KR20140132241A - Sulfone based block copolymer and method for preparing the same - Google Patents

Sulfone based block copolymer and method for preparing the same Download PDF

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KR20140132241A
KR20140132241A KR1020130051542A KR20130051542A KR20140132241A KR 20140132241 A KR20140132241 A KR 20140132241A KR 1020130051542 A KR1020130051542 A KR 1020130051542A KR 20130051542 A KR20130051542 A KR 20130051542A KR 20140132241 A KR20140132241 A KR 20140132241A
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carbon atoms
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block copolymer
substituted
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최진우
진영섭
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제일모직주식회사
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Priority to PCT/KR2013/007586 priority patent/WO2014181931A1/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20Polysulfones
    • C08G75/23Polyethersulfones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
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Abstract

The sulfonic-based block copolymer of the present invention contains an ether sulfone unit and a radical polymer unit, which are condensation polymers, and contains a unit represented by the above-mentioned formula (1).

Description

TECHNICAL FIELD [0001] The present invention relates to a sulfonated block copolymer and a method for producing the same,

The present invention relates to a sulfonic-based block copolymer and a process for producing the same. More particularly, the present invention relates to a sulfonic-based block copolymer comprising an ether sulfone unit and a radical polymer unit, which are condensation polymers, and a process 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. To overcome these problems, it is necessary to develop block copolymers containing blocks that can compensate for insufficient physical properties.

A block copolymer refers to a copolymer having a structure in which a polymer made by a second type of unit structure is connected to the end of a polymer molecule made by any single type of unit structure. Unlike the random copolymer, the block copolymer locally has both the structure and properties of the homopolymer of each component (unit structure), and thus can exhibit both characteristics.

Since the block copolymer is usually formed by chain polymerization such as radical polymerization or ionic polymerization, a conventional method for producing a block copolymer includes a dihalogenenediphenyl sulfone compound and a dihydroxydiphenyl sulfone compound It is impossible to prepare a block copolymer containing a polyether sulfone produced by condensation polymerization of the polyether sulfone. Accordingly, the physical properties of the polyethersulfone are controlled not by the block copolymer but by the modification or substituent of the backbone.

Therefore, it is necessary to develop a sulfonic-based block copolymer containing both an ether sulfone unit and a radical polymer unit such as a polyether sulfone, which is a condensation polymer, and a production method thereof.

An object of the present invention is to provide a sulfonic-based block copolymer comprising an ether sulfone unit and a radical polymer unit which are condensation polymers.

Another object of the present invention is to provide a process for producing the sulfonic-based block copolymer.

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 sulfonic-based block copolymers. The sulfonated block copolymer may include a unit represented by the following formula (1)

[Chemical Formula 1]

Figure pat00001

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, R 3 is a hydrogen atom or a methyl group, R 4 Is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, Y is

Figure pat00002
or
Figure pat00003
(Wherein R is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, -OH, -OR 5 (wherein R 5 is an alkyl or aryl group having 1 to 10 carbon atoms), -NH 2 , -COOH , -COOR 6 (wherein R 6 is an alkyl group or an aryl group having 1 to 10 carbon atoms), or -CONH 2 , and * represents a bonding site, a and b are each independently an integer of 0 to 4, m and n are each independently an integer of 3 or more.

In the specific examples, m and n each independently represent an integer of 4 to 50 in the sulfonic-based block copolymer represented by the general formula (1).

Another aspect of the present invention relates to a method for producing the sulfonic-based block copolymer. The process comprises the steps of polymerizing a sulfonic compound represented by the following formula (2) and a vinyl monomer represented by the following formula (3)

(2)

Figure pat00004

In Formula 2, 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

Figure pat00005
or
Figure pat00006
(Wherein R is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, -OH, -OR 5 (wherein R 5 is an alkyl or aryl group having 1 to 10 carbon atoms), -NH 2 , - COOH, -COOR 6 (wherein R 6 is an alkyl group or an aryl group having 1 to 10 carbon atoms), or -CONH 2 , and * represents a bonding site, a and b are each independently an integer of 0 to 4, n is an integer of 3 or more;

(3)

Figure pat00007

In Formula 3, R 3 is a hydrogen atom or a methyl group, and R 4 is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms.

In an embodiment, the polymerization may be a radical polymerization.

In an embodiment, the molar ratio of the sulfonic compound and the vinyl monomer (Formula 2: Formula 3) may be 1: 10 to 500.

In an embodiment, the sulfone compound represented by Formula 2 may be prepared by reacting a sulfone compound represented by Formula 4 and a halogen compound represented by Formula 5:

[Chemical Formula 4]

Figure pat00008

[Chemical Formula 5]

Figure pat00009

Wherein R 1 , R 2 , X, Z, a, b, and n are as defined in Formula 2, and X 2 is a halogen atom.

In an embodiment, the sulfone compound represented by Formula 4 may be prepared by reacting a dihydroxydiphenyl sulfone compound represented by Formula 6 with an alkali metal compound to produce dihydroxydiphenylsulfone salt; And reacting the dihydroxydiphenylsulfone salt and a dihalogenenediphenyl sulfone compound represented by the following general formula (7) to prepare a sulfone compound represented by the general formula (2):

[Chemical Formula 6]

Figure pat00010

(7)

Figure pat00011

In the formulas (6) and (7), R 1 , R 2 , X, a and b are as defined in the above formula (2).

The present invention has the effects of the invention providing a sulfonic-based block copolymer comprising an ether sulfone unit and a radical polymer unit, which are condensation polymers, and a process for producing the same.

1 is a 1 H-NMR spectrum of a sulfonic compound prepared according to Production Example 1 of the present invention.
2 is a 1 H-NMR spectrum of an H signal of an end group of an sulfonic compound prepared according to Production Example 1 of the present invention.
3 is a 1 H-NMR spectrum of a sulfonic-based block copolymer prepared according to Example 1 of the present invention.
4 is a 1 H-NMR spectrum of an aromatic portion of a sulfonic-based block copolymer prepared according to Example 1 of the present invention.
5 is a 1 H-NMR spectrum of an aliphatic portion of a sulfonic-based block copolymer prepared according to Example 1 of the present invention.

Hereinafter, the present invention will be described in detail.

The sulfonic-based block copolymer according to the present invention comprises an ether sulfone unit and a radical polymer unit, which are condensation polymers, and may include a unit represented by the following general formula (1).

[Chemical Formula 1]

Figure pat00012

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, preferably 1 to 6 carbon atoms, and R 3 is hydrogen And R 4 is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, preferably 4 carbon atoms, with or without a hetero atom such as an oxygen atom (O), a sulfur atom (S) and a nitrogen atom (N) To 50 carbon atoms, Y is

Figure pat00013
or
Figure pat00014
(Wherein R is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, -OH, -OR 5 (wherein R 5 is an alkyl or aryl group having 1 to 10 carbon atoms), -NH 2 , -COOH , -COOR 6 (wherein R 6 is an alkyl group or an aryl group having 1 to 10 carbon atoms), or -CONH 2 , and * represents a bonding site, a and b are each independently an integer of 0 to 4, m and n are each independently an integer of 3 or more, preferably an integer of 4 to 50, more preferably an integer of 6 to 30.

In the specification of the present invention, "ethersulfone unit" means a unit containing a sulfone group (-SO 2 -) and an ether group (-O-) in a chain, for example, , And "radical polymer unit" means a unit formed by radical polymerization. In the specification of the present invention, "hydrocarbon group" means a linear, branched or cyclic saturated or unsaturated hydrocarbon group, and "substituted" means that a hydrogen atom is an oxygen atom (O), a sulfur atom (S) , A hetero atom such as a nitrogen atom (N), an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, combinations thereof, 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 an embodiment, the sulfonic-based block copolymer may be a block copolymer in which m and n in Formula (1) are each independently an integer of 4 to 50. For example, the sulfonated block copolymer may have a weight average molecular weight of 100,000 to 150,000 g / mol as measured by gel permeation chromatography (GPC), but is not limited thereto.

In an embodiment, the sulfonic-based block copolymer of the present invention contains only Y, the ether sulfone unit and the radical polymer unit, and is not a randomly repeating constituent unit.

When the R 4 in the formula (1) is an aromatic group or an alkyl group, the sulfonic acid type block copolymer may have improved physical properties such as solubility, chemical resistance and tensile strength. When R 4 in the formula (1) is an acrylamide type or the like , Physical properties such as hydrophilicity and chemical resistance can be improved.

The method for preparing a sulfonic-based block copolymer according to the present invention comprises polymerizing a sulfonic compound represented by the following general formula (2) and a vinylic monomer represented by the following general formula (3).

(2)

Figure pat00015

Wherein R 1 , R 2 , a, b, and n are as defined in Formula 1, X is a halogen atom, and Z is

Figure pat00016
or
Figure pat00017
(Wherein R and * are the same as defined in Formula 1).

Here,

Figure pat00018
For example,
Figure pat00019
(Wherein R 5 is independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, -OH, -OR 3 (wherein R 3 is an alkyl or aryl group having 1 to 10 carbon atoms), -NH 2 , -COOH, -COOR 4 (wherein R 4 is an alkyl group or an aryl group having 1 to 10 carbon atoms), or -CONH 2 ,
Figure pat00020
Or the like, but is not limited thereto.

(3)

Figure pat00021

Wherein R 3 and R 4 are the same as defined in the above formula (1).

Specific examples of the vinyl-based monomer represented by the general formula (3)

Figure pat00022
,
Figure pat00023
,
Figure pat00024
,
Figure pat00025
,
Figure pat00026
But the present invention is not limited thereto.

In a specific example, the polymerization may be carried out, for example, by adding the vinyl monomer and the radical initiator represented by the formula (3) and then adding the sulfone compound represented by the formula (2) Lt; / RTI > The heating may vary depending on the vinyl monomers, sulfonic compounds, etc. used, but may be carried out, for example, at 30 to 200 ° C for 1 to 20 hours. Specifically, the sulfone-based compound and the vinyl-based monomer can be simply used to form the sulfone-based polymer of the present invention using a conventional bulk radical polymerization method, a solution radical polymerization method, a suspension polymerization method or an emulsion polymerization method, Block copolymers can be prepared. For example, it can be prepared according to the following examples, but it is not limited thereto. Such a polymerization method can be easily carried out by a person having ordinary skill in the art to which the present invention belongs.

Examples of the radical initiator include, but are not limited to, 2,1'-azobis (isobutyronitrile) (AIBN), benzoyl peroxide (BPO), hydrogen peroxide H 2 O 2 ), copper bromide (CuBr), copper bromide (II) (CuBr 2 ) copper iodide (CuI), and the like.

When a solvent is used in the production of the block copolymer (such as solution radical polymerization), the solvent may be a sulfoxide-based solvent such as dimethylsulfoxide or hexamethylene sulfoxide, N, N-dimethylformamide, N, N- Amide solvents such as dimethylformamide and dimethylformamide, amide solvents such as dimethylacetamide, piperidone solvents such as N-methyl-2-pyrrolidone and N-methyl-2-piperidone, 2- Imidazolinone solvents, sulfolane solvents such as sulfolane, mixtures of two or more thereof, and the like, but the present invention is not limited thereto. The content of the 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)).

In the preparation of the block copolymer, the molar ratio of the sulfonic compound and the vinyl monomer (Chemical Formula 2) may vary depending on the degree of physical properties such as chemical resistance to be included in the polyether sulfone, , From 1:10 to 500, preferably from 1:15 to 150. The desired properties may be included in the sulfonated block copolymer prepared in the above range. The content of the radical initiator may be, for example, 10 to 50 moles per 100 moles of the sulfone compound, but is not limited thereto.

In addition, when the sulfone compound of the present invention contains a halogen group (for example, X of the sulfone compound represented by the above formula (1)), the halogen group may be substituted with various substituents (terminal groups) have. Such substitution can be easily performed by a person having ordinary skill in the art to which the present invention belongs.

The sulfone compound represented by Formula 2 may be prepared by reacting a sulfone compound represented by Formula 4 and a halogen compound represented by Formula 5 below.

[Chemical Formula 4]

Figure pat00027

[Chemical Formula 5]

Figure pat00028

In the above formulas 4 and 5, R 1 , R 2 , X, Z, a, b and n are as defined in Formula 2 and X 2 is a halogen atom such as a chlorine atom (Cl) F), a bromine atom (Br), and an iodine atom (I), preferably a chlorine atom (Cl).

The reaction may be carried out by reacting the sulfone compound represented by Formula 4 and the halogen compound represented by Formula 5 in an organic solvent. The molar ratio of the sulfone compound represented by the formula (4) to the halogen compound represented by the formula (5) may be, for example, 1: 1 to 10, preferably 1: 1 to 3. The conversion of the terminal group (Z) of the sulfonic compound prepared in the above range is close to 100%, and the reaction yield is excellent.

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 (4 and 5).

The reaction may be carried out, if necessary, by further adding a conventional additive such as a catalyst. Examples of the catalyst include triethylamine (NEt 3 ) and the like. The amount of the catalyst to be used may be 0.1 to 1 part by weight based on 100 parts by weight of the total reactants (4 and 5) .

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 conversion of the terminal group (Z) of the sulfonic compound prepared in the above range is close to 100%, and the reaction yield is excellent.

The sulfone compound represented by the formula (4) may be a commercially available polyether sulfone compound or a monomer thereof. For example, a dihydroxydiphenyl sulfone compound represented by the following formula (6) and an alkali metal compound are reacted To produce a dihydroxydiphenylsulfonate salt; And a step of reacting the dihydroxydiphenylsulfone salt and a dihalogenenediphenyl sulfone compound represented by the following general formula (7) to prepare a sulfone compound represented by the general formula (4) Polyethersulfone) can be used.

[Chemical Formula 6]

Figure pat00029

(7)

Figure pat00030

In the formulas (6) and (7), R 1 , R 2 , X, a and b are as defined in the above formula (2).

The alkali metal compound is added to produce the metal salt of the dihydroxydiphenyl sulfone compound in order to increase the low reactivity (nucleophilic property) of the dihydroxydiphenyl sulfone compound. For example, alkali metal compounds such as alkali metal A carbonate, an alkali metal hydroxide, an alkali metal hydride, an alkali metal alkoxide and the like can be used, and an alkali metal carbonate such as potassium carbonate, sodium carbonate and the like 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 (4) 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. 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

Manufacturing example  One: Sulphonic system  Preparation of compounds

5 g (20 mmol) of bisphenol S and 6.08 g (44 mmol) of potassium carbonate (K 2 CO 3 ) were placed in a 250 ml round-bottom flask equipped with a condenser and a Dean-Stark trap. , 35 ml of N-methyl-2-pyrrolidone (NMP) and 30 ml of toluene were added to the mixture, and the mixture was heated at a temperature of 180 to 200 ° C under nitrogen (N 2 ) The mixture was heated for 2.5 hours, and the resulting water was removed by azeotropic distillation with toluene. Next, the temperature was lowered to 150 占 폚, 5.743 g (20 mmol) of dichlorodiphenylsulfone was added, and the reaction was carried out at a temperature of 220 占 폚 for 3 hours. The temperature of the reaction mixture was lowered to 100 占 폚, and then 1.62 ml (20 mmol) of acryloyl bromide was slowly added dropwise over 5 minutes and stirred for 1 hour. The reaction polymer solution showed a bright orange color. It was precipitated by adding 1 L of methanol, and the precipitate was filtered. The precipitate was again dissolved in NMP, and the precipitate was filtered repeatedly. The precipitate was filtered in a vacuum oven at 80 ° C for 10 hours Dried to obtain a polymer type sulfonic compound (a and b in formula (2) are 0, X is Cl, and Z is

Figure pat00031
(Yield: 98%, weight average molecular weight: 9,000 g / mol, polydispersity index (PDI): 1.7). It shows the 1 H-NMR spectrum by 1 H-NMR spectrum of the expanding signal H and the terminal groups of the produced sulfone compound in Figs.

Example  One: Sulphonic system  Preparation of block copolymers

10 g (96 mmol) of styrene monomer, 33 mg of benzoyl peroxide (BPO) and 2,2'-azobis (isobutyronitrile) (AIBN) dissolved in 10 ml of dimethylformamide (DMF) 33 mg were added and mixed, followed by stirring at 40 ° C for 2 hours. Subsequently, 1 g (0.11 mmol) of the sulfonate compound of Preparation Example 1 dissolved in 5 ml of dimethylformamide (DMF) was slowly added dropwise, followed by reaction at 100 ° C for 8 hours. After completion of the reaction, the reaction mixture was precipitated in 500 ml of methanol and washed with 1 L of water. The precipitate was filtered, and the filtered precipitate was vacuum-dried in a vacuum oven at 80 ° C for 10 hours to obtain a white sulfonated block copolymer (a and b in the formula (1), 0 and a ratio (m: n) Is about 10: 1, R 3 is a hydrogen atom, R 4 is a phenyl group, Y is

Figure pat00032
(R is a hydrogen atom) (yield: 52%, weight average molecular weight: 110,000 g / mol, polydispersity index (PDI): 3). The 1 H-NMR spectrum (FIG. 3) and the 1 H-NMR spectrum (FIGS. 4 and 5) of the aromatic and aliphatic portions of the prepared sulfonic-based block copolymer are shown in FIGS. 3 to 5 Respectively.

Example  2: Sulphonic system  Preparation of block copolymers

5 g (48 mmol) of styrene monomer dissolved in 7 ml of dimethylformamide (DMF), 18 mg of benzoyl peroxide (BPO), 2,2'-azobis (isobutyronitrile) (AIBN) 18 mg, and the mixture was stirred at 40 ° C for 2 hours. Subsequently, 1 g (0.11 mmol) of the sulfonate compound of Preparation Example 1 dissolved in 5 ml of dimethylformamide (DMF) was slowly added dropwise, followed by reaction at 100 ° C for 8 hours. After completion of the reaction, the reaction mixture was precipitated in 500 ml of methanol and washed with 1 L of water. The precipitate was filtered, and the filtered precipitate was vacuum-dried in a vacuum oven at 80 ° C for 10 hours to obtain a white sulfonated block copolymer (a and b in the formula (1), 0 and a ratio (m: n) Is about 5: 1, R 3 is a hydrogen atom, R 4 is a phenyl group, Y is

Figure pat00033
(Yield: 55%, weight average molecular weight: 43,000 g / mol, polydispersity index (PDI): 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 (7)

A sulfonated block copolymer comprising a unit represented by the following formula (1): < EMI ID =
[Chemical Formula 1]
Figure pat00034

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, R 3 is a hydrogen atom or a methyl group, R 4 Is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, Y is
Figure pat00035
or
Figure pat00036
(Wherein R is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, -OH, -OR 5 (wherein R 5 is an alkyl or aryl group having 1 to 10 carbon atoms), -NH 2 , -COOH , -COOR 6 (wherein R 6 is an alkyl group or an aryl group having 1 to 10 carbon atoms), or -CONH 2 , and * represents a bonding site, a and b are each independently an integer of 0 to 4, m and n are each independently an integer of 3 or more.
The sulfonated block copolymer according to claim 1, wherein m and n are each independently 4 to 50 in the sulfonated block copolymer represented by the formula (1).
A method for preparing a sulfonic-based block copolymer comprising a unit represented by the following formula (1), comprising the step of polymerizing a sulfonic compound represented by the following formula (2) and a vinyl monomer represented by the following formula
[Chemical Formula 1]
Figure pat00037

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, R 3 is a hydrogen atom or a methyl group, R 4 Is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, Y is
Figure pat00038
or
Figure pat00039
(Wherein R is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, -OH, -OR 5 (wherein R 5 is an alkyl or aryl group having 1 to 10 carbon atoms), -NH 2 , -COOH , -COOR 6 (wherein R 6 is an alkyl group or an aryl group having 1 to 10 carbon atoms), or -CONH 2 , and * represents a bonding site, a and b are each independently an integer of 0 to 4, m and n are each independently an integer of 3 or more;
(2)
Figure pat00040

In Formula 2, 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
Figure pat00041
or
Figure pat00042
(Wherein R is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, -OH, -OR 5 (wherein R 5 is an alkyl or aryl group having 1 to 10 carbon atoms), -NH 2 , - COOH, -COOR 6 (wherein R 6 is an alkyl group or an aryl group having 1 to 10 carbon atoms), or -CONH 2 , and * represents a bonding site, a and b are each independently an integer of 0 to 4, n is an integer of 3 or more;
(3)
Figure pat00043

In the general formula (3), R 3 is a hydrogen atom or a methyl group, and R 4 is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms.
The method for producing a sulfonated block copolymer according to claim 3, wherein the polymerization is a radical polymerization.
4. The method for preparing a sulfonated block copolymer according to claim 3, wherein the mole ratio of the sulfonic compound and the vinyl monomer is 1: 10-500.
4. The method according to claim 3, wherein the sulfonic compound represented by Formula 2 is prepared by reacting a sulfone compound represented by Formula 4 and a halogen compound represented by Formula 5 below, Coalescence Manufacturing method:
[Chemical Formula 4]
Figure pat00044

[Chemical Formula 5]
Figure pat00045

Wherein R 1 , R 2 , X, Z, a, b, and n are as defined in Formula 2, and X 2 is a halogen atom.
[7] The method of claim 6, wherein the sulfone compound represented by Formula 4 is produced by reacting a dihydroxydiphenyl sulfone compound represented by Formula 6 with an alkali metal compound to produce dihydroxydiphenylsulfonate; And reacting the dihydroxydiphenylsulfone salt and a dihalogenenediphenyl sulfone compound represented by the following general formula (7) to prepare a sulfone compound represented by the general formula (2). Method of preparing block copolymer:
[Chemical Formula 6]
Figure pat00046

(7)
Figure pat00047

In the formulas (6) and (7), R 1 , R 2 , X, a and b are as defined in the above formula (2).
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