JP2008088060A - End-capping compound useful for synthesis of telechelic oligomer by aromatic nucleophilic substitution reaction, telechelic oligomer containing the end-capping compound, and block copolymer of the telechelic oligomer and polyarylene - Google Patents

Abstract

上記式中、Ｘはフッ素を除くハロゲン原子等を示し；Yはフッ素原子または−NO₂ で表される基を示し；Zは酸素原子または硫黄原子、−SO₂−等からなる群から選ばれる２価の電子吸引基を示し；W¹およびW²は独立に水素原子または、−COAr、−CONHAr、-COO、−COOAr、−CN、および−SO₂Arからなる群から選ばれる１価の電子吸引基を示し、Arはフェニル基またはナフチル基を示し；R¹およびR²は独立に水素原子、アルキル基、アリール基、アルコキシ基またはアリーロキシ基を示す。
【選択図】なし[PROBLEMS] To improve the ductility of a high-strength, high-elasticity aromatic polymer by incorporating a novel halogenated aromatic compound as an end-capping compound of a telechelic polyarylene oligomer.
A specific novel halogenated aromatic compound represented by the following general formula (1) is useful as an end-capping compound in the preparation of a telechelic aromatic oligomer.

In the above formula, X represents a halogen atom or the like excluding fluorine; Y represents a fluorine atom or a group represented by —NO ₂ ; Z is selected from the group consisting of an oxygen atom, a sulfur atom, —SO ₂ — and the like. Represents a divalent electron-withdrawing group; W ¹ and W ² are each independently a hydrogen atom or a monovalent selected from the group consisting of —COAr, —CONHAr, —COO, —COOAr, —CN, and —SO ₂ Ar Represents an electron-withdrawing group, Ar represents a phenyl group or a naphthyl group; R ¹ and R ² independently represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group.
[Selection figure] None

Description

  As used herein, “telechelic oligomer” means a relatively low molecular weight polymer having at least one, usually two reactive functional groups at the end of the polymer molecule. When two or more terminal reactive groups are present, these terminal reactive groups may be the same or different.

  The present invention relates to a novel end-capping compound useful for synthesizing a telechelic oligomer by an aromatic nucleophilic substitution reaction, a telechelic oligomer containing the end-capping compound, and a block copolymer of the telechelic oligomer and polyarylene. Regarding coalescence.

There is a direct relationship between the flexibility of the polymer chain at the molecular level and the macroscopic mechanical properties such as elastic modulus and tensile strength. That is, if the polymer has a sufficient molecular weight, the higher the energy barrier to main chain folding, the higher the stiffness and strength of the polymer. As such a rigid polymer, poly (1,4-phenylene-1,4-terephthalamide) (PPTA) is well known. In the polymer, an elongated polymer structure is energetically advantageous because of the presence of para-phenylene groups and amide bonds. Poly (para-phenylene) (PPP) is also known and the polymer is ca. It is considered to be a rigid polymer with a molecular length of 20 nm (BL Farmer, BR Chapman, DS Dudis, and WW Adams
, Polymer, 34, 1588 (1993)). A very good elastic modulus is obtained by the rigid polymer chain, but synthesis and processing characteristics are greatly limited. PPTA is soluble only in very limited types of solvents, and the processing means is limited to the spinning method. Unsubstituted PPP is also very difficult to handle.

  Depending on the application, there is a need for materials that are high-strength, high-rigidity, chemically and thermally inert and that can be processed by conventional methods such as molding, extrusion and film casting. In order to improve the mechanical and chemical strength, composite materials composed of a matrix made of a relatively soft polymer and a filler such as carbon, silica or clay are widely used. Further, by introducing glass fibers or carbon fibers into the polymer matrix, a composite material having high rigidity and high strength can be obtained.

  On the other hand, the preparation and processing of composite materials takes a little more time and effort than non-reinforced materials, leading to increased costs. In general, composite materials are difficult to repair and cannot be reused, which can lead to unexpected collapse and disaster. Furthermore, it is difficult for the film-like composite material to maintain the reproduction characteristics when the film thickness is about the same as the filler particle diameter.

  A similar reinforcing effect can be obtained by introducing rigid molecules into the soft polymer matrix. A so-called molecular composite material can be considered as an equivalent of a fiber-reinforced composite material in a microscopic sense, and a rigid molecule plays the role of a fiber. On the other hand, the soft polymer component has the purpose of dispersing the rigid polymer and prevents molecular aggregation. Since the molecular composite material does not contain fibers and particles, it can be easily processed at a lower cost than the macro composite material and can be reused.

Similar to macrocomposites, molecular composites are obtained by blending a rigid polymer component and a soft polymer component. However, it is known that few polymers can be mixed with each other. Other materials, including rigid / soft polymer mixtures, undergo macrophase separation when blended. Moreover, although the initial physical properties of the obtained blend are preferable, there is a high possibility that unexpected deterioration will occur with the passage of time, particularly in an erosion environment in a proton electrolyte membrane for a fuel cell or a light emitting diode. In the molecular composite material used for these purposes, high durability is the most important issue.

  By using a block copolymer containing incompatible soft and rigid blocks, macrophase separation can be prevented. Such a polymer structure promotes microphase separation morphology. The morphology exhibits the combined characteristics of high strength and high elasticity derived from rigid microdomains and high flexibility and high yield strength derived from a soft matrix. Since rigid PPP segments have high strength and excellent chemical stability, it is required to introduce PPP segments into molecular composite materials. Side chain-substituted PPP is soluble in various solvents and is usually obtained by dehalogenation polycondensation reaction of substituted 1,4-dihalobenzene (Y. Wang and RP Quirk, Macromolecules, 28, 3495 (1995)). . The corresponding block copolymer can be obtained by the following two steps. First, a rigid or soft oligomer precursor with appropriately functionalized chain ends is synthesized, and then the functionalized oligomer is reacted with the remaining comonomer to form a segmented multi-block structure. A polymer having is obtained.

  Patent Document 1 discloses a rigid macromonomer having a reactive end group, which is useful for modifying an industrial thermoplastic resin. The macromonomer is represented by formula (i):

In the above formula, G ₁ to G ₄ independently represent a solubilizing side group or a hydrogen atom, E represents a reactive functional group, and the number average degree of polymerization DP _n is about 6 or more.
US Pat. No. 5,973,075

  Poly (phenylene) is a polymer composed of phenylene groups in which the main chain is directly bonded. With this structure, poly (phenylene) is durable to high temperatures, acids, bases, light, and other factors that degrade the polymer backbone. Poly (phenylene) having a relatively bulky side group can be obtained in a high molecular weight by a known method. In addition, the polymer is soluble in various solvents and can be processed into a film, a fiber, or a molded product. Due to such characteristics, it can be suitably used in applications where high durability in an erosive environment is the most important issue, such as materials such as light emitting diodes, optoelectronics, polymer electrolyte membranes, protective membranes, and reinforcing materials.

However, poly (phenylene) is inherently fragile because it has a rigid backbone, limiting its use. In order to obtain ductility, a plasticizer may be mixed with the brittle polymer. The plasticizer is usually a liquid having a low molecular weight and a high boiling point, and is sufficiently mixed with the polymer to lower the glass transition temperature of the polymer. However, these low molecular weight mixtures are prone to degradation under the conditions of use and lead to premature deterioration of the material, so in most cases they cannot be used for poly (phenylene) applications. As the plasticizer, those derived from a polymer are preferable. A material combining such a rigid polymer component and a soft polymer component is defined as a molecular composite material. Molecular composites are similar in many respects to fiber reinforced plastics. In the molecular composite material, the rigid molecule serves as a fiber, and the soft polymer component has the purpose of dispersing the rigid polymer and prevents aggregation of the molecules.

  By blending a polymeric plasticizer with poly (phenylene), a molecular composite can be easily produced, but the resulting composite is usually not uniform due to phase separation. Some low molecular weight additives improve the compatibility of the blend components, but using them is not preferred for the same reason as using low molecular weight plasticizers.

  If the soft segment and the rigid segment of the molecular composite material are chemically bonded as a graft copolymer or block copolymer, the problem of the polymer blend can be solved. By chemical bonding, a uniform material having various microphase separation morphologies depending on the nature and size of the components can be obtained. With microphase separation, the mechanical properties of the corresponding molecular composite material are obtained by the combination of high strength and high elasticity derived from rigid poly (phenylene) domains and high ductility derived from a soft matrix. From a chemical point of view, block copolymers of poly (phenylene) and other rigid aromatic polymers with soft polymers are easier to produce by conventional polycondensation reactions than graft copolymers. can do. Further, the longer the chain length of the block copolymer main chain, the higher the degree of entanglement of the main chain, and as a result, the elastic properties are improved.

  As a method for producing a rigid-soft block copolymer, a polycondensation reaction has attracted attention. In a normal method, synthesis is performed in two stages. In order to avoid random copolymerization, either or both of the soft block and the rigid block are produced independently as telechelic oligomers, usually having a degree of polymerization of 4 to 100 and functionalized with appropriate end groups. In the second step, the telechelic oligomer is reacted with the other monomer having a complementary end group or another telechelic oligomer to obtain a multiblock copolymer.

Attempts have been made to produce telechelic oligomers with good reactivity and their rigid / soft multi-block copolymers, but sufficient results have not been obtained. Patent Document 1 describes a method for producing a rigid macromonomer having a polycyclic aromatic main chain, a solubilizing side group, and a reactive end group. The above compounds are designed for the purpose of modifying the tensile properties of the resin by copolymerizing with a commercially available thermoplastic resin. However, when the above oligomer is used, a step of deprotecting the terminal group is further required to make the terminal group reactive, which may be accompanied by an undesirable side reaction. Furthermore, this method allows only a relatively small amount of rigid components to be introduced into the thermoplastic matrix due to the incompatibility of the macromonomer. In order to obtain a high molecular weight multi-block copolymer, it is necessary to supply the macromonomer in an accurate quantitative ratio. However, since the macromonomer has few reactive sites and the molecular weight is polydisperse, It is relatively difficult to ensure the quantity ratio.

  The inventor of the present invention can selectively react a terminal halogenated aromatic compound represented by the following general formula (1) with another polymerizable compound by a known aromatic nucleophilic substitution reaction. The present inventors have found that a novel telechelic oligomer having physical properties useful as a precursor for forming and forming a polyarylene and a high-strength / high-elastic molecular composite material can be obtained. The halogenated aromatic compound is represented by the following general formula (1):

In the above formula, X represents a halogen atom excluding fluorine, a group selected from the group consisting of —OSO ₂ CH ₃ and —OSO ₂ CF ₃ ; Y represents a fluorine atom or a group represented by —NO ₂ ; Z oxygen atom or a sulfur atom, or, the _{- (CF 2) k, -C} (CF 3) 2 -, - SO- and -SO ₂ - a divalent electron-withdrawing group selected from the group consisting of; W ¹ and W ² is independently a hydrogen atom or --COC _k H _{2k + 1} , --COAr, --CONHC _k H _{2k + 1} , --CONHAr, --COOC _k H _{2k + 1} , --COOAr, --CN, --CHO, --C _k F _{2k + 1} , -SOC _k H _{2k + 1}
, -SOAr, a monovalent electron withdrawing group selected from the group consisting of -SO ₂ C _k H _{2k + 1} and -SO ₂ Ar, where k is an integer of from 1 to 10, Ar is a phenyl group or Represents a naphthyl group; R ¹ and R ² independently represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group;

The novel telechelic oligomer can be copolymerized with other polymerizable compounds by a known dehalogenated aryl-aryl coupling reaction, and the resulting block copolymer is useful as a high-strength, high-elastic molecular composite material It is.
Halogenated aromatic compound The halogenated aromatic compound used in the present invention is represented by the following general formula (1):

In the above formula, X represents a halogen atom excluding fluorine, a group selected from the group consisting of —OSO ₂ CH ₃ and —OSO ₂ CF ₃ ; Y represents a fluorine atom or a group represented by —NO ₂ ; Z oxygen atom or a sulfur atom, or, the _{- (CF 2) k, -C} (CF 3) 2 -, - SO- and -SO ₂ - a divalent electron-withdrawing group selected from the group consisting of; W ¹ and W ² is independently a hydrogen atom or --COC _k H _{2k + 1} , --COAr, --CONHC _k H _{2k + 1} , --CONHAr, --COOC _k H _{2k + 1} , --COOAr, --CN, --CHO, --C _k F _{2k + 1} , -SOC _k H _{2k + 1}
, -SOAr, a monovalent electron withdrawing group selected from the group consisting of -SO ₂ C _k H _{2k + 1} and -SO ₂ Ar, where k is an integer of from 1 to 10, Ar is a phenyl group or Represents a naphthyl group; R ¹ and R ² independently represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group;

The halogenated aromatic compound of the above formula (1) has selective reactivity with respect to the aromatic nucleophilic substitution reaction. In the reaction, the reactive group Y is converted to an aryl ether or thioether bond, and the substituents X, Z, R ¹ , R ² , W ¹ and W ² do not change under the reaction conditions. Because of this selectivity, the halogenated aromatic compound (1) is useful as an end-capping compound for producing a telechelic oligomer.
Telechelic oligomer Telechelic oligomer is represented by the following general formula (2):

In the above formula, X represents a halogen atom excluding fluorine, a group selected from the group consisting of —OSO ₂ CH ₃ and —OSO ₂ CF ₃ ; Z represents an oxygen atom or a sulfur atom, or — (CF ₂ ) _k , — A divalent electron-withdrawing group selected from the group consisting of C (CF ₃ ) ₂ —, —SO— and —SO ₂ —; W ¹ and W ² are each independently a hydrogen atom or —COC _k H _{2k + 1} , -COAr, -CONHC _k H _{2k + 1} , -CONHAr, -COOC _k H _{2k + 1} , -COOAr, -CN, -CHO, -C _k F _{2k + 1} , -SOC _k H _{2k + 1} , -SOAr, 1 represents a monovalent electron withdrawing group selected from the group consisting of —SO ₂ C _k H _{2k + 1} and —SO ₂ Ar, wherein k is an integer of 1 to 10, and Ar represents a phenyl group or a naphthyl group. R ¹ and R ² independently represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group; A represents an oxygen atom or a sulfur atom; n represents an integer of 2 or more; q1), (q2 ) And mixtures thereof are shown:

P represents a structure selected from the following formulas (p1) and (p2):

In the above formula, B and C independently represent a divalent atom, an organic electron withdrawing group or a direct bond; R ³ to R ²⁵ may be the same or different, and each represents a hydrogen atom, a fluorine atom, an alkyl group or an aromatic group. Indicates a group. Examples of the alkyl group include methyl, ethyl, propyl, butyl, amyl and hexyl groups, and among them, methyl and ethyl groups are preferable. Aromatic groups include phenyl, naphthyl, pyridyl, phenoxy, biphenyl and naphthoxyphenyl groups. B is preferably a direct bond or —CONH—, — (CF ₂ ) _k — (where k
Is an integer of 1 to 10), —C (CF ₃ ) ₂ —, —COO—, —SO—, —SO ₂ — and the following formula (b
Is an organic group selected from the group represented by:

In the above formula, R ²⁶ to R ³³ may be the same or different and each represents a hydrogen atom, a fluorine atom, an alkyl group or an aromatic group.
The novel telechelic oligomer represented by the above formula (2) can be obtained by an aromatic nucleophilic substitution reaction.

The telechelic oligomer of the above formula (2) has selective reactivity for the dehalogenated aryl-aryl coupling reaction. In the reaction, the reactive group X is converted to a carbon-carbon direct bond and the other substituents do not change under the reaction conditions. Because of this selectivity, the telechelic oligomer of formula (2) is useful as a component for forming block copolymers with other compounds that can be polymerized by a dehalogenated aryl-aryl coupling reaction.
Polyarylene The polyarylene of the present invention may be composed only of repeating units composed of the novel telechelic oligomer of formula (2), and the novel telechelic oligomer of formula (2) and dehalogenated aryl-aryl coupling It may be a block copolymer with another halogenated compound that can be polymerized by reaction.

  When the polyarylene is a block copolymer of the repeating unit of the formula (2) and the halogenated compound, the repeating unit other than the repeating unit of the formula (2) is represented by, for example, the following formula (3). Is:

In the above formula, E is a direct bond or —CO—, —CONH—, — (CF ₂ ) _p — (wherein p is an integer of 1 to 10), —C (CF ₃ ) ₂ —, —COO—. Represents an organic electron withdrawing group selected from the group consisting of -SO- and -SO _2- ; Ar is selected from the group consisting of phenyl, naphthyl, pyridyl, phenoxyphenyl, phenylphenyl and naphthoxyphenyl groups L represents a hydrogen atom, a fluorine atom or —CN, —CHO, —C _p F _{2p + 1} , —OC _p H _{2p + 1} , —SC _p H _{2p + 1} ,
-NHCOC _p H _{2p + 1} , -NHSO ₂ C _p H _{2p + 1} , -OCOC _p H _{2p + 1} , -CONHC _p H _{2p + 1} , -COOC _p H _{2p + 1} , -SOC _p H _{2p + 1} , (where p is is an integer of 1 to _{10) -SO 2 C p H 2p +} 1 and -SO ₃ C _p H _{2p + 1} represents a monovalent organic group selected from the group consisting of; k is 0 It is an integer of 3.

  The novel halogenated aromatic compound of the present invention can be used for producing a telechelic oligomer by forming a terminal blocking group with respect to a specific known polyarylene oligomer. The telechelic oligomer can be copolymerized with a known polyarylene suitable for production of a high-strength, high-elasticity aromatic polymer, and the resulting block copolymer is a high-strength, high-elasticity aromatic polymer. It is useful for the production of

The compounds of the present invention and telechelic oligomers using them will be described with reference to examples, but the present invention is not limited to these examples. The preparation of a specific polyarylene oligomer suitable for copolymerization by an aromatic nucleophilic substitution reaction and the preparation of a block copolymer using the polyarylene oligomer by a conventionally known method will be described by the following comparative examples. The synthesis of the novel halogenated aromatic compounds of the present invention is illustrated by Examples 1 and 2. In Example 3, an example in which the novel halogenated aromatic compound of Example 1 is used as a terminal blocking compound for a polyarylene oligomer of poly (ether) sulfone will be described. In Example 4, an example in which the novel halogenated aromatic compound of Example 2 is used as a terminal blocking compound in a polyarylene oligomer of poly (ether) ketone will be described. In Example 5, the novel halogenated aromatic compound of Example 2 was used to seal the ends of the telechelic poly (ether nitrile) oligomer. In Example 6, the terminal of the telechelic oligomer of the random copolymer of poly (ether ether ketone) was sealed using the novel halogenated compound. In Examples 7 and 8, a method of synthesizing a block copolymer using a telechelic oligomer and 2,5-dichloro-4′-phenoxybenzophenone or 3,5-dichlorophenylisobutylsulfone will be described, respectively.

  By synthesizing the novel aromatic compound of the present invention, the present inventor has found a compound useful for forming a telechelic oligomer by sealing the end of the polyarylene oligomer. The present inventor has also found that the telechelic oligomer is useful for producing a high-strength and high-elasticity aromatic polymer with improved ductility.

The best mode for carrying out the present invention includes a first step of synthesizing a novel aromatic compound. The synthesis of the novel compounds of the present invention is illustrated by Examples 1 and 2, but the synthesis method is not limited to these Examples. Novel halogenated aromatic compounds can be used for end-capping polyarylene oligomers, and end-capped oligomers can be used to produce aromatic polymers with improved strength and elasticity. Can do.
[Example]
[Comparative Example 1] Synthesis of hydroxyl-terminated poly (ether ether sulfone) oligomer

4,4′-dichlorodiphenylsulfone (17.23 g, 60 mmol), 4,4′-dihydroxydiphenylsulfone (13.01 g, 52 mmol) and
A mixture of K ₂ CO ₃ (9.67 g, 60 mmol) was added to NMP / toluene (50/40
mL) and stirred under a nitrogen atmosphere for 2 hours with gentle reflux. During stirring, the toluene / water azeotrope was collected in a Dean-Stark trap. When water was no longer collected in the trap, excess toluene was distilled off, and stirring was continued at 180 ° C. for another 6 hours. The reaction mixture was cooled to 80 ° C., filtered through celite, and precipitated in 10 volumes of methanol. The resulting light red fine suspension was carefully acidified with hydrochloric acid. The precipitate was filtered and dried until constant weight. As a result, a poly (ether sulfone) oligomer was obtained as a pale yellow powder. ¹ H-NMR confirmed that the oligomer was quantitatively end-capped with a phenol group. Yield: 24.57 g (91%); GPC: M _n = 4220, M _w = 8800
[Comparative Example 2] Synthesis of 4-fluorobenzoyl-terminated polyarylene oligomer

2,5-dichloro-4′-phenoxybenzophenone (21.10 g, 61.47 mmol), 4-chloro-4′-fluorobenzophenone (1.60 g, 6.83 mmol), Ni (PPh ₃ ) ₂ Cl ₂ (1 .27 g, 1.94 mmol), PPh ₃ (6.81 g, 25.96 mmol), NaI (0.30 g, 1.94 mmol) and zinc powder (10.61 g, 162 m).
mol) was added dry DMAc (75 mL) under a dry nitrogen stream. The reaction mixture was mechanically stirred at 80 ° C. for 4 hours. The obtained suspension of moderate viscosity was diluted with 100 mL of DMAc, stirred vigorously for 30 minutes, and then filtered through a celite pad to remove excess zinc. The obtained transparent solution was coagulated in 10 times the amount of methanol to obtain a yellow powdery oligomer. Yield: 15.20 g (84%); GPC: M _n = 10500, M _w = 21500
[Comparative Example 3] Production of poly (ether sulfone) -poly (1,4-phenylene) block copolymer Telechelic oligomer (2.110 g, 0.50 mmol) of Comparative Example 1 and Telechelic oligomer of Comparative Example 2 ( 5.250 g, 0.50 mmol) and K ₂ CO ₃ (0.173
g, 1.25 mmol) was stirred in NMP / toluene (12/8 mL) for 4 hours under a nitrogen atmosphere with gentle reflux. During stirring, the toluene / water azeotrope was collected in a Dean-Stark trap. Excess toluene was distilled off, and stirring was continued at 165 ° C. for another 20 hours until no increase in viscosity was observed. The reaction mixture was treated in the same manner as in Comparative Example 1 to obtain a polymer having the desired composition as an off-white powder. Yield: 6.61 g (90%); GPC: M _n = 24200, M _w = 54200
Example 1 Production of 2- (3-chlorophenoxy) -6-fluorobenzonitrile (1)

To a solution of 3-chlorophenol (12.86 g, 100 mmol) in dry DMAc (80 mL) was added sodium hydride (dispersed in mineral oil at a concentration of 60%, 4.00 g, 100 mmol) at room temperature under a nitrogen atmosphere. Added in small portions. The reaction mixture was stirred at room temperature until the solids were completely dissolved and 2,6-difluorobenzonitrile (80.0 g, 575 mmol) was added. The reaction mixture was gradually heated to 120 ° C. and stirred for 3 hours until the phenolate was completely consumed. Inorganic by-products were removed by filtration and DMAc and excess 2,6-difluorobenzonitrile were distilled off under vacuum. The residue was recrystallized from methanol and then hexane / ethyl acetate to obtain Compound 1 as colorless crystals. Yield: 17.01 g (69%); IR: Chart 1; ¹ H-NMR: Chart 2
IR and ¹ H-NMR spectra are shown in FIGS. 1 and 2, respectively.
Example 2 Synthesis of (3-chloro-6-methoxyphenyl) (4-fluorophenyl) sulfone (3)

To a solution of 4-chloroanisole (36.64 g, 256 mmol) and 4-fluorobenzenesulfonyl chloride (50.00 g, 256 mmol) in CH ₂ Cl ₂ (200 mL), a small amount of aluminum chloride (42.66 g, 320 mmol) was added. It was added in portions and stirred at room temperature until completely dissolved. The solvent was distilled off, and the resulting rubbery mixture was stirred at 90 ° C. for 2 hours and cooled. The cooled mixture was redissolved in CH ₂ Cl ₂ and quenched with ice / HCl. Solids were separated by decantation and the residue was extracted with toluene (500 mL). A combination of the separated solid and the extract was recrystallized using toluene (200 mL) to obtain phenol 2 as colorless crystals. Yield: 55.62 g (75%)
The resulting crude product was purified from iodomethane (50.0 g, 350 mmol) and K ₂ CO ₃ (3
4.55 g) in acetone (500 mL) for 3 hours and filtered, and then the solvent and excess iodomethane were distilled off. The solid residue was recrystallized from methanol (200 mL) to give sulfone 3 as colorless crystals. Yield: 46.57 g (80%); IR: Chart 3; ¹ H-NMR: Chart 4; ¹⁹ F-NMR: Chart 5
The IR spectrum is shown in FIG. ¹ H-NMR spectra are shown in FIGS.
[Example 3] Synthesis of 3-chlorophenoxy-terminated poly (ether sulfone) oligomer

4,4′-dichlorodiphenylsulfone (12.92 g, 45 mmol), 4,4′-dihydroxydiphenylsulfone (12.51 g, 50 mmol) and
A mixture of K ₂ CO ₃ (8.29 g, 60 mmol) was added to NMP / toluene (50/30
In a nitrogen atmosphere, the toluene / water azeotrope was collected in a Dean-Stark trap at 180 ° C. for 8 hours, and stirred until the formation of the hydroxyl-terminated oligomer was completed. The reaction mixture was cooled to 80 ° C., the solid end-capping compound of Example 1 (4.95 g, 20 mmol) was added in one portion, and the mixture was further stirred at 165 ° C. for 4 hours. The polycondensation product was separated by precipitation in methanol and fractionated by stirring in THF (300 mL). As a result, a telechelic poly (ether sulfone) oligomer was obtained as a pale yellow powder. ¹ H-NMR confirmed that the oligomer was quantitatively end-capped with a 3-chlorophenoxy group. Yield: 21.67 g (89%); GPC: M _n = 7160, M _w = 12700
Example 4 Synthesis of 3-chlorophenylsulfone terminated poly (ether ether ketone) oligomer

A mixture consisting of 4,4′-difluorobenzophenone (41.49 g, 190 mmol), 4,4 ′-(hexafluoroisopropylidene) diphenol (67.25 g, 200 mmol) and K ₂ CO ₃ (33.17 g, 240 mmol) DMAc / toluene (
The mixture was stirred at 150 ° C. for 8 hours in a nitrogen atmosphere until the formation of the hydroxyl-terminated oligomer was completed. The reaction mixture was cooled to 80 ° C. and the solid end-capping compound of Example 2 (10.53 g, 35 mmol) was added in one portion and further stirred at 135 ° C. for 4 hours. The obtained product was treated in the same manner as in Example 3 to obtain a white powder telechelic oligomer. From the ¹ H-NMR spectrum of the oligomer, it was confirmed that it had only a 3-chloro-6-methoxyphenylsulfone unit as a terminal group. Yield: 96.03 g (96%); GPC: M _n = 14000, M _w = 19100
[Example 5] Synthesis of 3-chlorophenylsulfone-terminated poly (ether ether nitrile) oligomer

2,6-difluorobenzonitrile (26.43 g, 190 mmol), 4,4 ′-(hexafluoroisopropylidene) diphenol (67.25 g, 200 mmol), K ₂ CO ₃ (33.17 g, 240 mmol) and examples 2 end-capping compound (10.53 g
35 mmol), telechelic oligomers were produced in the same manner as in Example 4 and separated as white fine particles. Yield: 82.00 g (86%); GPC: M _n = 9200, M _w = 13200
[Example 6] Synthesis of 3-chlorophenoxy-terminated poly (ether ketone) oligomer

Telechelic oligomers were prepared in the same manner as in Examples 3-5. That is, 4,4′-difluorobenzophenone (104.74 g, 480 mmol), resorcinol (44.59 g, 405 mmol) 9, 9-bis (4-hydroxyphenyl) fluorene (47.31 g, 135 mmol) and K ₂ CO ₃ ( A mixture consisting of 89.56 g (648 mmol) was stirred in DMAc / toluene at 145 ° C. for 6 hours, and then the end-capping compound of Example 1 (49.53 g, 180 mmol) was added, followed by further stirring for 2 hours. Yield: 141.30 g (86%); GPC: M _n = 3860, M _w = 5400
[Example 7] Synthesis of poly (ether sulfone) -poly (1,4-phenylene) block copolymer 2,5-dichloro-4'-phenoxybenzophenone (16.79 g, 48.93 mmol) of Example 3 3-Chlorophenoxy-terminated poly (ether sulfone) oligomer (7.55 g, 1.16 mmol), Ni (PPh ₃ ) ₂ Cl ₂ (0.98 g, 1.50 mmol), PPh ₃ (5.26 g, 20.04 mmol) , NaI (0.23 g, 1.50 mmol) and zinc powder (8.19 g, 125.23 mmol) were added dry DMAc (57 mL) under a stream of dry nitrogen and the reaction mixture was heated at 80 ° C. at 40 ° C. When the mixture was mechanically stirred, it was estimated that the viscosity of the solution increased significantly and a high polymer was produced. The reaction mixture was stirred for an additional hour, diluted with 200 mL of DMAc, stirred vigorously until a uniform suspension, then filtered through a celite pad to remove excess zinc. The resulting transparent solution was coagulated in 6 times the amount of methanol to obtain a yellow fibrous polymer. Yield: 19.75 g (95%); GPC: M _n = 43800, M _w = 137000
As can be seen from this example, the poly (ether sulfone) -poly (1,4-phenylene) block copolymer according to the present invention performs an aromatic nucleophilic substitution reaction without using a novel halogenated aromatic compound. Compared with the block copolymer of Comparative Example 3 having a similar composition synthesized by the above, it has a high molecular weight and can be obtained in a short reaction time.
[Example 8] Synthesis of poly (ether ether ketone) -poly (1,3-phenylene) block copolymer 3,5-Dichlorophenylisobutylsulfone (12.00 g, 44.93 mmol), 3-chloro of Example 6 Phenoxy-terminated poly (ether ketone) oligomer (23.41 g, 6.07 mmol), Ni (PPh ₃ ) ₂ Cl ₂ (1.00 g, 1.53 mmol), PPh ₃ (5.35 g, 20.40 mmol), NaI ( 0.23 g, 1.53 mmol) and zinc powder (
8.33 g, 127.5 mmol) was used for polymerization in dry DMAc (60 mL) as in Example 7. Yield: 28.61 g (90%); GPC: M _n = 29400, M _w = 65200

The IR spectrum of the compound obtained in Example 1 is shown. 1 shows the ¹ H-NMR spectrum of the compound obtained in Example 1. The IR spectrum of the compound obtained in Example 2 is shown. ¹ shows the ¹ H-NMR spectrum of the compound obtained in Example 2. ¹ shows the ¹ H-NMR spectrum of the compound obtained in Example 2.

Claims (10)

A halogenated aromatic compound represented by the following general formula (1):

In the above formula, X represents a halogen atom excluding fluorine, a group selected from the group consisting of —OSO ₂ CH ₃ and —OSO ₂ CF ₃ ; Y represents a fluorine atom or a group represented by —NO ₂ ; oxygen atom or a sulfur atom, or, the _{- (CF 2) k, -C} (CF 3) 2 -, - SO- and -SO ₂ - a divalent electron-withdrawing group selected from the group consisting of; W ¹ and W ² is independently a hydrogen atom or --COC _k H _{2k + 1} , --COAr, --CONHC _k H _{2k + 1} , --CONHAr, --COOC _k H _{2k + 1} , --COOAr, --CN, --CHO, --C _k F _{2k + 1} , -SOC _k H _{2k + 1} ,
1 represents a monovalent electron-withdrawing group selected from the group consisting of —SOAr, —SO ₂ C _k H _{2k + 1} and —SO ₂ Ar, wherein k is an integer of 1 to 10, and Ar is a phenyl group or naphthyl R ¹ and R ² independently represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group. A halogenated aromatic compound represented by the above formula (1), wherein Z is an oxygen atom or a sulfur atom which is meta to the substituents X and Y, . A halogenated aromatic compound represented by the above formula (1), wherein Z represents —SO ₂ —, R ¹ is an alkoxy group, and the substituent Y is para to Z. A halogenated aromatic compound. Telechelic oligomer compound represented by the following general formula (2):

In the above formula, X represents a halogen atom excluding fluorine, a group selected from the group consisting of —OSO ₂ CH ₃ and —OSO ₂ CF ₃ ; Z represents an oxygen atom or a sulfur atom, or — (CF ₂ ) _k , — A divalent electron-withdrawing group selected from the group consisting of C (CF ₃ ) ₂ —, —SO— and —SO ₂ —; W ¹ and W ² are each independently a hydrogen atom or —COC _k H _{2k + 1} , -COAr, -CONHC _k H _{2k + 1} , -CONHAr, -COOC _k H _{2k + 1} , -COOAr,
_{-CN, -CHO, -C k F 2k} + 1, -SOC k H 2k + 1, -SOAr, 1 monovalent electron withdrawing selected from the group consisting of -SO ₂ C _k H _{2k + 1} and -SO ₂ Ar Wherein k is an integer of 1 to 10, Ar represents a phenyl group or a naphthyl group; R ¹ and R ² independently represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group A represents an oxygen atom or a sulfur atom; n represents an integer of 2 or more; Q represents a structure selected from the following formulas (q1), (q2) and a mixture thereof:

P represents a structure selected from the following formulas (p1) and (p2):

In the above formula, B and C independently represent a divalent atom, an organic electron withdrawing group or a direct bond; R ³ to R ²⁵ may be the same or different, and each represents a hydrogen atom, a fluorine atom, an alkyl group or an aromatic group. Indicates a group. B in the structure represented by the above formula (q1) is a direct bond, or _{-CONH -, - (CF 2)} k -
(Where k is an integer of 1 to 10), —C (CF ₃ ) ₂ —, —COO—, —SO—, —SO ₂ — and an organic group selected from the group represented by the following formula (b) Compound according to claim 4, characterized in that it is a group:

In the above formula, R ²⁶ to R ³³ may be the same or different and each represents a hydrogen atom, a fluorine atom, an alkyl group or an aromatic group. C in the structure represented by the formula (p1) is a direct bond or -CO -, - SO -, - SO 2 -, - CO (CH 2) k CO -, - CO (CF 2) k CO- (Wherein k is an integer of 1 to 10) and an organic group selected from the group represented by the following formula (c):

In the above formula, D represents a direct bond, a sulfur atom or an oxygen atom; m is an integer of 0 to 2; R ³⁴ to R ⁴¹ may be the same or different and each represents a hydrogen atom, a fluorine atom or an alkyl group. Or an aromatic group is shown.   5. The compound according to claim 4, which has a structure consisting of a structure (Q1) represented by the above formula (q1) and a structure (Q2) represented by the above formula (q2). The structure (Q1) and the structure (Q2) are contained in amounts of 99 to 20 mol% and 1 to 80 mol%, respectively, with respect to a total of 100 mol% of the structures (Q1) and (Q2). The compound according to claim 7. A polyarylene comprising a repeating unit represented by the following formula (2 ′):

In the above formula, Z is an oxygen atom or a sulfur atom, or a divalent electron withdrawing group selected from the group consisting of — (CF ₂ ) _k —, —C (CF ₃ ) ₂ —, —SO— and —SO ₂ —. W ¹ and W ² independently represent a hydrogen atom or —COC _k H _{2k + 1} , —COAr, —CONHC _k H _{2k + 1} , —CONHAr, —COOC _k H _{2k + 1} , —COOAr, —CN, A monovalent electron withdrawing group selected from the group consisting of —CHO, —C _k F _{2k + 1} , —SOC _k H _{2k + 1} , —SOAr, —SO ₂ C _k H _{2k + 1} and —SO ₂ Ar is shown. Where k is an integer of 1 to 10, Ar represents a phenyl group or a naphthyl group; R ¹ and R ² independently represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group; N represents an integer of 2 or more; P represents a structure selected from the following formulas (p1) and (p2):

In the above formula, B and C independently represent a divalent atom, an organic electron withdrawing group or a direct bond; R ³ to R ²⁵ may be the same or different, and each represents a hydrogen atom, a fluorine atom, an alkyl group or an aromatic group. Q represents a structure selected from the following formulas (q1), (q2) and mixtures thereof:

The polyarylene according to claim 9, comprising a repeating unit represented by the following general formula (3):

In the above formula, E is a direct bond or —CO—, —CONH—, — (CF ₂ ) _p — (wherein p is an integer of 1 to 10), —C (CF ₃ ) ₂ —, —COO—. Represents an organic electron withdrawing group selected from the group consisting of -SO- and -SO _2- ; Ar is selected from the group consisting of phenyl, naphthyl, pyridyl, phenoxyphenyl, phenylphenyl and naphthoxyphenyl groups It indicates the aromatic group; L is a hydrogen atom, a fluorine atom or a _{-CN, -CHO, -C p F 2p} + 1, -OC p H 2p + 1, -SC p H 2p + 1, -NHCOC p H 2p ₊₁ , -NHSO ₂ C _p H _{2p + 1} , -OCOC _p H _{2p + 1} , -CONHC _p H _{2p + 1} , -COOC _p H _{2p + 1} , -SOC _p H _{2p + 1} , -SO ₂ C _p 1 represents a monovalent organic group selected from the group consisting of H _{2p + 1} and —SO ₃ C _p H _{2p + 1} (where p is an integer of 1 to 10); k is an integer of 0 to 3 .

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