KR101657270B1 - Sulfone based compound containing hydrocarbon core and method for preparing the same - Google Patents
Sulfone based compound containing hydrocarbon core and method for preparing the same Download PDFInfo
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- KR101657270B1 KR101657270B1 KR1020130040127A KR20130040127A KR101657270B1 KR 101657270 B1 KR101657270 B1 KR 101657270B1 KR 1020130040127 A KR1020130040127 A KR 1020130040127A KR 20130040127 A KR20130040127 A KR 20130040127A KR 101657270 B1 KR101657270 B1 KR 101657270B1
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Abstract
The sulphonic compound of the present invention is represented by the following formula 1. The sulphonic compound is a compound containing a hydrocarbon core and an ether sulfone unit and can be modified into a hydrocarbon core to improve the rigidity, It is possible to improve or impart physical properties such as chemical resistance.
[Chemical Formula 1]
Wherein R 1 and R 2 are each independently a sulfonyl (-SO 3 H) group or a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, X is a halogen atom, and Z is a substituted or unsubstituted A and b are each independently an integer of 0 to 4, m is an integer of 1 or more, and n is an integer of 2 to 10. The term " a "
Description
The present invention relates to a sulfone-based compound and a method for producing the same. More specifically, the present invention relates to a compound containing a hydrocarbon core and an ether sulfone unit, which comprises a hydrocarbon core capable of modifying a hydrocarbon core to improve or impart properties such as rigidity, flexibility, solubility and chemical resistance of a sulfonic compound And a method for producing the same.
Polyethersulfone (PES) is super engineering plastics with high heat resistance, such as polyether etherketone (PEEK), and is widely used as separation membrane, medical device material, automotive parts material, aircraft parts material, It is widely used for special purposes such as containers. In addition, the demand for secondary fuel cell membrane and general membrane separator business, which have recently emerged as a new alternative energy field, is increasing, but it is used for limited use due to limitations of physical properties. In order to overcome this problem, it is possible to impart or improve insufficient physical properties through compounding, blending or the like, but it is impossible to solve the fundamental problem in a temporary manner. Accordingly, the present invention proposes a method of adjusting the center unit of the main chain by a property change method of a sulfonic compound.
When aromatic compounds such as bezene, biphenyl, and aromatic compounds having a fused aromatic ring are used as the hydrocarbon core (core molecule) of the polymer main chain, By acting as an anchor in the chain and requiring a lot of energy to rotate, it reduces the rotational motion of the polymer chains (Acs. Macro. Letts, 2012, 1, 194-197). The main chain of polymer with slowed motion increases the intramolecular interaction and intermolecular interaction of the polymer, thereby increasing the rigidity of the polymer main chain. As a result, , The rigidity, heat resistance and glass transition temperature (Tg) of the whole polymer.
Also, when the aliphatic compound such as an alkyl group, which is not an aromatic compound, is located at the center of the main chain of the polymer, the rotational motion in the polymer or the polymer becomes relatively active, and the polymer is twisted to have a random chain structure. This form can minimize the intramolecular interaction and the intermolecular interaction of the polymer, and as a result, the physical properties related to the solubility and flexibility of the polymer can be increased.
Thus, it is necessary to study sulfone-based compounds capable of manifesting various physical properties by including various hydrocarbon cores and methods for producing the same.
An object of the present invention is to provide a sulfone-based compound capable of modifying a hydrocarbon core to impart physical properties such as rigidity, flexibility, solubility and chemical resistance, as a compound containing a hydrocarbon core and an ether sulfone unit.
Another object of the present invention is to provide a process for preparing the above sulfonic compound.
The above and other objects of the present invention can be achieved by the present invention described below.
One aspect of the present invention relates to sulfone-based compounds. The sulfone-based compound may be represented by the following Formula 1:
[Chemical Formula 1]
Wherein R 1 and R 2 are each independently a sulfonyl (-SO 3 H) group or a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, X is a halogen atom, and Z is a substituted or unsubstituted A and b are each independently an integer of 0 to 4, m is an integer of 1 or more, and n is an integer of 2 to 10. The term " a "
In an embodiment, Z may comprise a substituted or unsubstituted cyclic or aromatic hydrocarbon group having 5 to 50 carbon atoms.
In an embodiment, Z is
In an embodiment, the sulfonic compound represented by the formula (1) may be a high molecular weight sulfonic compound having m of 4 or more.
In an embodiment, the sulfonic compound represented by Formula 1 may be in the form of a dendrimer or star polymer having n of 3 or more.
Another aspect of the present invention relates to a method for producing the above sulfonic compound. The production method comprises reacting a sulfone compound represented by the following formula (2) and a compound represented by the following formula (3).
(2)
(3)
In the general formulas (2) and (3), R 1 , R 2 , X, a, b, m and n are as defined in Formula 1, and X 2 may be a good leaving group.
In an embodiment, the sulfone compound represented by Formula 2 may be prepared by reacting a dihydroxydiphenyl sulfone compound represented by Formula 4 and an alkali metal compound to produce dihydroxydiphenylsulfonate; And reacting the dihydroxydiphenylsulfone salt and a dihalogenenediphenyl sulfone compound represented by the following general formula (5) to prepare a sulfone compound represented by the general formula (2):
[Chemical Formula 4]
[Chemical Formula 5]
Wherein R 1 , R 2 , X, a and b are as defined in the above formula (1).
In an embodiment, the sulfone compound represented by Formula 2 may have m of 4 or more.
The present invention relates to a compound containing a hydrocarbon core and an ether sulfone unit and capable of modifying a hydrocarbon core to impart properties such as rigidity, flexibility, solubility and chemical resistance, and a method for producing the same, .
1 is a 1 H-NMR spectrum of a sulfonic compound prepared according to Example 1 of the present invention.
2 is a 1 H-NMR spectrum of an H region of an aromatic region of a sulfonic compound prepared according to Example 1 of the present invention.
3 is a 1 H-NMR spectrum of a sulfonic compound prepared according to Example 2 of the present invention.
4 is a 1 H-NMR spectrum of a sulfonic compound prepared according to Example 3 of the present invention.
5 is a 1 H-NMR spectrum of a sulfone compound prepared according to Comparative Example 1 of the present invention.
Hereinafter, the present invention will be described in detail.
The sulfone compound according to the present invention is a compound containing a hydrocarbon core (core molecule and ether sulfone unit) and can be represented by the following formula (1).
[Chemical Formula 1]
Wherein R 1 and R 2 are each independently a halogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and X is a halogen atom, for example, a chlorine atom (C1), fluorine atom (F), bromine atom (Br), and iodine atom (I), preferably chlorine atom (Cl), and Z is a hydrocarbon core, substituted or unsubstituted C1- And a and b are each independently an integer of 0 to 4, and m is an integer of 1 or more, for example, an integer of 2 or more, preferably an integer of 4 to 50, Is an integer of 6 to 30, and n is an integer of 2 to 10, preferably an integer of 2 to 6, more preferably an integer of 2 to 4.
In the specification of the present invention, the term "ether sulfone unit" means a unit including a sulfone group (-SO 2 -) and an ether group (-O-) in a chain, such as, for example, do.
Further, in the specification of the present invention, the term "hydrocarbon group" means a linear, branched or cyclic saturated or unsaturated hydrocarbon group. "Substitution" means that a hydrogen atom is replaced by a hetero atom such as an oxygen atom (O), a sulfur atom (S) or a nitrogen atom (N), an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group having 6 to 10 carbon atoms, And the like. The substituent may preferably be an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
In one embodiment, Z may comprise a substituted or unsubstituted cyclic or aromatic hydrocarbon group having 5 to 50, preferably 6 to 40 carbon atoms. In this case, it is possible to impart stiffness and enhanced heat resistance to the sulfone-based compound.
When Z contains a linear hydrocarbon group, the flexibility, solubility and the like of the sulfonic compound can be improved.
Specific examples of Z include
In an embodiment, the sulfonic compound represented by the formula (1) may be a high molecular weight sulfonic compound having m of 4 or more.
The sulfonic compound of the present invention may be substituted with various substituents at the terminal halogen group (X in the formula (1)), or when n is 3 or more It may also have a dendrimer or star polymer form. Such substitutions and modifications can be easily carried out by a person having ordinary skill in the art to which the present invention belongs.
The sulfone compound may be prepared according to the process for preparing a sulfonic compound according to the present invention. The method for producing a sulfonic compound of the present invention comprises reacting a sulfone compound represented by the following formula (2) and a compound represented by the following formula (3).
(2)
(3)
In Formula 2 and 3, R1, R2, are as defined in X, a, b, m and n have the general formula 1, X 2 is, for a good leaving group (good leaving group), for example, chlorine (Cl) , A halogen atom such as a fluorine atom (F), a bromine atom (Br) or an iodine atom (I), a mesylate group, a tosylate group or an imidazole group.
The compound represented by the general formula (3) includes Z (hydrocarbon core) having two or more hydrocarbon groups, and examples thereof include 1,4-dibromobutane, 1,2-dibromoethylbenzene, Di-p-xylene, 1,1-carbonyldiimidazole, and the like.
The reaction may be carried out by reacting the sulfone compound represented by Formula 2 and the compound represented by Formula 3 in an organic solvent. Here, the content ratio (molar ratio) of the compound represented by Formula 2 and the compound represented by Formula 3 may be, for example, 1: 2 to 10, preferably 1: 2 to 6, More preferably from 1: 2 to 4, and most preferably from 1: 2 to 2.2. The degree of substitution and the reaction yield are excellent in the above range.
Examples of the organic solvent used in the reaction include sulfoxide-based solvents such as dimethylsulfoxide and hexamethylene sulfoxide; amide-based solvents such as N, N-dimethylformamide and N, N-dimethylacetamide; Piperidone solvents such as pyrrolidone and N-methyl-2-piperidone, 2-imidazolidinone solvents such as 1,3-dimethyl-2-imidazolidinone, sulfolane solvents such as sulfolane , A mixture of two or more of them, and the like, preferably N-methyl-2-pyrrolidone. The content of the organic solvent may be 100 to 200 parts by weight, preferably 130 to 150 parts by weight, based on 100 parts by weight of the total reactants (formulas (2) and (3)).
The reaction may be carried out, if necessary, by further adding a conventional additive such as a catalyst. The catalyst may be triethylamine (NEt 3 ) or the like. The amount of the catalyst to be used may be, for example, 0.1 to 1 part by weight based on 100 parts by weight of the total reactants (Formulas 2 and 3) .
The reaction temperature may be, for example, 100 to 170 ° C, preferably 110 to 130 ° C, and the reaction time may be, for example, 1 to 16 hours, preferably 2 to 5 hours. The degree of substitution and the reaction yield are excellent in the above range.
The sulfone compound represented by the formula (2) used in the present invention may be a commercially available polyether sulfone compound or a monomer thereof. For example, a dihydroxydiphenyl sulfone compound represented by the following formula (4) and an alkali metal compound To produce a dihydroxydiphenylsulfonate salt; And a step of reacting the dihydroxydiphenylsulfone salt and a dihalogenenediphenyl sulfone compound represented by the following formula (5) to prepare a sulfone compound represented by the formula (2) Polyethersulfone) can be used.
[Chemical Formula 4]
[Chemical Formula 5]
Wherein R 1 , R 2 , X, a and b are as defined in the above formula (1).
The alkali metal compound is added to prepare the metal salt of the dihydroxydiphenyl sulfone compound in order to increase the low reactivity (nucleophilic property) of the dihydroxydiphenyl sulfone compound. For example, an alkali metal carbonate , Alkali metal hydroxides, alkali metal hydrides, alkali metal alkoxides and the like can be used, and preferably alkali metal carbonates such as potassium carbonate and sodium carbonate can be used. More preferably, alkali metal salt anhydrides such as potassium carbonate anhydride and sodium carbonate anhydride can be used.
The alkali metal compound may be used in an amount of 200 to 300 moles, preferably 210 to 220 moles per 100 moles of the dihydroxydiphenyl sulfone compound. Dihydroxydiphenylsulfonate can be prepared in the above range.
The dihydroxydiphenylsulfone salt may be prepared in a mixed solvent of an aprotic organic solvent and an azeotropic solvent. Examples of the aprotic organic solvent include conventional aprotic organic solvents used in polyethersulfone polymerization. Examples thereof include sulfoxide-based solvents such as dimethyl sulfoxide and hexamethylene sulfoxide; N, N- Amide solvents such as dimethylformamide and N, N-dimethylacetamide, piperidone solvents such as N-methyl-2-pyrrolidone and N-methyl-2-piperidone, Imidazolidinone solvents such as imidazolidinone, sulfolane solvents such as sulfolane, mixtures of two or more thereof, and the like, preferably N-methyl-2-pyrrolidone have.
In addition, a small amount of water at the time of polymerization, water coming from the outside during the reaction, and water generated at the time of polymerization inhibit the progress of the polymerization. Therefore, it is compatible with an aprotic polar solvent for the purpose of separating water in these reaction systems, An azeotropic solvent is used which forms an azeotropic mixture with water at a pressure of 0.101 MPa. Examples of such an azeotropic solvent include, but are not limited to, hydrocarbon solvents such as benzene, chlorobenzene and toluene, ether solvents such as diisopropyl ether, ethylbutyl ether and dioxane, acetyl acetone, methyl ethyl ketone and the like Ketones, alcohols such as ethanol, isopropanol, n-propanol, isobutyl alcohol, hexanol and benzyl alcohol, ester solvents such as ethyl acetate, methyl acetate, butyl acetate, butyl butyrate and methyl benzoate, , Carboxylic acid solvents such as acetic acid, propionic acid, valeric acid and benzoic acid, halogenated solvents such as chloroform, bromoform, 1,2-dichloroethane, 1,2-dichloroethane, carbon tetrachloride, chlorobenzene and hexafluoroisopropanol , An amine-based solvent such as ethylenediamine, aniline, pyridine, methylpyridine and the like, preferably a hydrocarbon, more preferably It may be used benzene, chlorobenzene, toluene, and one or more selected from, may most preferably be toluene.
The molar ratio of the total monomers (the dihydroxydiphenyl sulfone compound and the dihalogenenediphenyl sulfone compound) to the aprotic organic solvent is 1: 0.8 to 1.5, preferably 1: 1.0 to 1.3. Within the above range, desired linear polyethersulfone can be obtained, and the resulting polymer can be easily washed.
The amount of the azeotropic solvent to be used is not particularly limited as long as it is an amount capable of removing moisture in the system. For example, 0.01 to 10 parts by weight, preferably 0.02 to 5 parts by weight, based on 100 parts by weight of the total monomers have.
The sulfone compound represented by the formula (2) used in the present invention has an H signal (7.79 to 7.76 ppm) adjacent to the halogen group of the halogenophenyl group when measured using a 300 MHz 1 H-NMR apparatus in a solvent of methylsulfoxide (DMSO) Signal) adjacent to the hydroxyl group of the hydroxyphenyl group and an H signal (6.94 to 6.91 ppm signal) adjacent to the hydroxy group of the hydroxyphenyl group is 40 to 60:40 to 60, for example, 50:50 (see FIG. 5). As described above, the sulfone compound has H signal (peak) derived from terminal hydroxyl group (-OH) at 10.4 to 10.8 ppm in 1 H-NMR measurement. That is, the linear polyethersulfone of the present invention is a substance in which H signal near 10.4 to 10.8 ppm exists, which is derived from terminal hydroxyl group (-OH) appearing in bisphenol S, and further end group control is possible.
Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.
The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.
Example
Example One
5 g (20 mmol) of bisphenol S, 6.08 g (44 mmol) of potassium carbonate (K 2 CO 3 ), and 0.58 g (44 mmol) of potassium carbonate were added to a 250 ml round bottom flask equipped with a condenser and a Dean- 35 ml of N-methyl-2-pyrrolidone (NMP) and 30 ml of toluene were added and the mixture was heated at a temperature of 180 to 200 ° C under a nitrogen (N 2 ) atmosphere for 2.5 hours , And the resulting water was removed by azeotropic distillation with toluene. Next, the temperature was lowered to 150 캜, 5.743 g (20 mmol) of dichlorodiphenylsulfone was added, and the reaction was carried out at a temperature of 220 캜 for 2.5 to 3 hours. After the reaction, 0.596 ml (5 mmol) of 1,4-dibromobutane was slowly added dropwise over 2 minutes, and the mixture was stirred at 170 ° C for 5 hours. The reaction polymer solution was precipitated in 800 mL of a mixed solvent of water and methanol, and the precipitate was filtered. The precipitate was again dissolved in NMP, and the precipitate was repeatedly filtered. The precipitate was vacuum-dried in a vacuum oven at 80 ° C. for 10 hours, (Z in formula (1)
Example 2
Except that 1.32 g (5 mmol) of (1,2-dibromoethyl) benzene was used in place of the above-mentioned 1,4-dibromobutane, (Z in formula (1)
Example 3
Except that 0.81 g (5 mmol) of 1,1-carbonyldiimidazole was used in place of the above-mentioned 1,4-dibromobutane, the polymer type sulfone compound ( Z in formula (1)
Comparative Example One
5 g (20 mmol) of bisphenol S, 6.08 g (44 mmol) of potassium carbonate (K 2 CO 3 ) and 10 g of N-methylpyrrolidone were added to a 100 ml round bottom flask equipped with a condenser and a Dean- 35 ml of N-methyl-2-pyrrolidone (NMP) and 15 ml of toluene were added and the mixture was heated at a temperature of 180 to 200 ° C under a nitrogen (N 2 ) atmosphere for 2.5 hours , And the produced water was completely removed by azeotropic distillation with toluene. Next, the temperature was lowered to 150 캜, 5.743 g (20 mmol) of dichlorodiphenylsulfone was added, and the reaction was carried out at a temperature of 220 캜 for 2.5 to 3 hours. The reaction product was precipitated in 800 ml of a 10% hydrochloric acid aqueous solution, and the precipitate was filtered. The precipitate was again dissolved in NMP, and the precipitate was filtered repeatedly. The precipitate was vacuum-dried in a vacuum oven at 80 ° C for 10 hours, (Yield: 98%, weight average molecular weight: 10,000 g / mol) was prepared. The 1 H-NMR spectrum of the sulfone compound thus prepared is shown in FIG.
(2)
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
[Chemical Formula 1]
Wherein R 1 and R 2 are each independently a sulfonyl (-SO 3 H) group or a hydrocarbon group having 1 to 10 carbon atoms, X is a halogen atom, and Z is
[Chemical Formula 1]
Wherein R 1 and R 2 are each independently a sulfonyl (-SO 3 H) group or a hydrocarbon group having 1 to 10 carbon atoms, X is a halogen atom, and Z is
(2)
(3)
Wherein R 1 , R 2 , X, Z, a, b, m and n are as defined in Formula 1 and X 2 is a good leaving group.
[Chemical Formula 4]
[Chemical Formula 5]
Wherein R 1 , R 2 , X, a and b are as defined in the above formula (1).
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| KR1020130040127A KR101657270B1 (en) | 2013-04-11 | 2013-04-11 | Sulfone based compound containing hydrocarbon core and method for preparing the same |
| PCT/KR2013/007521 WO2014168297A1 (en) | 2013-04-11 | 2013-08-22 | Sulfone-based compound having hydrocarbon core and production method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1428404A (en) | 1972-04-11 | 1976-03-17 | Ici Ltd | Haloaromatic compounds |
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| US3966851A (en) * | 1970-07-15 | 1976-06-29 | Imperial Chemical Industries Limited | Phenol precursors |
| US4486576A (en) * | 1982-04-22 | 1984-12-04 | Union Carbide Corporation | High-temperature, aromatic coating materials from aryl polyhalides |
| US5091480A (en) * | 1984-03-06 | 1992-02-25 | The B. F. Goodrich Company | Comb-like polymers and graft copolymers from polyarylene polyether macromonomers |
| DE112009001216T5 (en) * | 2008-05-21 | 2011-03-24 | Sumitomo Chemical Company, Limited | Polymer, polyarylene block copolymer, polymer electrolyte, polymer electrolyte membrane and fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1428404A (en) | 1972-04-11 | 1976-03-17 | Ici Ltd | Haloaromatic compounds |
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| Macromolecules, 1997, Vol.30, pp.5970-5975 |
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