas separation membranes using polymer membranes have various advantages such as low manufacturing cost, installation cost, high energy efficiency, small installation space and simple process control. However, polymer membranes have disadvantages in that they are difficult to apply to gas separation due to their low permeation selectivity. Therefore, it is required to improve the permeation selectivity by controlling the chemical structure of the polymer.
In relation to membranes using organic polymers in polymer membranes, Separation Science and Technology, Vol. 38, (2003) pp. 3225-3238 discloses a method for producing a polymeric material such as polysulfone, polystyrene, poly (methyl methacrylate), poly (vinylidene fluoride), poly (dimethyl siloxane) The hydrogen selectivity (H 2 / N 2 ) of the separator using polyethylene (poly (ethylene)], poly (vinyl acetate), and polystyrene co-butadiene It has a low selectivity in the range of 1 ~ 40 and in
Journal of Membrane Science 238, (2004) pp.153-163 shows that the performance of the separator using polyimide tends to decrease as H 2 / N 2 selectivity increases as the hydrogen permeability increases. In this study, we investigated the effect of the inorganic polymer on the membrane. 46, No. 5 (2009) pp. 462-466 for a polysilazane membrane. However, there is a problem that the selectivity (H 2 / N 2 ) is 4 to 5 in the selective separation of the hydrogen gas.
In order to overcome the above disadvantages, polymeric membranes utilizing polynorbornene, which has excellent mechanical, thermal and chemical resistance and relatively good separation performance, and which is produced by using petrochemical by-product DCPD (Dicyclopentadiene) To prepare a membrane. More specifically, the separation performance is improved by controlling the structure of the polymer to introduce a structure having a high free volume volume into the polynorbornene.
In order to solve the above problems, it is an object of the present invention to provide a hydrogen-permeable norbornene-based membrane having improved hydrogen permeability and hydrogen / nitrogen selectivity, and a method for producing the same.
In order to accomplish the above object, the present invention relates to a hydrogen-permselective norbornene-based membrane comprising a polymer film produced by using a polynorbornene-based polymer satisfying the following formula (1) or (2)
[Chemical Formula 1]
(2)
(Wherein Ar is a substituted or unsubstituted aryl group having two or more benzene rings, and n is a real number of 150 to 3200).
According to another aspect of the present invention, there is provided a process for preparing a norbornene-based amic acid by reacting a) a first reaction solution containing exo-norbornene-5,6-dicarboxylic acid anhydride, a polycyclic aromatic amine compound and a first organic solvent, Synthesizing a compound; b) Imidizing the norbornene amic acid compound to synthesize a norbornene-based cyclic imide monomer compound; c) polymerizing the second reaction solution comprising the norbornene cyclic imide monomer compound, the ruthenium catalyst and the second organic solvent to synthesize a polynorbornene polymer satisfying the following formula (1); And d) preparing a polymer film using the polynorbornene-based polymer. The present invention also relates to a process for producing a hydrogen-permeable norbornene-based membrane.
[Chemical Formula 1]
(Wherein Ar is a substituted or unsubstituted aryl group having two or more benzene rings, and n is a real number of 150 to 3200).
The hydrogen permselective norbornene-based membrane according to the present invention has an advantage of having excellent hydrogen gas separation performance as it has an improved hydrogen permeability and a high hydrogen / nitrogen selectivity.
1 is a photograph of a norbornene polymer film produced according to Example 2,
2 is a field emission scanning electron microscope (FE-SEM) image of a norbornene polymer film produced according to Example 2,
3 is NMR data of norbornene cyclic imide monomer compound (BP-NDI) prepared according to Synthesis Example 1,
4 is NMR data of a polynorbornene-based polymer (Poly-BP-NDI) prepared according to Synthesis Example 1,
5 is NMR data of a hydrogenated polynorbornene-based polymer (H-Poly-BP-NDI) prepared according to Synthesis Example 2,
6 is NMR data of norbornene cyclic imide monomer compound (Ph-NDI) prepared according to Comparative Synthesis Example 1,
7 is NMR data of a polynorbornene-based polymer (Poly-Ph-NDI) prepared according to Comparative Synthesis Example 1,
8 is NMR data of a hydrogenated polynorbornene-based polymer (H-Poly-Ph-NDI) prepared according to Comparative Synthesis Example 2. FIG.
BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a hydrogen-permselective norbornene-based membrane according to the present invention and a method for producing the same will be described in detail with reference to the accompanying drawings.
The following drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention is not limited to the following drawings, but may be embodied in other forms, and the following drawings may be exaggerated in order to clarify the spirit of the present invention. Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.
The term "substituted" or "substituted" as set forth below means that at least one hydrogen atom in the functional group is substituted with a halogen atom (F, Cl, Br, I), a C1- , A halogenated alkyl group of C1 to C10, a cycloalkyl group of C3 to C20, a cycloalkenyl group of C3 to C20, an aryl group of C6 to C30, a hydroxyl group, an amine group, a carboxylic acid group and an aldehyde group Or may be substituted with at least one substituent selected.
TECHNICAL FIELD The present invention relates to a hydrogen gas permeable membrane for improving the selective permeability of hydrogen gas, and more particularly, to a hydrogen permeable norbornene membrane exhibiting improved hydrogen permeability and high selective permeability through FFV (Fraction Free Volume) control .
In detail, the hydrogen-permeable norbornene-based membrane according to the present invention may include a polymer film produced by using a polynorbornene-based polymer satisfying the following formula (1) or (2).
[Chemical Formula 1]
(2)
(Wherein Ar is a substituted or unsubstituted aryl group having two or more benzene rings, and n is a real number of 150 to 3200).
With this structure, the hydrogen permeable norbornene-based membrane according to the present invention has an excellent hydrogen permeability and a high hydrogen / nitrogen selectivity, and thus has an excellent hydrogen gas separation performance.
More specifically, in the above formula (1) or (2), Ar may be a substituted or unsubstituted aryl group having 2 to 4 benzene rings, and in a non-limiting example, the aryl group may be a biphenyl group, a naphthyl group, An anthracenyl group or a pyrene group, more preferably a biphenyl group. By having such a substituent, hydrogen selectivity can be maintained while improving hydrogen permeability. On the other hand, when the benzene ring is one, that is, the phenyl group, there is a disadvantage that the hydrogen permeability can be lowered. When the number of benzene rings is five or more, it is dissolved in an organic solvent such as dimethylformamide and N-methyl-2-pyrrolidone, but the polymer stiffs and the polymer film easily breaks or cracks, There are difficult disadvantages.
In one example of the present invention, the thickness of the polymer film may be 10 to 300 탆, and more preferably 80 to 120 탆. If the thickness of the polymer film is too thin, the hydrogen permeability is good, but the hydrogen selectivity can be significantly lowered. If the thickness of the polymer film is too thick, the hydrogen selectivity is good, but the hydrogen permeability can be significantly lowered.
The number average molecular weight (Mn) of the polynorbornene-based polymer satisfying the formula (1) or (2) may be 50,000 to 1,000,000 g / mol, the mass average molecular weight may be 100,000 to 1,000,000 g / mol, (PDI, Mw / Mn) may be from 1 to 3. More preferably, the number average molecular weight (Mn) of the polynorbornene polymer satisfying the formula (1) or (2) may be 100,000 to 500,000 g / mol and the mass average molecular weight (Mw) may be 150,000 to 500,000 g / The molecular weight distribution (PDI, Mw / Mn) may be 1.2-2. By satisfying the above range, it is possible to have improved hydrogen permeability and hydrogen gas selectivity when used as a hydrogen gas permeable membrane, and also to have excellent mechanical properties and physical properties.
In one example of the present invention, the hydrogen permeable norbornene-based membrane may have a hydrogen gas permeability of 5 barrels or more, more preferably 8 barrels or more. The upper limit is not particularly limited, but may be, for example, 30 barrels or less.
In this case, the hydrogen gas permeability is an index representing the permeation rate of hydrogen to the membrane. The unit may be expressed by the following formula (1), and may be a temperature measured at 30 ° C and a value measured at 500 to 1000 torr.
[Equation 1]
Barrel = 10 -10 cm3 (STP) cm / cm2 sec cmHg
(In the formula (1), ㎝ represents the thickness of the film, ㎠ represents the area of the film, sec represents the time (sec), and ㎝Hg represents the upper pressure.
In one example of the present invention, the hydrogen selectivity (hydrogen gas permeability / nitrogen gas permeability) may be at least 40, and more preferably at least 60. The upper limit is not particularly limited, but may be, for example, 95 or less. At this time, the nitrogen gas permeability may also be a value measured in the same manner as the hydrogen gas permeability.
The hydrogen permeable norbornene-based membrane having such improved hydrogen permeability and high hydrogen selectivity can be prepared by the following method.
A process for producing a hydrogen-permselective norbornene-based membrane according to an embodiment of the present invention comprises the steps of: a) mixing a first reaction solution containing exo-norbornene-5,6-dicarboxylic acid anhydride, a polycyclic aromatic amine compound and a first organic solvent To synthesize a norbornene-based amic acid compound; b) Imidizing the norbornene amic acid compound to synthesize a norbornene-based cyclic imide monomer compound; c) polymerizing the second reaction solution comprising the norbornene cyclic imide monomer compound, the ruthenium catalyst and the second organic solvent to synthesize a polynorbornene polymer satisfying the following formula (1); And d) preparing a polymer film using the polynorbornene-based polymer.
[Chemical Formula 1]
(Wherein Ar is a substituted or unsubstituted aryl group having two or more benzene rings, and n is a real number of 150 to 3200). As described above, the hydrogen- Since the hydrogenated membrane has an enhanced hydrogen permeability and a high hydrogen / nitrogen selectivity, it can have excellent hydrogen gas separation performance.
First, a step of synthesizing a norbornene-based amic acid compound by reacting a) a first reaction solution comprising a) exo-norbornene-5,6-dicarboxylic acid anhydride, a polycyclic aromatic amine compound and a first organic solvent is performed .
Synthesis of amic acid compound using exo-norbornene-5,6-dicarboxylic acid anhydride and polycyclic aromatic amine compound and imidation can synthesize norbornene dicarboximide with polycyclic aromatic group introduced And a polymer membrane having improved hydrogen permeability and hydrogen selectivity can be produced by polymerizing the polymer.
In one example of the present invention, the polycyclic aromatic amine compound may be Ar-NH 2 , wherein Ar may be a substituted or unsubstituted aryl group having two or more benzene rings, more preferably 2 to 4 benzene Or a substituted or unsubstituted aryl group having a ring. In one non-limiting embodiment, the polycyclic aromatic amine compound may be aminobiphenyl, aminonaphthalene, aminoterphenyl, aminoanthracene or aminopyrene, and more preferably aminobiphenyl. By having such a substituent having two or more benzene rings, hydrogen selectivity can be maintained while improving hydrogen permeability. On the other hand, in the case of an amine compound having one benzene ring, that is, an aniline, there is a disadvantage that hydrogen permeability can be lowered when it is used as a gas permeable membrane. When the number of benzene rings is five or more, it is dissolved in an organic solvent such as dimethylformamide and N-methyl-2-pyrrolidone, but the polymer stiffs and the polymer film easily breaks or cracks, There are difficult disadvantages.
The polycyclic aromatic amine compound according to an example of the present invention may be added in an amount of 0.8 to 1.2 moles per mole of exo-norbornene-5,6-dicarboxylic acid anhydride, preferably exo-norbornene-5,6 -Dicarboxylic acid anhydride: polycyclic aromatic amine compound is preferably added in a molar ratio of 1: 1. In this range, it is possible to maximize the improvement of the hydrogen permeability.
The first organic solvent according to an exemplary embodiment of the present invention is not particularly limited as long as it is commonly used in the art, and examples thereof include toluene, xylene, chloroform, dichloromethane, dichloroethane, tetradecane, octadecene, chlorobenzene , Dichlorobenzene, chlorobenzoic acid, and the like can be used, and toluene can be preferably used. The amount of the exo-norbornene-5,6-dicarboxylic acid anhydride to be added is not particularly limited, but 0.1 to 5 ml of the first organic solvent per 1 mmol of exo-norbornene-5,6-dicarboxylic acid anhydride may be added, -Dicarboxylic acid anhydride in an amount of 0.2 to 1 ml per 1 mmol of the first organic solvent.
In one embodiment of the present invention, in the step a), the reaction may be carried out at a temperature of 70 to 200 ° C for 30 minutes to 24 hours, preferably at a temperature of 80 to 120 ° C for 1 to 3 hours Can be performed. The synthesis reaction proceeds effectively within the above-mentioned range of conditions, and the synthesis efficiency of the norbornene-based amic acid compound can be improved.
Next, a step of synthesizing a norbornene-based cyclic imide monomer compound can be carried out by imidating a bombardment of the norbornene-based amic acid compound.
The imidization reaction can be performed by a thermal imidization method or a chemical imidization method, and in the present invention, a norbornene-based cyclic imide monomer compound can be synthesized through a chemical imidization method. Since the thermal imidation method by the heating method generally requires a high temperature of 300 to 400 ° C. and molding is difficult after forming the polyimide, it is necessary to imidize the polyimide film on the component material to be formed, In the case where the polyimide forming site is not suitable for the high temperature process, the polyimide formation itself has difficult limitations.
That is, step b) according to an exemplary embodiment of the present invention can synthesize a norbornene cyclic imide monomer compound through a chemical imidization method. Specifically, step b) is carried out at a temperature of 70 to 200 ° C , The reaction may be carried out for 1 to 24 hours, preferably at a temperature of 70 to 110 ° C for 5 to 9 hours.
In this case, the dehydrating agent is not particularly limited as long as it is ordinarily used in the chemical imidization method. As a non-limiting example, acetic anhydride, hydroxyphenylacetic acid anhydride, sodium acetate anhydride, pyridine, picoline, isoquinoline , Trimethylamine, triethylamine, tributylamine, dimethylimidazole, and the like. As for the amount of the dehydrating agent to be added, it is preferable to add the norbornene-based amic acid compound: dehydrating agent at a molar ratio of 1: 5 to 30, more preferably 1: 10 to 25 at a molar ratio. In this range, the imidization reaction can be effectively performed. In particular, it is preferable to use acetic anhydride and sodium acetate anhydride together, wherein the molar ratio of norbornene-based amic acid compound: acetic anhydride: sodium acetate anhydride may be 1: 0.3 to 1: 3 to 20, 1: 0.3 to 0.5: 3 to 10.
Next, a step of polymerizing a second reaction solution containing c) a norbornene-based cyclic imide monomer compound, a ruthenium catalyst and a second organic solvent may be carried out to synthesize a polynorbornene-based polymer.
The ruthenium catalyst according to an embodiment of the present invention may satisfy the following formula (3).
(3)
(Ph in the above formula (3) is a phenyl group.)
In one embodiment of the present invention, the ruthenium catalyst may be added in an amount of 0.0005 to 0.01 moles, more preferably 0.001 to 0.005 moles per mole of the norbornene-based cyclic imide monomer compound. By using a ruthenium catalyst in such a range, the polymerization can be easily proceeded, and a polynorbornene polymer having a higher number average molecular weight or mass average molecular weight can be synthesized. Further, the gas permeability can be further improved by increasing entanglement phenomena, increasing chain stiffness, and decreasing packing density due to the increase in number average molecular weight or mass average molecular weight.
The second organic solvent according to an exemplary embodiment of the present invention is not particularly limited as long as it is commonly used in the art, and examples thereof include toluene, xylene, chloroform, dichloromethane, dichloroethane, tetradecane, octadecene, chlorobenzene , Dichlorobenzene, chlorobenzoic acid, and the like can be used, and dichloroethane can be preferably used. The amount of the norbornene-based cyclic imide monomer compound to be added is not particularly limited, but 0.1 to 10 ml of the second organic solvent per 1 mmol of the norbornene-based cyclic imide monomer compound may be added, preferably 1 to 5 Ml of a second organic solvent is preferably added.
In one embodiment of the present invention, in the step c), the reaction may be carried out at a temperature of 15 to 40 ° C for 30 minutes to 4 hours, preferably at a temperature of 20 to 30 ° C for 1 to 2 hours Can be performed. The polymerization reaction proceeds effectively within the above-mentioned range of conditions, and the polymerization efficiency of the polynorbornene-based polymer can be improved.
Also, a method for producing a hydrogen-selective norbornene-based membrane according to an embodiment of the present invention is characterized in that after step c), c-1) hydrogenation of a polynorbornene polymer satisfying the above formula (1) And then synthesizing a norbornene-based polymer.
(2)
(Wherein Ar is a substituted or unsubstituted aryl group having two or more benzene rings, and n is a real number of 150 to 3200).
The hydrogenation reaction is a reaction in which hydrogen is added to an unsaturated bond contained in a polynorbornene polymer satisfying the formula (1). The hydrogenation reaction can be hydrogenated using a commonly used method, Can be improved.
In one embodiment, step c-1) may be carried out in the presence of a hydrogenation catalyst at a temperature of 100 to 200 ° C for 12 to 48 hours, more preferably at a temperature of 120 to 150 ° C, The reaction may be carried out for 30 hours. In this range, the hydrogenation reaction can be effectively carried out.
In this case, the hydrogenation catalyst is toluenesulfonyl hydrazide (toluenesulfonyl hydraziade), chloro-tris (triphenylphosphine) rhodium (Ⅰ) [chlorotris (triphenylphosphine) rhodium (I)], Pd / C (palladium on carbon), PtO 2 platinum dioxide, Al / Ni (NiAl alloy), and the like, but the present invention is not limited thereto. The addition amount of the hydrogenation catalyst may be varied depending on the unsaturated bond contained in the polynorbornene polymer satisfying the formula (1). Specifically, the addition amount of the hydrogenation catalyst is preferably 1.8 to 2.5 mol per 1 mol of the repeating unit of the polynorbornene polymer satisfying the formula Of the hydrogenation catalyst may be added, more preferably 2 to 2.2 times the hydrogenation catalyst may be added. In this case, the repeating unit may satisfy the following formula (4).
[Chemical Formula 4]
(In the formula (4), Ar is a substituted or unsubstituted aryl group having at least two benzene rings.)
In one embodiment of the present invention, the step (c-1) may be a hydrogenation reaction of a third organic solvent with a polynorbornene-based polymer and a hydrogenation catalyst, And the solvent is not particularly limited as long as it is commonly used in a solvent such as dimethylformamide, toluene, hexane, cyclohexane, methylene chloride, tetrahydrofuran, methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, Dichlorobenzene, and the like can be used, and dichloroethane can be preferably used. The addition amount is not particularly limited, but it is possible to add a third organic solvent of 1 to 20 ml per 1 mmol of the recurring unit of the polynorbornene-based polymer satisfying the formula (1), preferably the polynorbornene-based polymer satisfying the formula It is preferable to add 5 to 10 ml of the second organic solvent per 1 mmol of the repeating unit.
In one example of the present invention, the number average molecular weight (Mn) of the polynorbornene-based polymer prepared from step c) or step c-1) may be 50,000 to 1,000,000 g / mol and the weight average molecular weight (Mw) To 1,000,000 g / mol, and the molecular weight distribution (PDI, Mw / Mn) may be from 1 to 3. More preferably, the number average molecular weight (Mn) of the polynorbornene polymer satisfying the formula (1) or (2) may be 100,000 to 500,000 g / mol and the mass average molecular weight (Mw) may be 150,000 to 500,000 g / The molecular weight distribution (PDI, Mw / Mn) may be 1.2-2. By satisfying the above range, it is possible to have improved hydrogen permeability and hydrogen gas selectivity when used as a hydrogen gas permeable membrane, and also to have excellent mechanical properties and physical properties.
Next, a step of producing a polymer film using the d) polynorbornene-based polymer may be performed.
Specifically, step d) may be performed by casting a polymer solution in which the polynorbornene-based polymer is dissolved in a fourth organic solvent. At this time, the casting method can be performed in a conventional manner.
More specifically, the content of the polynorbornene-based polymer in the polymer solution may be 1 to 10% by weight, and more preferably 2 to 5% by weight. The polymer film having excellent mechanical properties and physical properties within the above range can be produced. When used as a gas film, it can have improved hydrogen permeability and hydrogen selectivity.
In this case, the fourth organic solvent may be a ketone-based solvent having a boiling point of 100 ° C or higher, more preferably a ketone-based solvent having a boiling point of 100 to 300 ° C. In one nonlimiting embodiment, the ketone-based solvent may be any one or more selected from dimethylformamide, methylisobutylketone, and N-methyl-2-pyrrolidone, but is not limited thereto. Particularly preferably, dimethylformamide is used for producing a polymer film having smooth surface and no bonding. As described above, the gas permeability and hydrogen selectivity can be further improved by using a smooth surface and a defect-free polymer film as a gas permeable membrane. On the other hand, when a solvent such as chloroform having a boiling point lower than 100 ° C. is used, the polymer can be dissolved well, but the boiling point is low, and the film surface may not be smooth and the film may be wrinkled It is not good.
On the other hand, the thickness of the polymer film produced by such a method may be 10 to 300 탆, and more preferably 80 to 120 탆. If the thickness of the polymer film is too thin, the hydrogen permeability is good, but the hydrogen selectivity can be significantly lowered. If the thickness of the polymer film is too thick, the hydrogen selectivity is good, but the hydrogen permeability can be significantly lowered.
In one example of the present invention, the hydrogen permeable norbornene-based membrane may have a hydrogen gas permeability of 5 barrels or more, more preferably 8 barrels or more. The upper limit is not particularly limited, but may be, for example, 30 barrels or less.
In this case, the hydrogen gas permeability is an index representing the permeation rate of hydrogen to the membrane. The unit may be expressed by the following formula (1), and may be a temperature measured at 30 ° C and a value measured at 500 to 1000 torr.
[Equation 1]
Barrel = 10 -10 cm3 (STP) cm / cm2 sec cmHg
(In the formula (1), ㎝ represents the thickness of the film, ㎠ represents the area of the film, sec represents the time (sec), and ㎝Hg represents the upper pressure.
In one example of the present invention, the hydrogen selectivity (hydrogen gas permeability / nitrogen gas permeability) may be at least 40, and more preferably at least 60. The upper limit is not particularly limited, but may be, for example, 95 or less. At this time, the nitrogen gas permeability may also be a value measured in the same manner as the hydrogen gas permeability.
Hereinafter, the hydrogen-permselective norbornene-based membrane according to the present invention and its preparation method will be described in more detail with reference to the following examples. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.
Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, the unit of the additives not specifically described in the specification may be% by weight.
The properties of the hydrogen-permeable norbornene-based membrane prepared through the following examples and comparative examples were measured as follows.
[NMR measurement method]
300 MHz NMR (Bruker Advance spectrometer), and the solvent of the sample was CDCl 3 or DMSO-d 6 .
[Method for measuring GPC]
Using dimethylformamide (DMF) as the eluent and polymethyl methacrylate (PMMA; Mw = 2,580, 10,100, Respectively.
[Synthesis Example 1]
2 g of exo-norbornene-5,6-dicarboxilic anhydride (exo-NDA) was added to a 500 ml three-necked flask equipped with a reflux under a nitrogen atmosphere mmol) were dissolved in 10 ml of toluene. 2 g (11.8 mmol) of 4-aminobiphenyl was dissolved in 5 ml of toluene, and the solution was slowly added to the reaction vessel and stirred at 100 ° C. for about 1 hour. After lowering to about 25 캜, the precipitate was filtered and dried to obtain amic acid. A 500 ml three-necked flask equipped with a reflux condenser was charged with the resulting mixture of amic acid: sodium acetate anhydride: acetic anhydride in a molar ratio of 2: 1: 15, followed by stirring at 90 ° C for 6 hours. After lowering the temperature to about < RTI ID = 0.0 > 25 C, < / RTI > Washed several times with distilled water and recrystallized in toluene to obtain a pure norbornene cyclic imide monomer compound (BP-NDI; N-Biphenyl-exo-norbornene-5,6-dicarboximide).
Next, 1.51 g of BP-NDI and 0.0035 g (0.0048 mmol) of ruthenium catalyst as a polymerization initiator were dissolved in 9 ml of 1,2-dichloroethane in a schlenk reaction tube under a nitrogen atmosphere and stirred at room temperature for 1 hour Respectively. The reaction was quenched with a very small amount of ethyl vinyl ether and precipitated in excess methanol. The solution was dissolved in chloroform containing 5 drops of 1N HCl, purified, and precipitated again in methanol to obtain a polynorbornene-based polymer (Poly-BP-NDI; Poly (N-Biphenyl-exo-norbornene-5,6-dicarboximide)] was synthesized.
1 H NMR measurement and GPC measurement were carried out to confirm whether or not a compound was produced for each reaction. The NMR measurement results were shown in FIGS. 3 and 4, and the GPC measurement results were attached to Table 1 below.
[Synthesis Example 2]
Poly-BP-NDI was synthesized in the same manner as in Synthesis Example 1, and hydrogenation was carried out.
Specifically, 2 g of Poly-BP-NDI and 2.6 g (13.95 mmol) of p-toluenesulfonyl hydrazide were placed in a round bottom flask equipped with a reflux condenser and dissolved in 40 ml of dimethylformamide (DMF) Lt; / RTI > The reaction was allowed to proceed at 135 DEG C for 24 hours, the temperature was gradually lowered, and the precipitate was precipitated in methanol. Then, the solution was purified and dried to obtain a hydrogenated polynorbornene-based polymer [H-Poly-BP-NDI; Hydrogenated poly (N-Biphenyl-exo-norbornene-5,6-dicarboximide) was synthesized.
1 H NMR measurement and GPC measurement were performed to confirm whether or not the compound was produced. The results of NMR measurement and GPC measurement are shown in FIG. 5 and Table 1, respectively.
[Comparative Synthesis Example 1]
Synthesis was carried out in the same manner as in Synthesis Example 1 except that aniline instead of 4-aminobiphenyl was used.
Specifically, exo-norbornene-5,6-dicarboxilic anhydride (exo-NDA) was added to a 500 ml three-necked flask equipped with a reflux under a nitrogen atmosphere, 2g (12.2 mmol) was added thereto and dissolved in 10 ml of toluene. 2 g (11.8 mmol) of aniline was dissolved in 5 ml of toluene and stirred at 100 캜 for about 1 hour while gradually adding to the reaction vessel. After lowering to about 25 캜, the precipitate was filtered and dried to obtain amic acid. A 500 ml three-necked flask equipped with a reflux condenser was charged with amic acid: sodium acetate anhydride: acetic anhydride 2: 1: 15 and stirred at 90 ° C for 6 hours. After lowering the temperature to about < RTI ID = 0.0 > 25 C, < / RTI > Washed several times with distilled water and recrystallized in toluene to obtain a pure norbornene-based cyclic imide monomer compound (Ph-NDI; N-Phenyl-exo-norbornene-5,6-dicarboximide).
Next, 1.9 g of Ph-NDI and 0.0058 g (0.008 mmol) of ruthenium catalyst as a polymerization initiator were dissolved in 9 ml of 1,2-dichloroethane in a schlenk reaction tube under a nitrogen atmosphere and stirred at room temperature for 1 hour Respectively. The reaction was quenched with a very small amount of ethyl vinyl ether and precipitated in excess methanol. 5 drops of 1N HCl were dissolved in chloroform to purify and then precipitate again in methanol to obtain a polynorbornene-based polymer [Poly-Ph-NDI; Poly (N-phenyl-exo-norbornene-5,6-dicarboximide)] was synthesized.
1 H NMR measurement and GPC measurement were carried out to confirm whether or not a compound was produced for each reaction. The NMR measurement results are shown in FIGS. 6 and 7, and the GPC measurement results are shown in Table 1 below.
[Comparative Synthesis Example 2]
The synthesis of Poly-Ph-NDI was carried out in the same manner as in Comparative Synthesis Example 1, and hydrogenation was carried out.
In detail, 2 g of Poly-Ph-NDI and 3.42 g (18.39 mmol) of p-toluenesulfonyl hydrazide were placed in a round bottom flask equipped with a reflux condenser and dissolved in 40 ml of dimethylformamide and stirred. The reaction was allowed to proceed at 135 DEG C for 24 hours, the temperature was gradually lowered, and the precipitate was precipitated in methanol. Then, the solution was purified and dried to obtain a hydrogenated polynorbornene-based polymer [H-Poly-BP-NDI; Hydrogenated poly (N-Biphenyl-exo-norbornene-5,6-dicarboximide) was synthesized.
1 H NMR measurement and GPC measurement were conducted to confirm whether or not the compound was formed. The results of NMR measurement and GPC measurement are shown in FIG. 8 and Table 1, respectively.
(Mn: number average molecular weight (g / mol), Mw: mass average molecular weight (g / mol), PDI:
[Example 1]
The polynorbornene-based polymer prepared in Synthesis Example 1 was dissolved in 3% by weight of DMF and stirred for 4 hours. After stirring, it was filtered, poured into a clean glass chalet, and sufficiently dried in an oven (60 ° C). The remaining solvent was removed by drying in an oven at 80 캜 for one day to obtain a polynorbornene polymer film having a thickness of about 100 탆.
[Example 2]
All processes except that the polynorbornene polymer prepared in Synthesis Example 2 was used were carried out in the same manner as in Example 1 to obtain a polynorbornene polymer film. The transparent polynorbornene polymer film obtained through Example 2 is shown in Fig.
[Comparative Example 1]
All processes except that the polynorbornene polymer prepared in Comparative Synthesis Example 1 was used were carried out in the same manner as in Example 1 to obtain a polynorbornene polymer film.
[Comparative Example 2]
All processes except that the polynorbornene polymer prepared in Comparative Synthesis Example 2 was used were carried out in the same manner as in Example 1 to obtain a polynorbornene polymer film.
[Measurement of membrane characteristics]
The gas permeability and hydrogen selectivity of the polynorbornene polymer film prepared in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 were measured and shown in Tables 2 and 3.
The gas permeability is an exponent of the permeation rate of hydrogen and nitrogen in the polymer film, and the unit is expressed by the following equation (1). (The measurement data is at 30 ° C, 500 torr for hydrogen measurement, and 1000 torr for nitrogen measurement.)
[Equation 1]
Barrel = 10 -10 cm3 (STP) cm / cm2 sec cmHg
Cm in the equation (1) represents the thickness of the film; Cm < 2 > represents the area of the film; sec represents the time in seconds; CmHg represents the upper pressure.
The selectivity is expressed by the ratio of the gas permeability measured by hydrogen and nitrogen alone, respectively, to the same membrane. The measured gas permeability and selectivity are shown in Tables 2 and 3 below.
Fractional free volume (FFV) is the distance between polymer chains, calculated by the bondi group contribution method, and the equation is as shown below.
V is the specific volume (1 / ρ), and V 0 is calculated from van der Waals volume Vw = V 0 = 1.3V w using van Krevelen's data.
Comparative Example 1 In contrast to Example 1, the introduction of a biphenyl group increased the FFV from 0.177 to 0.190, which not only increased the permeability to hydrogen to 1.41 times, but also increased hydrogen selectivity.
In Example 2 and Comparative Example 2, the hydrogenation reaction was improved by decreasing the FFV and decreasing the permeability to hydrogen and nitrogen through hydrogenation reaction, as compared with Example 1 and Comparative Example 1. In Comparative Example 2, the decrease in permeability to hydrogen was 2.74 times and the decrease in permeability to nitrogen was 6.33 times that in Comparative Example 1. On the other hand, in Example 2, the permeability to nitrogen was 2.2 times and the decrease in permeability to nitrogen was 3.13 times Respectively. As a result, hydrogen selectivity can be improved within a range where the gas permeability is not significantly decreased.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, Various modifications and variations may be made thereto by those skilled in the art.
Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .
Claims (16)
[Chemical Formula 1]
(2)
(Wherein Ar is a substituted or unsubstituted aryl group having two or more benzene rings, and n is a real number of 150 to 3200).
Wherein the aryl group is a biphenyl group, a naphthyl group, a terphenyl, an anthracenyl group or a pyrene group.
b) Imidizing the norbornene amic acid compound to synthesize a norbornene-based cyclic imide monomer compound;
c) polymerizing the second reaction solution comprising the norbornene cyclic imide monomer compound, the ruthenium catalyst and the second organic solvent to synthesize a polynorbornene polymer satisfying the following formula (1); And
d) preparing a polymer film using the polynorbornene-based polymer;
Permeable norbornene-based membrane.
[Chemical Formula 1]
(Wherein Ar is a substituted or unsubstituted aryl group having two or more benzene rings, and n is a real number of 150 to 3200).
The production method may further comprise, after step c)
c-1) synthesizing a polynorbornene-based polymer satisfying the following formula (2) by hydrogenating a polynorbornene-based polymer satisfying the formula (1).
(2)
(Wherein Ar is a substituted or unsubstituted aryl group having two or more benzene rings, and n is a real number of 150 to 3200).
Wherein the reaction is carried out at a temperature of 100 to 200 DEG C for 12 to 48 hours in the step (c-1), in the presence of a hydrogenation catalyst.
Wherein the hydrogenation catalyst is toluene sulfonyl hydrazide, chlorotris (triphenylphosphine) rhodium (I), Pd / C, PtO 2 or Al / Ni.
Wherein the polycyclic aromatic amine compound is aminobiphenyl, aminonaphthalene, aminoterphenyl, aminoanthracene or aminopyrene.
Wherein the polycyclic aromatic amine compound is added in an amount of 0.8 to 1.2 moles per mole of exo-norbornene-5,6-dicarboxylic acid anhydride.
Wherein the step a) is carried out at a temperature of 70 to 200 ° C for 30 minutes to 24 hours.
Wherein the reaction is carried out at a temperature of 70 to 200 DEG C for 1 to 24 hours under the addition of a dehydrating agent in the step b).
Wherein the dehydrating agent is selected from the group consisting of acetic anhydride, hydroxyphenylacetic anhydride, sodium acetate anhydride, pyridine, picoline, isoquinoline, trimethylamine, triethylamine, tributylamine and dimethylimidazole A method for producing a permeable norbornene-based membrane.
In the step c), the ruthenium catalyst is added in an amount of 0.0005 to 0.01 moles per mole of the norbornene-based cyclic imide monomer compound.
Wherein the step c) is carried out at a temperature of 15 to 40 DEG C for 30 minutes to 4 hours.
Wherein the step d) is carried out by casting a solution of the polymer in which the polynorbornene-based polymer is dissolved in a fourth organic solvent.
Wherein the fourth organic solvent is a ketone-based solvent having a boiling point of 100 ° C or higher.
Wherein the ketone solvent is at least one selected from the group consisting of dimethylformamide, methyl isobutyl ketone and N-methyl-2-pyrrolidone.
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