KR20120060965A - Sulfonated Bisphenylsulfonyl-1,1'-Biphenyl Compounds and Their Manufacturing Methods - Google Patents
Sulfonated Bisphenylsulfonyl-1,1'-Biphenyl Compounds and Their Manufacturing Methods Download PDFInfo
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- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
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Abstract
The present invention relates to a sulfonated bis (phenylsulfonyl) -1,1'-biphenyl compound and a method for preparing the same, and more specifically, to a compound represented by the following [Formula 2] The present invention relates to a sulfonated bis (phenylsulfonyl) -1,1'-biphenyl compound represented by the following [Formula 1] by reacting with sulfuric acid followed by substitution reaction with an aqueous alkali metal solution, and a method for preparing the same.
In the above Formula 1, each of the four aromatic rings has 0 to 1 SO 3 M, and is selected at the 3,3 'or 2,2' position, wherein M is -H, -Li,- Na, -K, -Rb, -Cs or -Fr;
In [Formula 1] and [Formula 2], R is -H or halogen substituted C 1 ~ C 50 alkyl group, C 6 ~ C 50 aryl group, C 1 ~ C 50 alkyl group Selected at position 3,3 'or at position 2,2';
X is amine (-NH 2 ); amide; alkyl carboxylic acid or aryl carboxylic acid; alkyl carboxylic esters or aryl carboxylic esters; azide (N 3 ); boronic acid (-B (OH) 3 ); boronic esters; phosphate; phosphoric acid; sulfate; sulfuric acid; hydroxy (-OH); thiohydroxy (-SH); trialkyltin; tosyl; mesyl; nitro (-NO 2 ); Or a halogen group, where halogen is -F, -Cl, -Br or -I, and X is in the 4,4 'position.
Description
The present invention relates to a sulfonated bis (phenylsulfonyl) -1,1'-biphenyl compound and a method for preparing the same, and more specifically, to a compound represented by the following [Formula 2] fuming sulfuric acid, chloride sulfonic acid or The present invention relates to a sulfonated bis (phenylsulfonyl) -1,1'-biphenyl compound represented by the following [Formula 1] by reacting with sulfuric acid followed by substitution reaction with an aqueous alkali metal solution, and a method for preparing the same.
In the
In [Formula 1] and [Formula 2], R is -H or halogen substituted C 1 ~ C 50 alkyl group, C 6 ~ C 50 aryl group, C 1 ~ C 50 alkyl group Selected at position 3,3 'or at position 2,2';
X is amine (-NH 2 ); amide; alkyl carboxylic acid or aryl carboxylic acid; alkyl carboxylic esters or aryl carboxylic esters; azide (N 3 ); boronic acid (-B (OH) 3 ); boronic esters; phosphate; phosphoric acid; sulfate; sulfuric acid; hydroxy (-OH); thiohydroxy (-SH); trialkyltin; tosyl; mesyl; nitro (-NO 2 ); Or a halogen group, where halogen is -F, -Cl, -Br or -I, and X is in the 4,4 'position.
Unlike ordinary cells, fuel cells do not need to be replaced or recharged. Instead, fuel cells supply fuel such as hydrogen, methanol, or other organic substances and use oxygen or air as an oxidant to generate electrons from a redox reaction. It is a device that produces electric power by converting chemical energy into electrical energy using.
Fuel cells have the advantages of high efficiency (60% energy conversion efficiency? 60%), eco-friendly, pollution-free energy source, various fuels available, small footprint and short construction period, and power supply for mobile devices, transportation for automobiles, etc. The range of applications ranges from distributed generation to power generation for home and power businesses.
There are various types of fuel cells, but the general classification of fuel cells is largely alkaline fuel cell (AFC), phosphate fuel cell (PAFC), and molten carbonate fuel cell (MCFC) depending on the type of electrolyte used. , Solid oxide fuel cells (SOFC), polymer electrolyte fuel cells (PEMFC), and direct methanol fuel cells (DMFC).
Among these fuel cells, a polymer electrolyte membrane fuel cell and a direct methanol fuel cell are a type of direct current that directly converts chemical energy of a fuel into electrical energy by an electrochemical reaction. It is composed of a continuous composite of an electrode-membrane assembly (MEA), such as the heart of a fuel cell, and a bipolar plate that collects and supplies the generated electricity.
The electrode membrane assembly (MEA) refers to a conjugate of an electrode in which an electrochemical catalytic reaction between a fuel (hydrogen or methanol aqueous solution) and an oxidant (oxygen or air) occurs and a polymer electrolyte membrane in which hydrogen ions are transferred.
The polymer electrolyte fuel cell uses the polymer as an electrolyte, so there is no risk of corrosion or evaporation by the electrolyte, and a high current density can be obtained per unit area. Therefore, the output characteristics are much higher and the operating temperature is lower than other fuel cells. In order to use it as a portable power source for automobiles, distributed power sources (on-site) for homes and public buildings, and small power sources for electronic devices, the development of this is being actively conducted in the United States, Japan, and Europe.
Among the polymer membranes used in the electrode membrane assembly (MEA) of polymer electrolyte fuel cells, DuPont developed Nafion, a perfluorine-based hydrogen ion exchange membrane, as the ion-conducting polymer electrolyte membrane in the early 1960s. It has been. Asahi Glass Co., Ltd., in Japan, developed a Flemion having a carboxyl group instead of a sulfonic acid group as a cation exchanger, and showed high ion selectivity close to 100%, but lower than Nafion in conductivity. These perfluorine-based polymer electrolyte membranes have chemical resistance, oxidation resistance, and excellent ion conductivity, and have advantages as commercialized materials, but there are problems of environmental pollution due to high price and toxicity of intermediate products generated during manufacturing. In addition, the polymer membrane applied to the fuel cell has to play a role of preventing the migration of fuel from the anode to the cathode in addition to the role of the hydrogen ion electrolyte membrane. Therefore, the polymer electrolyte membrane used in the fuel cell should have chemical, thermal, mechanical and electrochemical stability as well as hydrogen ion conductivity as a cation exchange membrane.
In order to compensate for the above-mentioned defects of the perfluorine-based polymer membrane, a polymer electrolyte membrane in which a carboxyl group, a sulfonic acid group, or the like is introduced into an aromatic polymer has been studied. Examples include sulfonated polyaryleneether sulfones (Journal of Membrane Science, 83, 211, 1993), sulfonated polyimides (USP 6,245,881), sulfonated polyetherether ketones (JP 6-93114, USP). 5,438,082).
Among them, polyarylene ether polymers (poly (arylene ether) s) is a polymer that can be applied to many fields because of excellent thermal and chemical stability. In particular, the polyarylene ether polymer may be used as a material for forming a hydrogen ion exchange membrane (membrane) for a fuel cell, and more preferably, a sulfonated polyarylene ether polymer may be used. The stability of a fuel cell using such a sulfonated polyarylene ether polymer membrane depends on the position of sulfonic acid groups in the polymer constituting the membrane.
Aromatic sulfonation, which introduces sulfonic acid groups into aromatic rings, is a reversible reaction, and consequently, the linkage between the aromatic ring and the sulfonic acid group may be weakest at the site where the sulfonic acid group is most easily introduced. For example, in the case of sulfonation of a polyarylene ether-based polymer, ortho to an oxygen link (ether bond), since this tendency is shown at the ortho site for an oxygen link (ether bond) on an aromatic ring. The sulfonic acid groups present at the (ortho) site readily fall off the aromatic ring. Therefore, when a fuel cell adopting a polyarylene ether-based polymer sulfonated at an ortho position to an oxygen link (ether bond) on an aromatic ring as an electrolyte membrane is driven for a long time, a phenomenon in which sulfonic acid groups are separated from the polymer occurs. This may cause degradation of the electrolyte membrane.
Due to this problem, there is a need for developing a monomer for preparing a sulfonated polyarylene ether polymer of a more stable form. In particular, there is a need for a monomer in which sulfonic acid groups are introduced at a less activated position in the aromatic ring, thereby avoiding phonation of the polymer later. In addition, sulfonation is a manufacturing step required to rapidly move a large amount of hydrogen ions to exhibit high ionic conductivity. A conductive polymer having a high degree of sulfonation exhibits high ionic conductivity, but is highly resistant to water and organic solvents. It has the disadvantage of being easily melted and thermally unstable.
In general, sulfonated polyarylene ether-based polymers are prepared by polymerization by using monomers having 1 or 2 sulfonic acid groups as starting materials, or are described later on the polymers obtained by polymerizing monomers having no sulfonic acid groups. (post sulfonation). As described later, in the process of introducing the sulfonic acid group into the aromatic group, dehydration by heat or acid easily occurs, and it is difficult to control the degree of sulfonation. The polymer having a multi-substituted sulfonic acid group exhibits higher hydrogen ion conductivity than the polymer membrane having a single or double-substituted sulfonic acid group, and thus is easy to prepare a conductive polymer membrane.
The present invention can be used for the preparation of polymers by nucleophilic aromatic substitution polymerization, and each of the four aromatic rings has 0-1 sulfonated bis (phenylsulfonyl) -1,1 '. It is intended to provide a biphenyl compound and a preparation method thereof. In particular, in the polymer produced by the polymerization reaction using the sulfonated bis (phenylsulfonyl) -1,1'-biphenyl compound, less activated than the ortho site of the polymer chain. The present invention provides a bis (phenylsulfonyl) -1,1′-biphenyl compound having a multi-substituted sulfonic acid group in place and capable of adjusting the degree of sulfonation and a method of preparing the same.
An object of the present invention can be used for the preparation of polymers by nucleophilic aromatic substitution polymerization, and bis (phenyl) having 0 to 1 sulfonic acid group or alkali metal of sulfonic acid in each of four aromatic rings It is intended to provide a sulfonyl) -1,1'-biphenyl compound and a preparation method thereof.
Another object of the present invention is to provide less activated activity in the polymer prepared by the polymerization reaction using sulfonated bis (phenylsulfonyl) -1,1'-biphenyl compound compared to the ortho site of the polymer chain. The present invention provides a bis (phenylsulfonyl) -1,1'-biphenyl compound having a multi-substituted sulfonic acid group in the (activated) position and capable of controlling the degree of sulfonation and a method of preparing the same.
The present invention is a sulfonated bis (phenylsulfonyl) represented by the following [formula 1] by reacting the compound represented by the following [Formula 2] with fuming sulfuric acid, chloride sulfonic acid or sulfuric acid and then substituted with an alkali metal aqueous solution It is intended to provide a) -1,1'-biphenyl compound and a preparation method thereof.
In the
In [Formula 1] and [Formula 2], R is -H or halogen substituted C 1 ~ C 50 alkyl group, C 6 ~ C 50 aryl group, C 1 ~ C 50 alkyl group Selected at position 3,3 'or at position 2,2';
X is amine (-NH 2 ); amide; alkyl carboxylic acid or aryl carboxylic acid; alkyl carboxylic esters or aryl carboxylic esters; azide (N 3 ); boronic acid (-B (OH) 3 ); boronic esters; phosphate; phosphoric acid; sulfate; sulfuric acid; hydroxy (-OH); thiohydroxy (-SH); trialkyltin; tosyl; mesyl; nitro (-NO 2 ); Or a halogen group, where halogen is -F, -Cl, -Br or -I, and X is in the 4,4 'position.
The present invention can provide a sulfonated bis (phenylsulfonyl) -1,1'-biphenyl compound which can be used for the preparation of a polymer by nucleophilic aromatic substitution polymerization, and a method for preparing the same.
The sulfonated bis (phenylsulfonyl) -1,1'-biphenyl compound prepared according to the present invention can be used for the preparation of polymers by nucleophilic aromatic substitution polymerization, and such polymers can be used as electrode membrane assemblies in fuel cells. It can be used as a polymer film of.
1 is an FT-IR spectrum of the product prepared in Example 1. FIG.
2 is a 1 H-NMR spectrum of the product prepared in Example 1. FIG.
3 is a 13 C-NMR spectrum of the product prepared in Example 1. FIG.
4 is an FT-IR spectrum of the product prepared in Example 2. FIG.
5 is a 1 H-NMR spectrum of the product prepared in Example 2. FIG.
6 is a 13 C-NMR spectrum of the product prepared in Example 2
The present invention shows sulfonated bis (phenylsulfonyl) -1,1'-biphenyl compounds and methods for their preparation.
The present invention represents a sulfonated bis (phenylsulfonyl) -1,1'-biphenyl compound represented by the following [Formula 1] and a preparation method thereof.
Each of the four aromatic rings in the above [Formula 1] has 0-1 SO 3 M, wherein M is -H, -Li, -Na, -K, -Rb, -Cs or -Fr.
The present invention is a sulfonated bis (phenylsulfonyl) represented by the following [formula 1] by reacting the compound represented by the following [Formula 2] with fuming sulfuric acid, chloride sulfonic acid or sulfuric acid and then substituted with an alkali metal aqueous solution ) -1,1'-biphenyl compound and its preparation method are shown.
In the
In [Formula 1] and [Formula 2], R is -H or halogen substituted C 1 ~ C 50 alkyl group, C 6 ~ C 50 aryl group, C 1 ~ C 50 alkyl group Selected at position 3,3 'or at position 2,2';
X is amine (-NH 2 ); amide; alkyl carboxylic acid or aryl carboxylic acid; alkyl carboxylic esters or aryl carboxylic esters; azide (N 3 ); boronic acid (-B (OH) 3 ); boronic esters; phosphate; phosphoric acid; sulfate; sulfuric acid; hydroxy (-OH); thiohydroxy (-SH); trialkyltin; tosyl; mesyl; nitro (-NO 2 ); Or a halogen group, where halogen is -F, -Cl, -Br or -I and the position of X is the 4,4 'position.
2 to 80 moles of fuming sulfuric acid may be reacted at 10 to 200 ° C. for 2 to 60 hours with respect to 1 mole of the compound represented by [Formula 2], and then substituted with an alkali metal.
2 to 80 moles of sulfonic acid chloride may be reacted at 10 to 200 ° C. for 2 to 60 hours with respect to 1 mole of the compound represented by [Formula 2], and then substituted with an alkali metal.
2 to 100 mol of sulfuric acid is reacted for 2 to 60 hours at 10? 200 ° C. with respect to 1 mol of the compound represented by [Formula 2], and then substituted with an alkali metal.
In the above, fuming sulfuric acid may be used an aqueous solution showing a purity of 5 to 80%.
The aqueous solution which shows 10-99.99% purity of sulfonic chloride can be used above.
In the above, sulfuric acid may be used an aqueous solution showing a purity of 10 to 99.99%.
The alkali metal aqueous solution is an aqueous solution containing lithium (Li); An aqueous solution containing sodium (Na); An aqueous solution containing potassium (K); Aqueous solution containing rubidium (Rb); An aqueous solution containing cesium (Cs) or an aqueous solution containing francium (Fr) may be used, preferably an aqueous solution containing sodium (Na) or an aqueous solution containing potassium (K), and even more preferably sodium An aqueous solution containing (Na) can be used.
The aqueous solution containing lithium (Li) may be used lithium hydroxide (LiOH) aqueous solution or lithium chloride (LiCl) aqueous solution.
The aqueous solution containing sodium (Na) may be used sodium chloride (NaCl) aqueous solution or sodium hydroxide (NaOH) aqueous solution.
The aqueous solution containing potassium (K) may be used potassium hydroxide (KOH) aqueous solution or potassium chloride (KCl) aqueous solution.
The aqueous solution containing rubidium (Rb) may be an aqueous solution containing rubidium hydroxide (RbOH) aqueous solution or rubidium chloride (RbCl) of rubidium (Rb).
The aqueous solution containing cesium (Cs) in the water phase may use an aqueous solution containing cesium oxide (CsOH) or cesium chloride (CsCl) of cesium (Cs).
The aqueous solution containing francium (Fr) may be an aqueous solution containing francium hydroxide (FrOH) or francium chloride (FrCl) of francium (Fr).
Examples of the detailed synthesis of the compound represented by the above [Formula 1] of the present invention include 4,4'-bis [(4-chlorophenyl) sulfon] -1,1'-ratio which is a compound of the following [Formula 3]: The compound of [Formula 4] may be prepared by phenyl (4,4'-Bis [(4-chlorophenyl) sulfonyl] -1,1'-biphenyl) after sulfonation and substitution reaction with an aqueous alkali metal solution.
The preparation method of the compound represented by the above [Formula 4] can be represented as shown in the following [Scheme 1].
In
4,4'-bis [(4-chlorophenyl) sulfone] -1,1'-biphenyl of fuming sulfuric acid, chloride sulfonic acid or sulfuric acid by the sulfonation reaction of [Scheme 1] After the mixture was heated at 20-150 ° C for 2 to 60 hours, preferably at 80-120 ° C for 4-8 hours and then substituted with an aqueous alkali metal solution to obtain a compound represented by the above [Formula 4] Can be.
The molar ratio of fuming sulfuric acid is 2 to 80 with respect to 1 mole of 4,4'-bis [(4-chlorophenyl) sulfone] -1,1'-biphenyl in [Scheme 3] during the sulfonation reaction in [Scheme 1]. , Sulfonic acid chloride can be reacted at a molar ratio of 2 to 80, or sulfuric acid at a molar ratio of 2 to 100, respectively, wherein fuming sulfuric acid is an aqueous solution of 5 to 80% purity, an aqueous solution of 10 to 99.99% purity sulfuric acid, 10-99.99% purity aqueous solution can be used, More preferably, fuming sulfuric acid has a molar ratio of 4-8, 25-60% aqueous solution, chloride sulfonic acid has a molar ratio of 4-16 and an aqueous solution of 80-99% purity, Sulfuric acid may use an aqueous solution of 8-20 molar ratio and 80-95% purity.
After the sulfonation reaction in [Scheme 2] can be substituted by M using a conventional method. In [Scheme 2] it can be substituted with -Na using sodium chloride (NaCl) and / or sodium hydroxide (NaOH) aqueous solution.
The product prepared through the sulfonation reaction and the substitution reaction in [Scheme 1] can obtain a product almost white, and this product can be further purified through the recrystallization process. For example, the product may be recrystallized using water, aqueous sodium salt solution, aqueous potassium salt solution, water / alcohol, water / acetone, methylene chloride / alcohol and the like. Preferably, the product can be recrystallized using an aqueous solution of water / propanol, wherein the amount of aqueous solution of water: propanol is 1: 2-7 (w: w), preferably 1: 5 (w: w). The alcohol may be a lower alcohol having 1 to 10 carbon atoms, preferably methanol, ethanol or propanol.
As another example of the detailed synthesis of the compound represented by the above [Formula 1] of the present invention, 4,4'-bis [(4-chlorophenyl) sulfone] -1,1'- which is a compound of the following [Formula 3] Biphenyl (4,4'-Bis [(4-chlorophenyl) sulfonyl] -1,1'-biphenyl) may be substituted with a alkali metal aqueous solution after sulfonation to prepare a compound of [Formula 5].
The preparation method of the compound represented by the above [Formula 5] can be represented as follows [Scheme 2].
Scheme 2
In [Scheme 2], M is any one selected from -H, -Li, -Na, -K, -Rb, -Cs, or -Fr.
4,4'-bis [(4-chlorophenyl) sulfone] -1,1'-biphenyl of fuming sulfuric acid, chloride sulfonic acid or sulfuric acid by the sulfonation reaction of [Scheme 2] After the mixture was heated at 20-150 ° C. for 2 to 60 hours, preferably at 50-120 ° C. for 4 to 8 hours, and then substituted with an aqueous alkali metal solution to obtain a compound represented by the above [Formula 5]. Can be.
The molar ratio of fuming sulfuric acid is from 2 to 80 to 1 mole of 4,4'-bis [(4-chlorophenyl) sulfone] -1,1'-biphenyl in [Scheme 3] during the sulfonation reaction in [Scheme 2]. , Sulfonic acid chloride can be reacted at a molar ratio of 2 to 80, or sulfuric acid at a molar ratio of 2 to 100, respectively, wherein fuming sulfuric acid is an aqueous solution of 5 to 80% purity, an aqueous solution of 10 to 99.99% purity sulfuric acid, 10-99.99% purity aqueous solution can be used, More preferably, fuming sulfuric acid has a molar ratio of 4-8, 25-60% aqueous solution, chloride sulfonic acid has a molar ratio of 4-16 and an aqueous solution of 80-99% purity, Sulfuric acid may use an aqueous solution of 8-20 molar ratio and 80-95% purity.
After the sulfonation reaction in [Scheme 2] can be substituted by M using a conventional method. In [Scheme 2], it can be substituted with -Na using sodium chloride (NaCl) and / or sodium hydroxide (NaOH) aqueous solution.
In the above [Scheme 2], the product prepared through the sulfonation reaction and the substitution reaction can obtain a product which is almost white, and this product can be further purified through the recrystallization process. For example, the product may be recrystallized using water, aqueous sodium salt solution, aqueous potassium salt solution, water / alcohol, water / acetone, methylene chloride / alcohol and the like. Preferably, the product can be recrystallized using an aqueous solution of water / propanol, wherein the amount of aqueous solution of water: propanol is 1: 2-7 (w: w), preferably 1: 5 (w: w). The alcohol may be a lower alcohol having 1 to 10 carbon atoms, preferably methanol, ethanol or propanol.
The sulfonated bis (phenylsulfonyl) -1,1'-biphenyl compound represented by the above [Formula 1] prepared according to the production method of the present invention can be used for nucleophilic aromatic substitution polymerization. As such, the polymer prepared by using the compound represented by the above [Formula 1] is not particularly limited, and a sulfonated polyarylene ether-based polymer including a repeating unit represented by the following [Formula 6] as a non-limiting example ( sulfonated poly (arylene ether) s).
In [Formula 6] A is selected from O, S;
M is selected from -H, -Li, -Na, -K, -Rb, -Cs or -Fr;
R is the same as R 1 or selected from -H or a halogen substituted C 1 -C 50 alkyl group, C 6 -C 50 aryl group and C 1 -C 50 alkyl group;
n is 1-50,000.
Specifically, the sulfonated polyarylene ether-based polymer comprising a repeating unit represented by the above [Formula 6] is two or more in the compound and molecule represented by the above [Formula 1] prepared according to the production method of the present invention It can be prepared by reacting a compound having an electron donating group.
Compounds having two or more electron donating groups in the molecule may be simply represented by the formula A 1 -R 1 -A 2 . In this case, in Formula A 1 -R 1 -A 2 , R 1 is selected from an aryl group and an alkyl group; A 1 and A 2 are X in the above [Formula 1], or each independently an electron donating group selected from -OH and -SH. Preferably, R 1 may be selected from a phenyl group, a C 6 -C 50 aryl group and a C 1 -C 50 alkyl group, and may be a hybrid functional group thereof.
Therefore, nucleophilic aromatic substitution using a compound having two or more electron donating groups in the molecule, that is, the compound represented by Formula A 1 -R 1 -A 2 and the compound represented by [Formula 1] When the reaction is carried out, a polymerization reaction proceeds to produce a polymer. If this is expressed as a reaction scheme, it may be represented by the following [Scheme 3].
Scheme 3
In [Scheme 3], A is selected from O and S;
M is selected from -H, -Li, -Na, -K, -Rb, -Cs or -Fr;
R is the same as R 1 or selected from -H or a halogen substituted C 1 -C 50 alkyl group, C 6 -C 50 aryl group and C 1 -C 50 alkyl group;
n is 1-50,000.
Since the sulfonated bis (phenylsulfonyl) -1,1'-biphenyl compound in which the sulfonic acid group or the sulfonate already represented by the above [Scheme 3] is introduced is used in the nucleophilic aromatic substitution reaction, The polymer prepared in the reaction is sulfonated as a polymer having a sulfonic acid group or sulfonate selectively introduced at a specific site of a bis (phenylsulfonyl) -1,1'-biphenyl group and having up to four sulfonic acid groups or sulfonates. The degree can be controlled to produce a sulfonated polyarylene ether-based polymer.
However, if the polymer is prepared by nucleophilic aromatic substitution using an unsulfonated bis (phenylsulfonyl) -1,1'-biphenyl compound and then fonning is carried out later, the sulfonic acid group is identified on the aromatic ring of the polymer. It is not only introduced selectively at the position, but may also be introduced at unwanted positions on the aromatic ring. That is, in the case of later fonning of the polymer, the position selectivity of the sulfonic acid group to be introduced is inferior. In addition, it is not easy to control the degree of sulfonation.
As such, when the position selectivity of the sulfonic acid group introduced into the polymer is inferior, the sulfonic acid group may be introduced at the ortho site with respect to the oxygen link (ether bond) on the aromatic ring. As mentioned in the prior art there is a problem that can fall well in aromatic rings.
On the other hand, in the polymer prepared according to [Scheme 3], the sulfonic acid group (or sulfonate) is an oxygen link (ether bond) on an aromatic ring substituted with sulfonated bis (phenylsulfonyl) -1,1'-biphenyl. It is not introduced into the ortho site for R, but is selectively introduced into a specific site of the sulfonated bis (phenylsulfonyl) -1,1'-biphenyl group. Therefore, the sulfonic acid group (or sulfonate) in the polymer according to the present invention may be stably bound.
On the other hand, the polymer prepared as described above, in particular sulfonated polyarylene ether-based polymer may be used in the fuel cell field. Specifically, it may be used as a material of the electrolyte membrane which is one component of the membrane electrode assembly included in the fuel cell.
The method for preparing the sulfonated bis (phenylsulfonyl) -1,1'-biphenyl compound of the present invention was carried out under various conditions. In order to achieve the object of the present invention, sulfonated under the above-mentioned conditions It is preferable to provide a method for producing a bis (phenylsulfonyl) -1,1'-biphenyl compound.
Hereinafter, the present invention will be described in detail with reference to Examples and Test Examples. However, these are for the purpose of illustrating the present invention in more detail, and the scope of the present invention is not limited thereto.
≪ Example 1 >
Preparation of 4,4'-Bis (4-chloro-3-sulfonatophenylsulfonyl) biphenyl-2,2'-disulfonate (Formula 4)
3 g (5.96 mmol) 4,4'-bis [(4-chlorophenyl) sulfonyl] -1,1'-biphenyl is mixed with 10
The reaction was cooled to room temperature, poured into 100 ml of distilled water, and 2.4 g of sodium chloride was added thereto, followed by stirring. 10N sodium hydroxide (NaOH) was added thereto, neutralized and filtered under reduced pressure to obtain a product.
A water: propanol aqueous solution was added to the obtained product in an amount of 1: 5 (w: w), and then stirred at reflux for 24 hours, and then cooled to room temperature and filtered under reduced pressure. The resulting product was poured into 100 ml of acetone and stirred at reflux for 24 hours, then cooled to room temperature and filtered under reduced pressure to obtain a white precipitate product in about 70% yield (4.10 g, 4.16 mmol).
FT-IR, 1 H-NMR, 13 C-NMR and elemental analysis data were measured for the product obtained above, and the following results were obtained. The product obtained above was 4,4'-bis (4-chloro-3- It was confirmed that sulfonatophenylsulfonyl) biphenyl-2,2'-disulfonate.
FT-IR (KBr, cm -1 ) 3584, 3441, 3085, 3028, 2569, 2469, 2099, 1942, 1637, 1593, 1581, 1478, 1451, 1393, 1378, 1322, 1284, 1216, 1165, 1144, 1111, 1086, 1065, 1020, 912, 824, 810, 757, 711, 696, 676.
1 H-NMR (400 MHz, DMSO-d 6 ) δ 8.71 (2H, d, J = 1.48 Hz), 8.53 (2H, d, J = 8.28 Hz), 8.41 (2H, dd, J = 1.48, 8.32 Hz ), 8.40 (2H, d, J = 2.44 Hz), 8.12 (2H, dd, J = 8.28, 2.44 Hz), 7.73 (2H, d, J = 8.32 Hz).
13 C-NMR (100 MHz, DMSO-d 6 ) δ 146.47, 144.02, 143.91, 143.87, 139.70, 138.84, 138,52, 137.73, 137.47, 134.16, 134.10, 134.01, 133.87, 133.81, 132.53, 132.46, 130.14, 130.14 130.01, 129.75, 127.87, 125.98, 125.81, 121.85, 121.70.
Elem Anal Calcd for C 24 H 12 Cl 2 Na 4 O 16 S 6 : C, 31.62; H, 1.33; S, 21.10. Found: C, 31.94; H, 1.50; S, 20.13.
<Example 2>
Preparation of 4,4'-Bis (4-chloro-phenylsulfonyl) biphenyl-2,2'-disulfonate (Formula 5)
2g (3.97mmol) 4,4'-bis [(4-chlorophenyl) sulfonyl] -1,1'-biphenyl is mixed with 1.27ml chlorosulfuric acid (98% purity) and 5 hours at 80 ℃ The reaction was stirred by heating.
The reaction was cooled to room temperature, placed in 100 ml distilled water, and then added with 3.0 g sodium chloride and stirred. 10N sodium hydroxide was added thereto, neutralized and filtered under reduced pressure to obtain a product.
Water: propanol aqueous solution was added to the obtained product in an amount of 1: 5 (w: w), followed by filtration under reduced pressure for 24 hours.
The resulting product was poured into 100 ml of acetone, and then refluxed for 24 hours, cooled to room temperature, filtered under reduced pressure, and the obtained solid was purified by column chromatography (100% of dichloromethane) to yield a white product of about 27% (0.99 g, 4.16 mmol). Got it.
FT-IR, 1 H-NMR, 13 C-NMR and elemental analysis data of the product obtained above were measured to obtain the following results. The obtained product was 4,4'-bis (4-chloro-phenylsulfonyl). It was confirmed that biphenyl-2,2'-disulfonate.
FT-IR (KBr, cm -1 ) 3612, 3440, 3093, 3059, 2969, 2924, 2854, 1924, 1724, 1591, 1477, 1449, 1394, 1322, 1282, 1181, 1160, 1142, 1107, 1085, 1012, 914, 894, 828, 808, 756, 708, 671.
1 H-NMR (400 MHz, DMSO-d 6 ) δ 8.75 (2H, d, J = 0.92 Hz), 8.57 (2H, d, J = 5.48 Hz), 8.47 (2H, dd, J = 0.92, 5.04 Hz ), 8.15 (2H, d, J = 5.48 Hz), 7.75 (2H, d, J = 5.96 Hz).
13 C-NMR (100 MHz, DMSO-d 6 ) δ 144.05, 139.67, 138.75, 138.52, 133.95, 133.86, 130.11, 129.99, 125.76, 121.90.
Elem Anal Calcd for C 24 H 14 Cl 2 Na 2 O 10 S 4 : C, 40.74; H, 1.99; S, 18.13. Found: C, 40.95; H, 2.18; S, 17.50.
<Example 3> Preparation of Tetrasulfonated poly (arylene biphenylsulfone ether) polymer using [Scheme 3]
2.63 g (2.68 mmol) of the compound of [Formula 4] obtained in Example 1, 3.00 g (8.92 mmol) of 4,4 '-(hexafluoroisopropylidene) diphenol, 1.79 g (6.25 mmol) of bis (4-chlorophenyl) sulfone, and K 2 2.71 g (19.63 mmol) of CO 3 , 45 ml (0.2 M) of toluene and 18 ml (N, N-dimethylacetamide) of N, N-dimethylacetamide were mixed, followed by Dean-Stark. stark) and a reflux condenser, followed by heating at 150 ° C. for 6 hours and stirring. Thereafter, the temperature was raised to 190 ° C. and stirred at 100 rpm for 20 hours to obtain a reaction.
The reaction mixture was cooled to room temperature and slowly poured into 500 ml of water: methanol solution 1: 5 (w: w), stirred at 100 rpm for 20 hours at 60 ° C., cooled to room temperature, and filtered under reduced pressure to obtain a product. This recrystallization process was carried out twice.
As a product, a brown product was obtained in about 86% yield (6.38 g).
FT-IR and 1 H-NMR were measured for the product thus obtained, and the following results were obtained. The obtained product was confirmed to be a tetrasulfonated poly (arylene biphenylsulfone ether) polymer.
FT-IR (KBr, cm -1 ) 3604, 3453, 3090, 3074, 2922, 2037, 1910, 1675, 1613, 1587, 1509, 1488, 1467, 1410, 1391, 1325, 1297, 1247, 1205, 1172, 1150, 1105, 1073, 1028, 1018, 969, 953, 927, 875, 855, 830, 792, 745, 731, 717, 705.
1 H-NMR (400 MHz, DMSO-d 6 ) δ 8.56 (1.0H, s), 8.25-8.45 (4.3H, m), 8.07-8.25 (2.3H, m), 7.96 (13.8H, d, J = 7.32 Hz), 7.75-7.90 (0.85H, m), 7.47-7.70 (1.23H, m), 7.39 (17.82H, d, J = 8.28 Hz), 7.21 (28.47H, s), 7.00-7.14 ( 3.52H, m).
The average molecular weight, sulfonation degree (DS), water uptake, ion exchange capacity (IEC), and hydrogen ion conductivity (conductivity) of the electrolyte membrane were measured for the polymer obtained as described above (Polymer 51, 463 ?? 468). , (2010)), and are listed in Table 1 below.
Molecular Weight
[g / mol]
Degree
(%)
(wt.%)
Exchange capacity
(meq / g)
Table 1 shows that the prepared aromatic hydrocarbon polymer had an average molecular weight of 61330 g / mol, a degree of sulfonation of 28.3%, a moisture content of 16.5 wt.%, An ion exchange capacity of 2.29 meq / g, and a hydrogen ion conductivity of The polymer electrolyte membrane exhibited a performance of 15.2 mS / cm at room temperature and 34.0 mS / cm at 90 ° C. and used as a monomer for the production of a polymer membrane of an electrode membrane assembly used for future fuel cells. It will be useful for manufacturing.
As described above, although preferred embodiments of the present invention have been described, those skilled in the art can variously modify and change the present invention without departing from the spirit and scope of the invention as set forth in the claims below. It will be appreciated.
The present invention can provide a sulfonated bis (phenylsulfonyl) -1,1'-biphenyl compound which can be used for the preparation of a polymer by nucleophilic aromatic substitution polymerization, and a method for preparing the same. The prepared sulfonated bis (phenylsulfonyl) -1,1'-biphenyl compound can be used for the production of polymers by nucleophilic aromatic substitution polymerization, and the polymers can be used as polymer membranes of electrode membrane assemblies of fuel cells. It can contribute to the improvement of the function of the fuel cell has the industrial applicability.
Claims (4)
In the above Formula 1, each of the four aromatic rings has 0 to 1 SO 3 M, and is selected at the 3,3 'or 2,2' position, wherein M is -H, -Li,- Na, -K, -Rb, -Cs or -Fr;
In [Formula 1] and [Formula 2], R is -H or halogen substituted C 1 ~ C 50 alkyl group, C 6 ~ C 50 aryl group, C 1 ~ C 50 alkyl group Selected at position 3,3 'or at position 2,2';
X is amine (-NH 2 ); amide; alkyl carboxylic acid or aryl carboxylic acid; alkyl carboxylic esters or aryl carboxylic esters; azide (N 3 ); boronic acid (-B (OH) 3 ); boronic esters; phosphate; phosphoric acid; sulfate; sulfuric acid; hydroxy (-OH); thiohydroxy (-SH); trialkyltin; tosyl; mesyl; nitro (-NO 2 ); Or a halogen group, where halogen is -F, -Cl, -Br or -I, and X is in the 4,4 'position.
2 to 80 moles of fuming sulfuric acid are reacted at 10 to 200 ° C. for 2 to 60 hours to 1 mole of the compound represented by [Formula 2], and then an aqueous alkali metal solution is added to perform a substitution reaction; 2 to 80 moles of sulfonic acid chloride are reacted at 10 to 200 ° C. for 2 to 60 hours to 1 mole of the compound represented by [Formula 2], and then an aqueous alkali metal solution is added to perform a substitution reaction; Or 2 to 100 moles of sulfuric acid with respect to 1 mole of the compound represented by [Formula 2] at 10 to 200 ° C. for 2 to 60 hours, and then sulfonated bis (2) characterized in that a substitution reaction is performed by adding an alkali metal. Method for preparing phenylsulfonyl) -1,1'-biphenyl compound.
The alkali metal aqueous solution may be an aqueous solution containing lithium hydroxide (LiOH) aqueous solution or lithium chloride (LiCl) lithium (Li); An aqueous solution containing sodium (Na) in an aqueous sodium chloride (NaCl) solution or an aqueous sodium hydroxide (NaOH) solution; An aqueous solution containing potassium hydroxide (KOH) or potassium chloride (KCl) potassium (K); An aqueous solution comprising rubidium hydroxide (RbOH) aqueous solution or rubidium (RbCl) rubidium chloride (RbCl); An aqueous solution comprising cesium hydroxide (CsOH) aqueous solution or cesium chloride (CsCl) cesium (Cs); Or an aqueous solution containing francium hydroxide (FrOH) or an aqueous solution containing francium (Fr) of francium chloride (FrCl). 2. A method for producing a sulfonated bis (phenylsulfonyl) -1,1′-biphenyl compound .
In the above Formula 1, each of the four aromatic rings has 0 to 1 SO 3 M, and is selected at the 3,3 'or 2,2' position, wherein M is -H, -Li,- Na, -K, -Rb, -Cs or -Fr;
In [Formula 1], R is selected from -H or halogen substituted C 1 -C 50 alkyl group, C 6 -C 50 aryl group, C 1 -C 50 alkyl group, 3, Selected at 3 'position or 2,2'position;
X is amine (-NH 2 ); amide; alkyl carboxylic acid or aryl carboxylic acid; alkyl carboxylic esters or aryl carboxylic esters; azide (N 3 ); boronic acid (-B (OH) 3 ); boronic esters; phosphate; phosphoric acid; sulfate; sulfuric acid; hydroxy (-OH); thiohydroxy (-SH); trialkyltin; tosyl; mesyl; nitro (-NO 2 ); Or a halogen group, where halogen is -F, -Cl, -Br or -I, and X is in the 4,4 'position.
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Cited By (5)
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| WO2013002274A1 (en) * | 2011-06-28 | 2013-01-03 | 東レ株式会社 | Aromatic sulfonic acid derivative, sulfonic acid group-containing polymer, block copolymer, polymer electrolyte material, polymer electrolyte molded body, and solid polymer fuel cell |
| KR101428550B1 (en) * | 2012-11-20 | 2014-08-11 | 우석대학교 산학협력단 | Polymer Electrolyte Membranes prepared from 4,4-Bis(4-chlorophenylsulfone)-1,1-biphenyl Compound for Fuel Cells and Their Manufacturing Methods |
| KR101517011B1 (en) * | 2012-11-21 | 2015-05-19 | 전북대학교산학협력단 | Tetrasulfonated poly(arylene biphenyl sulfone) copolymers, Manufacturing Method thereof and Proton Exchange Membrane for Fuel Cells comprising thereof |
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| US4785072A (en) | 1985-02-13 | 1988-11-15 | Amoco Corporation | Polyaryl ether sulphones |
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| JP5278618B2 (en) * | 2011-06-28 | 2013-09-04 | 東レ株式会社 | Aromatic sulfonic acid derivatives, sulfonic acid group-containing polymers, block copolymers, polymer electrolyte materials, polymer electrolyte molded articles, and solid polymer fuel cells |
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| CN107602860A (en) * | 2017-09-28 | 2018-01-19 | 黑泰（上海）材料科技有限公司 | More sulfuryl biphenyl type sulphonation polyether sulfones and preparation method and application |
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