JP4868787B2 - Polymer catalyst for acid-catalyzed conversion - Google Patents

Description

  The present invention relates to a polymer catalyst used in an acid-catalyzed conversion reaction of an organic compound.

  Conventionally, an acid-catalyzed conversion reaction of an organic compound [for example, (1) Friedel-Crafts reaction, (2) esterification reaction, (3) transesterification reaction, (4) etherification reaction, (5) hydration reaction, ( 6) Isomerization reaction etc.] As acid catalysts used, Lewis acids such as aluminum chloride, iron chloride and tin chloride (Non-patent Document 1), solid acids such as zeolite and silica-alumina (Non-patent Document 2), There have been proposed mineral acids such as sulfuric acid and phosphoric acid, and cation exchange resins such as Nafion (Patent Documents 1 and 2). However, these catalysts do not exhibit sufficient activity, and aluminum chloride used for acylation reaction in particular requires a catalyst amount of more than moles of reactants, and it is difficult to reuse the catalyst. There are also environmental problems such as the generation of waste catalyst.

JP-A-4-169552 JP 2000-281609 A Olah, G.A, Friedel-Crafts and Related Reactions; Wiley; NY (1963) Ono et al., Chemistry and Engineering of Zeolite; Kodansha Scientific (2000)

  An object of the present invention is to provide an environment-friendly catalyst that is widely and effectively used as an acid catalyst useful for an acid-catalyzed conversion reaction of an organic compound.

 As a result of intensive studies, the present inventors have a polymer catalyst having a repeating unit represented by the following general formula (1)

(Y represents a (k + 2) -valent aromatic residue, and P represents —CO—, —O—, —S—, —SO—, —SO ₂ —, —CONH—, —C (CF ₃ ) ₂ —. , A linking group selected from single bonds, k is an integer of 1 to 4, and the side chain portion Z in the formula is represented by the following general formula (2).
^{Z = - (X 1 Ar 1} (B 1)) - (X 2 Ar 2 (B 2)) - ··· - (X n-1 Ar n-1 (B n-1)) - (X n Ar ⁿ ) (2)
^{B 1 ~B n-1} in the general formula (2) in means a branched chain in the side chain moiety Z, is expressed by the following equation.
B ¹ = - ^{[(X 2 Ar 2 (B 2} )) - (X 3 Ar 3 (B 3)) - ··· - (X n-1 Ar n-1 (B n-1)) - (X ⁿ Ar ⁿ )] _f
B ² = - ^{[(X 3 Ar 3 (B 3} )) - ··· - (X n-1 Ar n-1 (B n-1)) - (
X ⁿ Ar ⁿ )] _f
・
・
・
B ⁿ⁻¹ = − [X ⁿ Ar ⁿ ] _f
In said general formula (2), n is an integer of 2-5 each independently,
f is each independently an integer of 0 to 5;
Ar ^{1 to} Ar ⁿ are each independently an aromatic residue,
X ^{1 to} X ⁿ are each independently —CO—, —CONH—, — (CF ₂ ) _p — (p is an integer of 1 to 10), —C (CF ₃ ) ₂ —, —COO—, —SO—. , —SO ₂ —.
Then, Z is a number greater than 1.0 of the -SO ₃ H group. )
Has been found to be extremely effective in the acid-catalyzed conversion reaction of organic substances in the liquid phase.
In particular, the present invention has been completed by finding that it is extremely active and effective as an acylation reaction catalyst which has been problematic in the past.
That is, the present invention is as follows.
1. A polymer catalyst used for an acid-catalyzed conversion reaction of an organic compound having at least a repeating unit represented by the following general formula (1).

(Y represents a (K + 2) -valent aromatic residue, and P represents —CO—, —O—, —S—, —SO—, —SO ₂ —, —CONH—, —C (CF ₃ ) ₂ —. , A linking group selected from single bonds, k is an integer of 1 to 4, and the side chain portion Z in the formula is represented by the following general formula (2).
^{Z = - (X 1 Ar 1} (B 1)) - (X 2 Ar 2 (B 2)) - ··· - (X n-1 Ar n-1 (B n-1)) - (X n Ar ⁿ ) (2)
^{B 1 ~B n-1} in the general formula (2) in means a branched chain in the side chain moiety Z, is expressed by the following equation.
B ¹ = - ^{[(X 2 Ar 2 (B 2} )) - (X 3 Ar 3 (B 3)) - ··· - (X n-1 Ar n-1 (B n-1)) - (X ⁿ Ar ⁿ )] _f
B ² = - ^{[(X 3 Ar 3 (B 3} )) - ··· - (X n-1 Ar n-1 (B n-1)) - (X n Ar n) ] _f
・
・
・
B ⁿ⁻¹ = − [X ⁿ Ar ⁿ ] _f
In said general formula (2), n is an integer of 2-5 each independently,
f is each independently an integer of 0 to 5;
Ar ^{1 to} Ar ⁿ are each independently an aromatic residue,
X ^{1 to} X ⁿ are each independently —CO—, —CONH—, — (CF ₂ ) _p — (p is an integer of 1 to 10), —C (CF ₃ ) ₂ —, —COO—, —SO—. , —SO ₂ —.
Then, Z is a number greater than 1.0 of the -SO ₃ H group. )

2. _2. The polymer catalyst according to item 1, wherein P is a linking group selected from —CO—, —O—, —S—, —SO ₂ —, and —C (CF ₃ ) ₂ —.
3. 3. The polymer catalyst as described in 1 or 2 above, wherein k is an integer of 1 to 2 and f is independently an integer of 0 to 2.
4). 4. The polymer catalyst according to item 3 above, wherein at least one f is 1 or 2. 4. The polymer catalyst according to item 3 above, wherein f is 0 or 1, and at least one f is 1.
6). 6. The polymer catalyst according to any one of items 1 to 5, wherein the acid-catalyzed conversion reaction is a Friedel-Crafts reaction.
7). 6. The polymer catalyst according to any one of items 1 to 5, wherein the acid-catalyzed conversion reaction is a transesterification reaction or a transesterification reaction.

  The catalyst of the present invention is (1) effective in small amounts because of high activity, (2) can be used for a long time without a decrease in activity, and (3) produces less waste by-product and does not generate halogen ions. Therefore, it contributes greatly to environmental conservation.

Hereinafter, the present invention will be described in detail.
The catalyst of the present invention includes at least a repeating unit (A) represented by the following general formula (1).

In the general formula (1), k is usually an integer of 1 to 4, and preferably 1 or 2. In the general formula (1), Y is a (k + 2) -valent aromatic residue, for example, a trivalent aromatic residue represented by the following general formula (7), a tetravalent aromatic residue represented by the following general formula (8) Aromatic residues, pentavalent aromatic residues represented by the following general formula (9), and the like can be mentioned. Hydrogen atoms alkyl groups of these aromatic residues, halogen atom, halogenated alkyl group, aryl group, halogenated aryl group, -CN, -NO _2, -COR, -COO R (R is selected from a hydrogen atom, an alkyl group, a halogenated alkyl group, and an aryl group), —CONRR ′ (R ′ is the same as R), —SO ₃ R, —SOR, —SO ₂ R in may be substituted, F, _{perfluoroalkyl, -CN, -NO 2, -COR,} -COO It is preferable that an electron-withdrawing group such as R, —CONRR ′, —SO ₃ R, —SOR, and —SO ₂ R is substituted.

In the general formulas (7) to (9), the divalent group Q is —CO—, —COO—, —O—, —S—, —SO—, —SO ₂ —, —CCR ¹ ₂ — (R ¹ Is selected from a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group and an aryl group) and a single bond, and preferably selected from —CO—, —O—, —S— and —SO ₂ —.
In the general formula (1), P is a linkage selected from —CO—, —O—, —S—, —SO—, —SO ₂ —, —CONH—, —C (CF ₃ ) ₂ —, and a single bond. A linking group selected from —CO—, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ —, and more preferably —CO—, —O—. , —S—, —SO ₂ —.
The side chain part Z in General formula (1) is represented by General formula (2).
^{Z = - (X 1 Ar 1} (B 1)) - (X 2 Ar 2 (B 2)) - ··· - (X n-1 Ar n-1 (B n-1)) - (X n Ar ⁿ ) (2)
^{B 1 ~B n-1} in the general formula (2) in means a branched chain in the side chain moiety Z, is expressed by the following equation.
B ¹ = - ^{[(X 2 Ar 2 (B 2} )) - (X 3 Ar 3 (B 3)) - ··· - (X n-1 Ar n-1 (B n-1)) - (X ⁿ Ar ⁿ )] _f
B ² = - ^{[(X 3 Ar 3 (B 3} )) - ··· - (X n-1 Ar n-1 (B n-1)) - (X n Ar n) ] _f
・
・
・
B ⁿ⁻¹ = − [X ⁿ Ar ⁿ ] _f

In the general formula (2), n independently represents an integer selected from 2 to 5, preferably selected from 2 to 4, and more preferably selected from 2 to 3. f represents an integer independently selected from 0 to 5, preferably from 0 to 2, and at least one f is 1 or 2, more preferably from 0 to 1, and at least One f is 1.
In the general formula (2), when f is 1 or more, the side chain represented by the general formula (2) has a branched structure in the aromatic residues Ar ^{1 to} Ar ^n-1 . Each branched chain may have a different chain length and branched structure. That is, the side chain represented by the general formula (2) of the present invention can have a structure represented by the following general formula (10), for example.

Ar ^{1 to} Ar ^n-1 in the general formula (2) represent an (f + 2) -valent aromatic residue, for example, a divalent aromatic residue represented by the following formula (11), 3 represented by the formula (7) Valent aromatic residues, tetravalent aromatic residues represented by formula (8), pentavalent aromatic residues represented by formula (9), and the like. Hydrogen atoms alkyl groups of these aromatic residues, halogen atom, halogenated alkyl group, aryl group, halogenated aryl group, -CN, -NO _2, -COR, -COO R (R is selected from a hydrogen atom, an alkyl group, a halogenated alkyl group, and an aryl group), —CONRR ′ (R ′ is the same as R), —SO ₃ R, —SOR, —SO ₂ R in may be substituted, F, _{perfluoroalkyl, -CN, -NO 2, -COR,} -COO It is preferable that an electron-withdrawing group such as R, —CONRR ′, —SO ₃ R, —SOR, and —SO ₂ R is substituted. Ar ^{1 to} Ar ^n-1 may be the same as or different from each other.

Further, Ar ⁿ in the general formula (1) represents an aryl group at the end of the side chain, and examples thereof include an aryl group represented by the following formula (12), and the hydrogen atom of the aryl group is an alkyl group, a halogen atom, or a halogenated group. alkyl group, aryl group, halogenated aryl group, -CN, -NO _2, -COR, -COO R (R is selected from a hydrogen atom, an alkyl group, a halogenated alkyl group, and an aryl group), —CONRR ′ (R ′ is the same as R), —SO ₃ R, —SOR, —SO ₂ R Ar ⁿ may be the same as or different from each other.

The ^X 1 to X ⁿ in the general formula (1) represents a divalent electron withdrawing group, for example, -CO -, - CONH -, - (CF 2) p - ( wherein, p is from 1 to 10 is an _{integer), - C (CF 3)} 2 -, - COO -, - SO -, - SO 2 - is like, preferably _{-CO -, - C (CF 3} ) 2 -, - SO-, -SO ₂ - and more preferably -CO -, - SO -, - SO 2 - and the like are used. X ^{1 to} X ⁿ may be the same as or different from each other. In the general formula (1) of the present invention, specific examples of the side chain represented by Z include a group of the following formula (13).

（上記式中、スルホン酸基は記載していない。）

(In the above formula, sulfonic acid groups are not described.)

As the polymer catalyst used in the present invention, a side chain selected from an unbranched side chain and a branched side chain is usually used, and a branched side chain is preferably used. The branched side chain (i) has a large number of terminal aromatic rings that are easily sulfonated, and it is possible to introduce a plurality of hydrophilic sulfonic acid groups into the same side chain, thus increasing the water content. Can be considered.
In the general formula (2), when f is 1 or more, the side chain represented by the general formula (2) has a branched structure in the aromatic residues Ar ^{1 to} Ar ^n-1 . Each branched chain may have a different chain length and branched structure. That is, the side chain represented by the general formula (2) of the present invention can have, for example, a structure represented by the formula (10).

  The polymer catalyst used in the present invention has at least the repeating unit (A) represented by the general formula (1), and usually contains 1 to 100 mol% of the repeating unit (A) represented by the general formula (1). And preferably 5 to 95 mol%, more preferably 10 to 80 mol%, particularly preferably 15 to 75 mol%, and the weight average molecular weight is 1,000 to 1,000,000, preferably 10,000 to 1,000,000, more preferably 2 Examples thereof include polymer catalysts that are 10,000 to 800,000, particularly preferably 30,000 to 400,000 polymers.

The method for producing the polymer catalyst used in the present invention is not particularly limited. For example,
(M1) Method of introducing a side chain by reacting a polymer with a side chain introduction agent -Y-P- (Y is a divalent aromatic, corresponding to the structure in which Z is not substituted in the general formula (1)) Z may be introduced by reacting a side chain introducing agent with a polymer having a residue, P as described above as a repeating unit, or -Y (M) -P in which a reactive substituent has been introduced in advance. Z may be introduced by reacting-(Y is a trivalent aromatic residue, M is a reactive group, and P is as described above) with a side chain introducing agent that reacts with M.
(M2) A method for polymerizing a monomer having at least a side chain

It can also be obtained by polymerizing the monomer corresponding to the repeating structural unit (A) and the monomer corresponding to the other repeating unit, and the oligomer corresponding to the repeating unit (A) and the monomer corresponding to the other repeating unit are first oligomers. And then reacting the oligomers with each other or with the oligomer and monomers. In addition, a monomer corresponding to a structure in which the repeating unit (A) and one or a plurality of other repeating units are linked is synthesized in advance, and homopolymerization of this monomer or polymerization of this with a monomer corresponding to another repeating structure. Can also be synthesized.
Specific examples of the method (M1) that are usually used are as follows. That is, by reacting a polymer having a repeating unit represented by the following general formula (3) with a side chain introducing agent represented by the following general formula (4), the polymer catalyst represented by the general formula (1) Can be manufactured. In this case, X in the general formula (2) is selected from —CO— and —SO ₂ —.

In the general formula (3), Y and P are the same as those described in the general formula (1), U is a reactive group selected from a hydrogen atom, —COX, and —SO ₂ X, and X is a halogen atom. It is selected from an atom, OR (R is a hydrogen atom, an alkyl group, or an aryl group), and a hydroxyl group.
Z'-V (4)
When U in the general formula (3) is a hydrogen atom, V is a reactive group selected from —COX and —SO ₂ X, and U is a reactive group selected from —COX and —SO ₂ X In the formula, V is a hydrogen atom, and Z ′ is represented by the following general formula (5).
^{Z '= - (Ar 1 (} B 1)) - (X 2 Ar 2 (B 2)) - ··· - (X n-1 Ar n-1 (B n-1)) - (X n Ar n (5)
In the general formula (5), Ar, B, and n are the same as those described in the general formula (2), and X is selected from the linking group and the linking group precursor described in the general formula (2). . )
A linking group precursor refers to a group that can be converted to a linking group. As a method for converting the linking group precursor into a linking group, a known method can be used. Table 1 shows an example.

The linking group precursor may be converted to the linking group at any point, but the following method is preferably used. That is, when the polymer having a repeating unit represented by the general formula (3) and the side chain introducing agent represented by the general formula (4) are reacted,
(I) The side chain introducing agent does not have a sulfonic acid group or a precursor thereof, and X of the side chain introducing agent is an electron donating linking group precursor, and is sulfonated after reacting with a polymer. Followed by converting the linking group precursor to an electron-withdrawing linking group, or
(Ii) when the side chain introducing agent has a sulfonic acid group or a precursor thereof, and X of the side chain introducing agent is (ii-1) an electron donating linking group precursor, By converting the linking group precursor into an electron-withdrawing linking group, (ii-2) when it is an electron-withdrawing linking group, the repeating unit represented by the general formula (1) It is a method of obtaining the polymer catalyst which has.

Examples of the polymer having a repeating unit represented by the general formula (3) used in the present invention are shown below.
U those hydrogen atoms: and a divalent aromatic residue selected from residues represented by the general formula (11), -CO -, - O -, - S -, - SO -, - SO 2 -, A polymer comprising a combination of —CONH—, —C (CF ₃ ) ₂ — and a linking group P selected from a single bond is usually used, and preferably a divalent aromatic residue selected from phenylene, naphthylene and biphenylene A combination of linking groups P selected from —CO—, —O—, —S—, —SO ₂ — is used, more preferably polyether ketone, polyether sulfone, polythioether ketone, polythioether sulfone, polyether ether. Sulfone and polyetheretherketone are used, and more preferably, a polymer represented by the following formula having Z as a hydrogen atom is used.

When U is —COX or —SO ₂ X: a divalent aromatic residue selected from the residues represented by the general formula (11), —CO—, —O—, —S—, —SO—, A polymer in which —COX or —SO ₂ X is introduced into a polymer composed of a combination of —SO ₂ —, —CONH—, —C (CF ₃ ) ₂ —, and a linking group P selected from a single bond is usually used. Is a polymer of a combination of a divalent aromatic residue selected from phenylene, naphthylene, and biphenylene and a linking group P selected from —CO—, —O—, —S—, and —SO ₂ —. which was introduced _{2 X} is used, more preferably polyether ketone, polyether sulfone, polythioether ketone, polythioether sulfone, polyether ether sulfone, polyether ether ketone Which was introduced COX or -SO ₂ X is used, or more preferably, those wherein Z in the polymer represented by the above formula was introduced -COX or -SO ₂ X is used. (A known introduction method can be used to introduce —COX or —SO ₂ X). X in the COX and SO ₂ X of the general formula (3) U is usually selected from a halogen atom, OR (R is a hydrogen atom, an alkyl group, or an aryl group), and a hydroxyl group, preferably from a halogen atom and a hydroxyl group. To be elected. Examples of the side chain introducing agent represented by the general formula (4) are shown below.
Reactivity in which the side chain introducing agent has a sulfonic acid group or a precursor thereof, X in the side chain introducing agent is an electron-withdrawing linking group, and V is selected from —COX and —SO ₂ X Examples of preferred Z′-V in the case of a group are shown in the following general formula (14) and the following general formula (15). Further preferred Z′-V is a branched structure represented by the following general formula (15). (In the formula, —SO ₃ R represents a sulfonic acid group or a precursor thereof, and R is selected from a hydroxyl group, an alkyl group, an alkali metal, and an alkaline earth metal.)

The side chain introducing agent does not have a sulfonic acid group or a precursor thereof, X of the side chain introducing agent is an electron donating linking group precursor, and V is from —COX and —SO ₂ X Examples of preferred Z′-V in the case of the selected reactive group are shown in the following general formula (16) and the following general formula (17). Further preferred Z ′ is a branched structure represented by the following general formula (17). Examples of preferred Z′-V in the case where V is a hydrogen atom are shown in the following general formula (18) and the following general formula (19).

X in V in the general formula (4) is usually selected from a halogen atom, OR (R is a hydrogen atom, an alkyl group, or an aryl group), and a hydroxyl group, and preferably selected from a halogen atom and a hydroxyl group.
The type of reaction when the side chain introduction agent is reacted with the polymer is not particularly limited. As a preferable method for reacting the polymer represented by the general formula (3) with the side chain introducing agent represented by the general formula (4), the following method may be mentioned.
(I) U in the general formula (3) is a hydrogen atom, V in the general formula (4) is —COX (X is a halogen atom or a hydroxyl group), or U in the general formula (3) is When -COX (X is a halogen atom) and V in the general formula (4) is a hydrogen atom: Friedel-Crafts-acylation reaction can be used.
(Ii) U in the general formula (3) is a hydrogen atom, V in the general formula (4) is —SO ₂ X (X is a halogen atom or a hydroxyl group), or in the general formula (3) When U is —SO ₂ X (X is a halogen atom) and V in the general formula (4) is a hydrogen atom: Friedel-Crafts type sulfonylation reaction can be used.
(Iii) U in the general formula (3) is a hydrogen atom, V in the general formula (4) is —COOH or —SO ₃ H, or U in the general formula (3) is —COOH or When —SO ₃ H and V in the general formula (4) are a hydrogen atom: a dehydration condensation reaction can be used.

A specific example of the method (M2) is shown below. That is, the polymer catalyst represented by the general formula (1) can be produced by polymerizing at least the monomer represented by the general formula (18).
The linking group precursor may be converted to the linking group at any point, but the following method is preferably used. That is, when polymerizing at least a monomer represented by the following general formula (6), (i) Z ″ does not have a sulfonic acid group or a precursor thereof, and X of Z ″ is an electron-donating linking group. A precursor, which is subjected to sulfonation after polymerization and subsequently converting the linking group precursor into an electron-withdrawing linking group, or (ii) Z ″ has a sulfonic acid group or its precursor. And when X of Z ″ is (ii-1) an electron-donating linking group precursor, the linking group precursor is subsequently converted into an electron-withdrawing linking group, whereby (ii) -2) In the case of an electron-withdrawing linking group, in this state, a polymer catalyst having a repeating unit represented by the general formula (1) is obtained.

[Wherein, k and Y are the same as those in the general formula (1), W and W ′ are a hydrogen atom, halogen, —COX (X is a halogen or OR (R is a hydrogen atom, an alkyl group, or an aryl group) ), —OH, —SH, —SO ₂ X (X is as defined above), which may be the same or different, and Z ″ is selected from the linking group and the linking group precursor described above. And is the same as Z in the general formula (1) except that Ar may have a sulfonic acid group.]
In the polymer of the present invention, any other repeating unit other than the repeating unit (A) can be used as long as it can be polymerized, and the repeating unit represented by the following general formula (20) (B ) Is preferably used.
-Y ² -P ² - (20)
In the formula, Y ² is selected from the same divalent aromatic residues as those shown in the general formula (11), and the hydrogen atom of the aromatic residue is an alkyl group, a halogen atom, a halogenated alkyl group, Or may be substituted with an aryl group, and P ² is —CO—, —O—, —S—, —SO—, —SO ₂ —, —COO—, —SO ₃ —, —CONH—, a single bond selected from, preferably -CO -, - O -, - S -, - SO 2 - is selected from. ]

In the preferred polymer of the present invention, the repeating unit (A) and other repeating units (hereinafter, for the sake of simplicity, Y side chain group Z is abbreviated in this paragraph), for example, —Y—P—Y ² —P ² —. As in Y—P—, Y or Y ² may be bonded to Y or Y ² via P or P ² , and an arbitrary repeating order can be taken. For _{example, - (Y-P) m} - (Y 2 -P 2) n - [m, n is a positive integer may be a block polymer such as, or may be a random polymer. The ratio of the repeating unit (A) to other repeating units is 5 to 95 mol%, preferably 10 to 80 mol%, more preferably 15 to 75 mol%, and 95 to 5 other repeating units. It is mol%, preferably 90 to 20 mol%, more preferably 85 to 25 mol%. When another repeating unit other than the repeating unit (A) is composed of the repeating unit (B), the same type of repeating unit (B) may be used, or a plurality of types of repeating units (B) may be used. Also good.

Hereinafter, an example of a synthesis method usually used as the method (M2) will be described.
[Synthesis Method-1] In the present invention, a coupling reaction between aromatic halides using a transition catalyst is preferably used as a reaction for producing a polymer in which the linking group P is a single bond. . For example, the methods described in Patent Document 3 and Patent Document 6 can be used.
[Synthesis Method-2] In the present invention, aromatic compounds of aromatic hydroxy compounds and aromatic halides are preferably used as a reaction for producing a polymer in which the linking group P and / or P ² is —O—. This is a synthesis reaction of an aromatic polyether by a group nucleophilic substitution reaction.
For example, the method described in Reference 1 (“High Performance Aromatic Polymer Material” edited by the Society of Polymer Science, Maruzen Co., Ltd., March 30, 1990, p. 128-132) can be used. As another method, a reaction in which aromatic halides are reacted with each other in the presence of a carbonate and a catalyst to synthesize an aromatic polyether can be used. For example, the method described in Reference 2 (Fukawa et al., Macromolecules, 1991, Vol. 24, p. 3838) can be used.

In Synthesis process -3 present invention, as preferably used reaction in the linking group P and / or P ² to produce a polymer which is -S-, an aromatic hydroxy compound in the synthesis method -2 Instead, an aromatic polysulfide is synthesized using an aromatic thiol compound. As another method, a reaction of synthesizing an aromatic polysulfide from aromatic dichloride and sodium sulfide can be used. For example, p. The method described in 133-134 can be used.
In Synthesis method -4] The present invention, linking groups P and / or P ² is -SO ₂ - to be preferably used as a reaction in the production of a is polymer, aromatic produced by the above synthesis method -3 In this method, sulfides are oxidized using an oxidizing agent such as hydrogen peroxide.
As another method, an aromatic compound having an aromatic ring having a hydrogen atom in an aromatic ring can be used by forming an aromatic sulfone bond by subjecting an aromatic sulfonic acid halide to an electrophilic substitution reaction. For example, p. The method described in 132-133 can be used.
[Synthesis Method-5] In the present invention, a Friedel-Crafts-acylation reaction is preferably used as a reaction for producing a polymer in which the linking group P and / or P ² is —CO—. For example, p. The method described in 132-133 can be used.

Next, an example of a preferred synthesis method by the method (M2) will be described. [Example of polymer-1] The polymer is composed of a repeating unit (A) and a repeating unit (B), and the linking groups P and P ² are In the case of -O-: For example, the reaction of the repeating unit (A) monomer represented by the following general formula (21) with the repeating unit (B) monomer represented by the following general formula (22), or the following general formula (23) Reaction of the repeating unit (A) monomer shown in FIG. 5 with the repeating unit (B) monomer shown in the following general formula (24), or the repeating unit (A) monomer shown in the following general formula (25), and the following general formula ( The polymer represented by the following general formula (27) comprising the repeating unit (A) and the repeating unit (B) can be obtained by the reaction with the repeating unit (B) monomer shown in (26).

［式中、Ｘはハロゲン原子を表し、Ｙ 、Ｙ² 、Ｚ”は前記のとおりである。］

[Wherein X represents a halogen atom, Y , Y ² and Z ″ are as described above.]

In addition, by using a raw material using a sulfur atom instead of the oxygen atom in the general formulas (22), (23), (25), and (26), all of the linking groups P and P ² are —S—. A polymer can be obtained.
Specific examples of the repeating unit (A) monomer represented by the general formula (21) include 2,5-dichloro-4 ′-(4-thiophenoxy-4-thiophenoxy) thiophenoxybenzophenone, 2,5- Dibromo-4 '-(4-thiophenoxy-4-thiophenoxy) thiophenoxybenzophenone, 2,5-diiodo-4'-(4-thiophenoxy-4-thiophenoxy) thiophenoxybenzophenone; 2,5-dichloro -4 '-(4-thiophenoxy) thiophenoxybenzophenone, 2,5-dibromo-4'-(4-thiophenoxy) thiophenoxybenzophenone, 2,5-diiodo-4 '-(4-thiophenoxy) thiophenoxy Benzophenone; 2,5-dichloro-4'-thiophenoxybenzophenone, 2,5-dibromo-4'-thiophene Xylbenzophenone, 2,5-diiodo-4′-thiophenoxybenzophenone; 2,5-dichloro-1- (4-thiophenoxy) thiophenoxybenzene, 2,5-dibromo-1- (4-thiophenoxy) thiophenoxy Benzene, 2,5-diiodo-1- (4-thiophenoxy) thiophenoxybenzene; 2,5-dichloro-1- (4-thiophenoxy-4-thiophenoxy) thiophenoxybenzene, 2,5-dibromo-1 -(4-thiophenoxy-4-thiophenoxy) thiophenoxybenzene, 2,5-diiodo-1- (4-thiophenoxy-4-thiophenoxy) thiophenoxybenzene; 2,5-dichloro-4 '-(4 -Benzoyl) benzoylbenzophenone, 2,5-dibromo-4 '-(4-benzoyl) benzoylbenzof Enone, 2,5-diiodo-4 ′-(4-benzoyl) benzoylbenzophenone; 2,5-dichloro-4′-benzoylbenzophenone, 2,5-dibromo-4′-benzoylbenzophenone, 2,5-diiodo-4 Examples include '-benzoylbenzophenone and regioisomers thereof.

  Specific examples of the repeating unit (A) monomer represented by the general formula (23) include 2,5-dihydroxy-4 ′-(4-thiophenoxy-4-thiophenoxy) thiophenoxybenzophenone; Dihydroxy-4 ′-(4-thiophenoxy) thiophenoxybenzophenone; 2,5-dihydroxy-4′-thiophenoxybenzophenone; 2,5-dihydroxy-1- (4-thiophenoxy) thiophenoxybenzene; Dihydroxy-1- (4-thiophenoxy-4-thiophenoxy) thiophenoxybenzene; 2,5-dihydroxy-4 ′-(4-benzoyl) benzoylbenzophenone; 2,5-dihydroxy-4′-benzoylbenzophenone and their And positional isomers.

Specific examples of the repeating unit (A) monomer represented by the general formula (25) include 2-chloro-5-hydroxy-4 ′-(4-thiophenoxy-4-thiophenoxy) thiophenoxybenzophenone, 2- Bromo-5-hydroxy-4 ′-(4-thiophenoxy-4-thiophenoxy) thiophenoxybenzophenone, 2-iodo-5-hydroxy-4 ′-(4-thiophenoxy-4-thiophenoxy) thiophenoxybenzophenone, 2-chloro-5-hydroxy-4 ′-(4-thiophenoxy) thiophenoxybenzophenone, 2-bromo-5-hydroxy-4 ′-(4-thiophenoxy) thiophenoxybenzophenone, 2-iodo-5-hydroxy -4 '-(4-thiophenoxy) thiophenoxybenzophenone; 2-chloro-5-hydroxy -4'-thiophenoxybenzophenone, 2-bromo-5-hydroxy-4'-thiophenoxybenzophenone, 2-iodo-5-hydroxy-4'-thiophenoxybenzophenone; 2-chloro-5-hydroxy-1- (4 -Thiophenoxy) thiophenoxybenzene, 2-bromo-5-hydroxy-1- (4-thiophenoxy) thiophenoxybenzene, 2-iodo-5-hydroxy-1- (4-thiophenoxy) thiophenoxybenzene; Chloro-5-hydroxy-1- (4-thiophenoxy-4-thiophenoxy) thiophenoxybenzene, 2,5-dibromo-1- (
4-thiophenoxy-4-thiophenoxy) thiophenoxybenzene, 2-iodo-5-hydroxy-1- (4-thiophenoxy-4-thiophenoxy) thiophenoxybenzene; 2-chloro-5-hydroxy-4′- (4-benzoyl) benzoylbenzophenone, 2-bromo-5-hydroxy-4 ′-(4-benzoyl) benzoylbenzophenone, 2-iodo-5-hydroxy-4 ′-(4-benzoyl) benzoylbenzophenone; 2-chloro- Examples include 5-hydroxy-4′-benzoylbenzophenone, 2-bromo-5-hydroxy-4′-benzoylbenzophenone, 2-iodo-5-hydroxy-4′-benzoylbenzophenone, and positional isomers thereof.

  Specific examples of the repeating unit (B) monomer represented by the general formula (22) include 4,4′-dihydroxybenzophenone, 2,4′-dihydroxybenzophenone, 3,3′-dihydroxybenzophenone; -Dihydroxydiphenyl ether, 2,4'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether; 4,4'-dihydroxydiphenyl thioether, 2,4'-dihydroxydiphenyl thioether, 3,3'-dihydroxydiphenyl thioether; 2,2 -Bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-hydroxyphenyl) hexafluoropropane; bis (hydroxyphenyl) difluoromethane; 4-hydroxybenzoic acid-4-hydroxyphenyl, -Hydroxybenzoic acid-3-hydroxyphenyl, 3-hydroxybenzoic acid-3-hydroxyphenyl, 3-hydroxybenzoic acid-4-hydroxyphenyl; bis (4-hydroxyphenyl) sulfoxide, bis (3-hydroxyphenyl) sulfoxide; Bis (4-hydroxyphenyl) sulfone, bis (3-hydroxyphenyl) sulfone; 2,5-dihydroxy4'-phenoxybenzophenone, p-dihydroxybenzene, 2,5-dihydroxytoluene, 2,5-dihydroxyp-xylene, 2,4-dihydroxybenzotrifluoride, 1,4-dihydroxy 2,3,5,6-tetrafluorobenzene; 4,4'-dihydroxybiphenyl; m-dihydroxybenzene, 2,4-dihydroxytoluene, 3,5- Dihydroxy Toluene, 2,6-dihydroxy-toluene and the like.

Specific examples of the repeating unit (B) monomer represented by the general formula (24) include 4,4'-dichlorobenzophenone, 2,4'-dichlorobenzophenone, 3,3'-dichlorobenzophenone, 4,4 ' -Dibromobenzophenone, 2,4'-dibromobenzophenone, 3,3'-dibromobenzophenone, 4,4'-diiodobenzophenone, 2,4'-diiodobenzophenone, 3,3'-diiodobenzophenone; 4,4 '-Dichlorodiphenyl ether, 2,4'-dichlorodiphenyl ether, 3,3'-dichlorodiphenyl ether, 4,4'-dibromodiphenyl ether, 2,4'-dibromodiphenyl ether, 3,3'-, dibromodiphenyl ether, 4,4' -Diiododiphenyl ether, 2,4'-diiododi Phenyl ether, 3,3′-diiododiphenyl ether; 4,4′-dichlorodiphenyl thioether, 2,4′-dichlorodiphenyl thioether, 3,3′-dichlorodiphenyl thioether, 4,4′-dibromodiphenyl thioether, 2, 4'-dibromodiphenyl thioether, 3,3'-, dibromodiphenyl thioether, 4,4'-diiododiphenyl thioether, 2,4'-diiododiphenyl thioether, 3,3'-diiododiphenyl thioether:
2,2-bis (4-chlorophenyl) hexafluoropropane, 2,2-bis (3-chlorophenyl) hexafluoropropane, 2,2-bis (4-bromophenyl) hexafluoropropane, 2,2-bis (3 -Bromophenyl) hexafluoropropane, 2,2-bis (4-iodophenyl) hexafluoropropane, 2,2-bis (3-iodophenyl) hexafluoropropane; bis (chlorophenyl) difluoromethane, bis (bromophenyl) Difluoromethane, bis (iodophenyl) difluoromethane; 4-chlorobenzoic acid-4-chlorophenyl, 4-chlorobenzoic acid-3-chlorophenyl, 3-chlorobenzoic acid-3-chlorophenyl, 3-chlorobenzoic acid-4-chlorophenyl 4-bromobenzoic acid-4-bromophenyl 4-bromobenzoic acid-3-bromophenyl, 3-bromobenzoic acid-3-bromophenyl, 3-bromobenzoic acid-4-bromophenyl; bis (4-chlorophenyl) sulfoxide, bis (3-chlorophenyl) sulfoxide, bis (4-bromophenyl) sulfoxide, bis (3-bromophenyl) sulfoxide, bis (4-iodophenyl) sulfoxide, bis (3-iodophenyl) sulfoxide;
Bis (4-chlorophenyl) sulfone, bis (3-chlorophenyl) sulfone, bis (4-bromophenyl) sulfone, bis (3-bromophenyl) sulfone, bis (4-iodophenyl) sulfone, bis (3-iodophenyl) Sulfone; 2,5-dichloro-4'-phenoxybenzophenone, p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, 2,5-dichlorotoluene, 2,5-dibromotoluene, 2,5-diiodo Toluene, 2,5-dichloro-p-xylene, 2,5-dibromo-p-xylene, 2,5-diiodo-p-xylene, 2,5-dichlorobenzotrifluoride, 2,5-dibromobenzotrifluoride, 2,5-diiodobenzotrifluoride, 1,4-dichloro-2,3,5,6-tetra Fluorobenzene, 1,4-dibromo-2,3,5,6-tetrafluorobenzene, 1,4-diiodo-2,3,5,6-tetrafluorobenzene; 4,4'-dichlorobiphenyl, 4,4 ' -Dibromobiphenyl, 4,4'-diiodobiphenyl, 4,4'-dibromooctafluorobiphenyl; m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 2,4-dichlorotoluene, 2,4- Dibromotoluene, 2,4-diiodotoluene, 3,5-dichlorotoluene, 3,5-dibromotoluene, 3,5-diiodotoluene, 2,6-dichlorotoluene, 2,6-dibromotoluene, 2,6 -Diiodotoluene, 1,3-dibromo-2,4,5,6-tetrafluorobenzene and the like. In addition, in the said specific example, what substituted one of two X in General formula (15) by the fluorine atom can be used preferably.
As a specific example of the repeating unit (B) monomer represented by the general formula (26), one of non-fluorine halogen atoms in the specific example of the repeating unit (B) monomer represented by the general formula (15). And a positional isomer thereof.

Specific examples of synthesis in the case where the polymer is composed of the repeating unit (A) and the repeating unit (B) and the linking groups P and P ² are both —O— are shown below. 2,5-Dichloro-4 ′-(4-thiophenoxy) thiophenoxybenzophenone is used as the monomer of the repeating unit (A), and p, p′-dihydroxybenzophenone is used as the monomer of the repeating unit (B). Both are copolymerized in the presence of potassium carbonate, then sulfonated using a sulfonated agent, and then oxidized to a sulfone by oxidizing the sulfide bond using an oxidant to form a linking group P = O, A sulfone oxide of a polymer (Q = —CO—) represented by the following general formula (28) where P ² ═O is obtained as a polymer catalyst.

［式中、Ｚ”は側鎖基を示す。］

[In the formula, Z ″ represents a side chain group.]

Similarly, Q is —O—, —S—, —SO ₂ —, —CR ¹ ₂ — (R ¹ is selected from a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, and an aryl group) or a single atom. A polymer that is a bond can be synthesized.
[Example of polymer-2] When the polymer is composed of a repeating unit (A) and a repeating unit (B), and both of the linking groups P and P ² are single bonds: the repeating unit represented by the following general formula (29) (A)
By reacting the monomer with the repeating unit (B) monomer represented by the following general formula (30), a polymer represented by the following general formula (31) comprising the repeating unit (A) and the repeating unit (B) is obtained. be able to. Specific examples of the repeating unit (A) monomer represented by the following general formula (29) include the same compounds as the specific examples for the general formula (21). Specific examples of the repeating unit (B) monomer represented by the following general formula (30) include compounds similar to the specific examples for the general formula (24).

［式中、Ｘ、Ｘ’は互いに同一であっても異なっていても良いハロゲン原子を表し、Ｙ、Ｙ² 、Ｚは前記のとおりである。］

[Wherein, X and X ′ represent the same or different halogen atoms, and Y, Y ² and Z are as defined above. ]

Specific examples of the case where the polymer is composed of the repeating unit (A) and the repeating unit (B) and the linking groups P and P ² are both single bonds are shown below. 2,5-Dichloro-4′-thiophenoxybenzophenone is used as the monomer of the repeating unit (A), and p, p′-dichlorodiphenylsulfone is used as the monomer of the repeating unit (B). Both are copolymerized in the presence of a catalyst containing a transition metal compound, then sulfonated using a sulfonated agent, and then oxidized by using an oxidant to convert the sulfide bond to a sulfone. A sulfone oxide of a polymer (Q = —SO ₂ —) represented by the following general formula (32) having the group P = single bond and P ² = single bond is obtained as a polymer catalyst.

［式中、Ｚ”は側鎖基を示す。］

[In the formula, Z ″ represents a side chain group.]

[Polymer Example-3] When the polymer is composed of a repeating unit (A) and a repeating unit (B) and both of the linking groups P and P ² are —CO—: for example, shown in the following general formula (33). Reaction of the repeating unit (A) monomer with the repeating unit (B) monomer shown in the following general formula (34), or the repeating unit (A) monomer shown in the following general formula (35) and the following general formula ( A polymer represented by the following general formula (37) consisting of the repeating unit (A) and the repeating unit (B) can be obtained by the reaction with the repeating unit (B) monomer shown in 36). In addition, by using a raw material using SO ₂ instead of CO in the following general formulas (34) and (35), the coupler P And a polymer in which both P ² are —SO ₂ — is obtained. [Wherein, X represents a halogen atom, and Y, Y ² and Z are as defined above. ]

As a specific example of the repeating unit (A) monomer represented by the general formula (33), -X in the specific example of the repeating unit (A) monomer represented by the general formula (21) is substituted with a hydrogen atom. And the positional isomers thereof.
Specific examples of the repeating unit (A) monomer represented by the general formula (35) include -X in the specific example of the repeating unit (A) monomer represented by the general formula (21) -COX (X Represents a halogen atom) and the positional isomers thereof.
Specific examples of the repeating unit (B) monomer represented by the general formula (34) include -X in the specific example of the repeating unit (B) monomer represented by the general formula (24) -COX (X Represents a halogen atom) and the positional isomers thereof.
As a specific example of the repeating unit (B) monomer represented by the general formula (36), X in the specific example of the repeating unit (B) monomer represented by the general formula (24) was substituted with a hydrogen atom. Examples include structures.

Specific examples of synthesis in the case where the polymer is composed of the repeating unit (A) and the repeating unit (B) and the linking groups P and P ² are both —CO— are shown below. 2- [4- (4-thiophenoxy) thiophenoxybenzoyl] terephthal chloride is used as the monomer of the repeating unit (A), and diphenyl ether is used as the monomer of the repeating unit (B). Both are copolymerized in the presence of a Friedel-Crafts catalyst such as aluminum chloride, then sulfonated with a sulfonated agent, and then oxidized with an oxidant to convert the sulfide bond to sulfone, A sulfone oxide of a polymer (Q = —O—) represented by the following general formula (38) having a linking group P═CO and P ² ═CO is obtained as a polymer catalyst.

［式中、Ｚ”は側鎖基を示す。］

[In the formula, Z ″ represents a side chain group.]

Similarly, Q is —CO—, —S—, —SO ₂ —, —CR ¹ ₂ — (R ¹ is selected from a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, and an aryl group) or a single atom. A polymer that is a bond can be synthesized.
[Example of polymer-4] When the polymer is composed of a repeating unit (A) and a plurality of repeating units (B), the linking group P is a single bond and the linking group P ² is —O—: 39), the repeating unit (A) monomer and the repeating unit (B) monomer represented by the following general formula (40) and the following general formula (41) are reacted with the repeating unit (A) and two kinds of repeating units. A polymer represented by the following general formula (42) consisting of the unit (B) can be obtained.

［式中、Ｘ、Ｘ’、Ｘ’’はハロゲン原子を表し互いに異なっていても同一でも良く、Ｙ² ’はＹ² と同様の基であり、Ｙ、Ｙ² 、Ｚは前記のとおりである。］

Wherein, X, X ', X'' may be the same or different from one another represent a halogen atom, Y ^2' is the same group as ^{Y 2, Y, Y 2,} Z is as defined above is there. ]

Specific examples of the repeating unit (A) monomer represented by the general formula (39) include compounds similar to the specific examples for the general formula (21). Specific examples of the repeating unit (B) monomer represented by the general formula (40) include compounds similar to the specific examples for the general formula (24). Specific examples of the repeating unit (B) monomer represented by the general formula (41) include the same compounds as the specific examples for the general formula (22).
Specific examples of the case where the polymer is composed of the repeating unit (A) and the repeating unit (B), the linking group P is a single bond, and the linking group P ² is —O— are shown below. 2,5-Dichloro-4′-thiophenoxybenzophenone is used as the monomer of the repeating unit (A), and 4-chlorofluorobenzene and 4,4′-dihydroxybenzophenone are used as the monomer of the repeating unit (B). First, bis [4- (4-chlorophenoxy) phenyl] sulfone is synthesized by reacting 4-chlorofluorobenzene and bis (4-hydroxyphenyl) sulfone in the presence of potassium carbonate. Next, this and 2,5-dichloro-4'-thiophenoxybenzophenone are copolymerized in the presence of a catalyst containing a transition metal compound, and then sulfonated with a sulfonated agent, and then a sulfide bond is formed. Oxidation using an oxidizing agent and conversion to sulfone allows sulfonation of a polymer (Q = —SO ₂ —) represented by the following general formula (43) having a linking group P = single bond and P ² = —O— bond. Is obtained as a polymer catalyst. In the polymer of the present invention, the proportion of the repeating unit (B) in the other repeating units is 10 to 100 mol%, preferably 20 to 100 mol%.

［式中、Ｚ”は側鎖基を示す。］

[In the formula, Z ″ represents a side chain group.]

The aromatic residue contained in the main chain of the polymer catalyst used in the present invention preferably has at least one electron withdrawing group bonded thereto. The electron withdrawing group in this case is, for example, —CO—, —CONH—, — (CF ₂ ) _p — (wherein p is an integer of 1 to 10), —C (CF ₃ ) ₂ —, — Divalent groups such as COO—, —SO—, —SO—, —SO ₂ —; F, perfluoroalkyl, —CN, —NO ₂ , —COR, —COOR (where R is hydrogen, alkyl group, halogenated) Selected from an alkyl group, an aryl group, and a halogenated aryl group), -CONRR '(R' is the same group as the above R), -SO ₃ R, -SOR, -SO ₂ R, etc. Groups.
Examples of the structure of the polymer catalyst used in the present invention are shown below. [In formula, Z shows the side chain represented by the said General formula (1). ]

  In the polymer catalyst used in the present invention, a sulfonic acid group is present in the side chain Z. And at least n ≧ 2, and the number of sulfonic acid groups exceeding 1.0 is introduced. In addition, when Z is linear, the sulfonic acid group may be introduce | transduced into several Ar group of the same side chain. Furthermore, the main chain may be further substituted with a sulfonic acid group. In the production method of the present invention, the method for introducing a sulfonic acid group is not limited. For example, (1) the polymer may be introduced by sulfonating, or (2) a monomer containing a sulfonic acid group is polymerized. Alternatively, (3) a sulfonic acid group can be introduced by polymerizing a monomer containing a group selected from a sulfonic acid group derivative and a sulfonic acid group precursor and then converting the group into a sulfonic acid group.

In the method for producing a polymer catalyst used in the present invention, as a method for introducing a sulfonic acid group, when a polymer not containing a sulfone group is introduced by sulfonating, a conventional sulfone with a sulfonating agent is used. Oxidation can be used. As a method for introducing a sulfonic acid group, for example, the above-described polymer having no sulfonic acid group is known by using a known sulfonating agent such as sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid, sulfuric acid, sodium hydrogen sulfite and the like. (In the present invention, sulfonation refers to a reaction in which a hydrogen atom of a group —H is substituted with SO ₃ H).

As the reaction conditions for the sulfonation, the polymer having no sulfonic acid group is reacted with the sulfonated agent in the absence of a solvent or in the presence of a solvent. Examples of the solvent include hydrocarbon solvents such as n-hexane, ether solvents such as tetrahydrofuran and dioxane, aprotic polar solvents such as dimethylacetamide, dimethylformamide, and dimethylsulfoxide, tetrachloroethane, dichloroethane, chloroform, And halogenated hydrocarbons such as methylene chloride. The reaction temperature is not particularly limited, but is usually −50 to 200 ° C., preferably −10 to 100 ° C. Moreover, reaction time is 0.5 to 1,000 hours normally, Preferably it is 1 to 200 hours.

The amount of sulfonic acid group in the sulfonic acid group-containing polymer of the present invention thus obtained is 0.5 to 5 milligram equivalent / g, preferably 0.7 to 4 milligram equivalent / g, more preferably 0.8-3 milligram equivalent / g. When the amount of sulfonic acid group is low, proton conductivity does not increase. On the other hand, when the amount of sulfonic acid group is high, hydrophilicity is improved, and depending on the structure, a water-soluble polymer is obtained. The amount of the sulfonic acid group can be adjusted by the reaction conditions (temperature, time) and the charged amount (composition).
In addition, the molecular weight of the polymer catalyst used in the present invention thus obtained before sulfonation or the precursor of the sulfonic acid is a weight average molecular weight in terms of polystyrene of 1,000 to 1,000,000, preferably 10,000 to 100. It is 10,000, more preferably 20,000 to 800,000, particularly preferably 30,000 to 400,000. If it is less than 1000, when producing a molded product, the molded product is easily broken, and there is also a problem in strength properties. On the other hand, when it exceeds 1,000,000, when used as a homogeneous catalyst, there are problems such as insufficient solubility, high solution viscosity, and poor processability.

The catalyst of the present invention can be used as either a homogeneous catalyst or a heterogeneous catalyst. When used as a heterogeneous catalyst, it can also be used by being supported on a carrier.
Examples of the acid-catalyzed conversion reaction of an organic compound in which the catalyst of the present invention is used include (1) Friedel-Crafts reaction, (2) esterification reaction, (3) transesterification reaction, (4) etherification reaction, Examples include (5) hydration reaction, (6) isomerization reaction, (7) dehydration condensation reaction such as O-glycosidation, and (8) polycondensation reaction. Examples of the polycondensation reaction include polymerization of olefins, synthesis of polyketone using diacyl halide, and polyoxymethylene synthesis reaction.
In particular, the catalyst of the present invention is highly active and uses a small amount of catalyst as compared with the aluminum chloride catalyst conventionally used in the Friedel-Crafts reaction, and the aromatic acylation reaction proceeds under mild conditions.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. In addition, the measurement item in an Example was calculated | required as follows.
[Weight Average Molecular Weight] The number average molecular weight and weight average molecular weight of the precursor polymer before sulfonation were determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

Reference Example 1 Production of Polymer Catalyst 1 (1) Synthesis of 2,5-dichloro-4 ′-(4-thiophenoxy) thiophenoxybenzophenone [Formula (44) below] 2,5-dichloro-4′- 10.8 g (40 mmol) of fluorobenzophenone, 8.7 g (40 mmol) of 4-phenylsulfanylthiophenol and 8.29 g (60 mmol) of potassium carbonate are placed in a three-necked flask equipped with a Dean-Stark tube, a condenser tube and a thermometer, and 50 g of dimethylacetamide is obtained. And a mixed solvent of 50 g of toluene were poured and stirred. Next, the temperature was raised to 130 ° C., and water produced was removed while heating under reflux. Furthermore, it was made to react at 150 degreeC for 4 hours, removing toluene out of the system. After confirming the completion of the reaction by TLC, the contents were cooled to room temperature, poured into water and stirred for 1 hour. The organic matter was separated from the mixture solution, and extracted with ethyl acetate. The extract layer was washed with water and brine, and then dried over anhydrous magnesium sulfate. After the inorganic salt was filtered off, the solvent was distilled off to obtain a crude product. Recrystallization was performed with a mixed solvent of ethyl acetate: n-hexane = 1: 5 (volume ratio) to obtain the desired product in a yield of 85% (15.8 g).

(2) Synthesis of bis [4- [4- (4-chlorophenylsulfonyl) phenoxy] phenyl] sulfone (2-1) Synthesis of 4-chlorophenyl-4′-fluorophenylsulfone 192 g (2.0 mol) of fluorobenzene and chloride 69.5 g (520 mmol) of aluminum was placed in a three-necked flask equipped with a thermometer, a dropping funnel and a three-way cock, and the atmosphere was replaced with nitrogen. The mixture was stirred with a mechanical stirrer while being cooled to 10 ° C. with ice water. 4-Chlorobenzenesulfonyl chloride (84.4 g, 400 mmol) was added dropwise using a dropping funnel over 30 minutes, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was poured into an aqueous solution of concentrated hydrochloric acid: ice = 1: 10 and stirred for 1 hour. The mixture was extracted with ethyl acetate, and the organic layer was washed with 5% aqueous sodium hydrogen carbonate solution, water and saturated brine. The organic layer was dried over anhydrous magnesium sulfate, then ethyl acetate was distilled off under reduced pressure, and recrystallized with a mixed solvent of hexane: ethyl acetate. The formation of the target product was confirmed by NMR and IR spectra. Yield 85% (92.0 g).

(2-2) Synthesis of bis [4- [4- (4-chlorophenylsulfonyl) phenoxy] phenyl] sulfone [the following formula (45)] 25.0 g (100 mmol) of bis (4-hydroxyphenyl) sulfone (bisphenol S) And 30.4 g (220 mmol) of potassium carbonate, 100 ml of dimethylacetamide, and 50 ml of toluene were placed in a three-necked flask equipped with a thermometer, a Dean-Stark tube, a reflux tube, and a three-way cock, and purged with nitrogen. Stirring while raising the temperature to 130 ° C. in an oil bath, water and toluene produced by the reaction were azeotroped and removed with a Dean-Stark tube. When no more water was observed, the temperature was raised to 150 ° C. and toluene was distilled off. After the reaction solution was cooled to 80 ° C., 67.6 g (250 mmol) of 4-chlorophenyl-4′-fluorophenylsulfone was added and stirred at 110 ° C. for 7 hours. After the inorganic salt as a by-product was removed by filtration, the filtrate was put into 500 ml of methanol, and the precipitate was filtered and recrystallized from toluene. The formation of the target product was confirmed by NMR and IR spectra. Yield 71% (51.0 g).

(3) Synthesis of polymer catalyst (3-1) Polymerization 25.17 g (35.0 mmol) of bis [4- [4- (4-chlorophenylsulfonyl) phenoxy] phenyl] sulfone obtained above, 2,5- Dichloro-4 '-(4-thiophenoxy) thiophenoxybenzophenone 16.3 g (35.0 mmol), bis (triphenylphosphine) nickel dichloride 1.43 g (2.2 mmol), sodium iodide 1.37 g (9. 14 mmol), 7.73 g (29.5 mmol) of triphenylphosphine, and 11.3 g (172 mmol) of zinc powder were placed in a reaction vessel, and the inside of the system was replaced with dry nitrogen. Polymerization was carried out by adding 0.2 liter of N-methyl-2-pyrrolidone (NMP), heating to 80 ° C., and stirring for 4 hours. The reaction solution after polymerization is diluted with tetrahydrofuran (THF), and a polymer is recovered by adding a mixed solution of hydrochloric acid and methanol. Then, washing with methanol is repeated four times, and the polymer dissolved in THF is reprecipitated with methanol. The polymer separated by filtration and dried in vacuo gave 34.7 g (95%) of the desired polymer. The number average molecular weight in terms of polystyrene determined by GPC (THF) was 40,000, and the weight average molecular weight was 145,000.

(3-2) Sulfonation of polymer 20.0 g of the polymer obtained above was put into a 0.5 liter reaction solution, 0.25 liter of 96% sulfuric acid was added, and stirring was continued at room temperature under nitrogen for 2 days. It was. The resulting solution was poured into 5 liters of ion exchange water to precipitate the polymer. The polymer was repeatedly washed with water until the pH of the washing solution reached 5. Drying gave 23.7 g (95%) of a sulfonated polymer.
(3-3) Oxidation of sulfonated polymer 20.0 g of the sulfonated polymer obtained above was placed in a 2 liter glass reaction vessel, 0.8 liter of acetic acid and 200 g of 34% aqueous hydrogen peroxide were added, The temperature was gradually raised while stirring, and the reaction was continued at 90 ° C. for 6 hours. After the reaction, the mixture was allowed to cool, and the polymer was filtered off, washed with water, and dried in vacuo to obtain 19.6 g (92%) of the desired polymer catalyst [sulfone oxide of the following formula (46)]. By structural analysis, it was confirmed that a plurality of sulfonic acid groups were introduced into the side chain per side chain.

[Reference Example 2] Production of polymer catalyst 2 (1) Synthesis of 2,5-dichloro-4'-thiophenoxybenzophenone [Formula (47) below] In place of 4-phenylsulfanylthiophenol, 4.4 g of thiophenol The target product was obtained in a yield of 83% using the same method as the synthesis of 2,5-dichloro-4 ′-(4-thiophenoxy) thiophenoxybenzophenone of Example 1 except that (40 mmol) was used. (11.9g)

(2) Synthesis of 4,4′-bis [4- (4-chlorobenzoyl) phenoxy] benzophenone (2-1) Synthesis of 4-chloro-4′-fluorobenzophenone 4-chlorobenzene instead of 4-chlorobenzenesulfonyl chloride A desired compound was obtained in the same manner as in Reference Example 1 except that 70.0 g (400 mmol) of benzoyl chloride was used. The structure was confirmed by NMR and IR spectra. Yield 79% (74.1 g). (2-2) Synthesis of 4,4′-bis [4- (4-chlorobenzoyl) phenoxy] benzophenone [formula (48)] 4-chloro-4′- in place of bis (4-hydroxyphenyl) sulfone A desired compound was obtained in the same manner as in Example 1 except that 58.6 g (250 mmol) of fluorobenzophenone was used. The structure was confirmed by NMR and IR spectra. Yield 75% (48.2 g).

(3) Synthesis of polymer catalyst (3-1) Polymerization Instead of bis [4- [4- (4-chlorophenylsulfonyl) phenoxy] phenyl] sulfone, 4,4′-bis [4- (4-Chlorobenzoyl) phenoxy] benzophenone 22.5 g (35.0 mmol) was used instead of 2,5-dichloro-4 ′-(4-thiophenoxy) thiophenoxybenzophenone. Using the same method as in Example 1 except that 12.6 g (35.0 mmol) of thiophenoxybenzophenone was used, 30.6 g (94%) of the desired polymer was obtained. The number average molecular weight was 44,000, and the weight average molecular weight was 150,000.
(3-2) Sulfonation of polymer A sulfonated polymer was obtained in the same manner as in Reference Example 1 except that the polymer obtained above was used (yield 96%).
(3-3) Oxidation of Sulfonated Polymer A desired polymer catalyst [sulfone oxide of the following formula (49)] was used in the same manner as in Reference Example 1 except that the sulfonated polymer obtained above was used. (92%) was obtained. Structural analysis confirmed that 2.6 sulfonic acid groups were introduced per side chain.

Reference Example 3 Production of Polymer Catalyst 3 (1) Synthesis of 2,5-dichlorophenyl-4′-thiophenylbenzene sulfide [Formula (50) below] Quinoline (0.5 liter) stirred under nitrogen And 120 g (0.5 mol) of sodium 4-phenylsulfanylthiophenolate were added to 36 g (0.2 mol) of 1,2,4-trichlorobenzene. The temperature was raised with stirring, and the mixture was stirred at a reaction temperature of 160 ° C. for 3 hours. The reaction mixture was poured into water, extracted with diisopropyl ether, and then the solvent was removed to obtain the desired product. Yield 90% (65.3 g).

(2) Synthesis of polymer catalyst (2-1) Polymerization 25.0 g (100 mmol) of bis (4-hydroxyphenyl) sulfone, 30.4 g (220 mmol) of potassium carbonate, 0.1 liter of dimethylacetamide and 0.05 liter of toluene Was placed in a three-necked flask equipped with a thermometer, Dean-Stark tube, reflux tube, and three-way cock, and purged with nitrogen. Stirring while heating in an oil bath at 130 ° C., water produced by the reaction was azeotroped with toluene and separated from the reaction system by a Dean-Stark tube. When water no longer formed, the oil bath temperature was set to 150 ° C. and toluene was distilled off. After cooling the reaction solution to 80 ° C., 36.3 g (100 mmol) of 2,5-dichlorophenyl-4′-thiophenylbenzene sulfide was added and stirred at an oil bath temperature of 150 ° C. for 20 hours. The inorganic salt as a by-product was separated by filtration, the filtrate was poured into 2 liters of methanol, the precipitate was filtered, washed with methanol, and vacuum dried to obtain the desired polymer (yield 87%). . The number average molecular weight was 48,000, and the weight average molecular weight was 150,000.
(2-2) Sulfonation of polymer A sulfonated polymer was obtained in the same manner as in Reference Example 1 except that the polymer obtained above was used (yield 95%).
(3-3) Oxidation of Sulfonated Polymer A desired polymer catalyst [sulfone oxide of the following formula (51)] was used in the same manner as in Reference Example 1 except that the sulfonated polymer obtained above was used. (94%) was obtained. Structural analysis confirmed that 2.1 sulfonic acid groups per side chain were introduced into the side chain.

Reference Example 4 Production of Polymer Catalyst 4 (1) Synthesis of Polymer Catalyst (1-1) Polymerization 4,4′-dihydroxybenzophenone was used instead of bis (4-hydroxyphenyl) sulfone, and 2,5 The desired polymer in the same manner as in Example 3, except that 2,5-dichloro-4 '-(4-thiophenoxy) thiophenoxybenzophenone was used instead of dichlorophenyl-4'-thiophenylbenzene sulfide (Yield 92%). The number average molecular weight was 51,000 and the weight average molecular weight was 160,000.
(1-2) Sulfonation of polymer A sulfonated polymer was obtained in the same manner as in Reference Example 1 except that the polymer obtained above was used (yield 95%).
(1-3) Oxidation of Sulfonated Polymer A desired polymer catalyst [sulfone oxide of the following formula (52)] was used in the same manner as in Reference Example 1 except that the sulfonated polymer obtained above was used. (92%) was obtained. By structural analysis, it was confirmed that 1.9 sulfonic acid groups per side chain were introduced into the side chain.

[Comparative Example 1]
Polyetheretherketone (ICI) was sulfonated in the same manner as in Reference Example 1 to obtain a sulfonated polyetheretherketone catalyst represented by the following formula (53).

Reference Example 5 Production of Polymer Catalyst 5 (1) Synthesis of 4- (4′-sulfonylphenylthio) benzenesulfonyl chloride [Formula (55) below]

A thermometer, a dropping funnel, and a three-necked flask equipped with a three-way cock were charged with 20.0 g (108 mmol) of diphenyl sulfide and 35 ml of chloroform, and the system was replaced with dry nitrogen. This solution was cooled to 5 ° C. with ice water, and 25.1 g (215 mmol) of chlorosulfuric acid was slowly added dropwise. When the reaction solution was stirred at 5 ° C. for 3 hours, a white solid was precipitated. After confirming that all of the diphenyl sulfide had reacted by thin layer chromatography, 25.6 g (215 mmol) of thionyl chloride was slowly added dropwise. After refluxing for 90 minutes, the solvent chloroform was distilled off and vacuum dried. Yield: 96% (37.8 g)
(2) Synthesis of 4- (4′-sulfonylphenylthio) benzenesulfonyl chloride [the above formula (55)] into polyethersulfone [Synthesis of the following formula (56)]

Polyethersulfone (manufactured by Solvay Advanced Polymers, Radel A-200) 2.0 g and nitrobenzene 30 ml were placed in a reaction vessel, and the system was replaced with dry nitrogen while heating and dissolving at 60 ° C. To this polymer solution, 6.28 g (17.24 mmol) of 4- (4′-sulfonylphenylthio) benzenesulfonyl chloride [the above formula (55)] was added and dissolved. To this solution, 2.54 g (18.80 mmol) of aluminum chloride was added little by little and stirred at 80 ° C. for 20 hours. The reaction solution was added to 500 ml of a mixed solution of methanol: hydrochloric acid = 10: 1, and the precipitated solid was stirred while being pulverized. The solid was filtered, washed several times with methanol, and dried in vacuo at 80 ° C. The yield was 2.22g.

(3) Sulfonation was performed in the same manner as in Reference Example 1 except that the solid obtained above (Formula (56) above) was used.
(4) Oxidation reaction [synthesis of the following formula (57)]
A two-necked flask equipped with a thermometer was charged with 1.0 g of the polymer described in the formula (56) subjected to side chain introduction reaction and 20 ml of acetic acid. To this mixture, 1000 mg (9.0 mmol) of 30% aqueous hydrogen peroxide was added and refluxed for 3 hours. The solid in the system was suction filtered, washed with water, and vacuum dried at 100 ° C. to obtain a polymer catalyst 5. From NMR and IR, it was confirmed that the side chain sulfide was converted to sulfone. It was also confirmed that a plurality of sulfonic acid groups per side chain were introduced into the side chain. Yield was 880 mg.

[Reference Example 6] Production of polymer catalyst 6 (1) Introduction reaction of 4- (4'-sulfonylphenylthio) benzenesulfonyl chloride [the above formula (55)] to polyethersulfone (2)
The synthesis was performed in the same manner as described in Reference Example 1- (2) except that the stirring temperature was 90 ° C. and the stirring time was 40 hours.
(2) Oxidation reaction An oxidation reaction was carried out in the same manner as described in Reference Example 1- (3) to obtain a polymer catalyst 6.
[Reference Example 7] Production of polymer catalyst 7 (1) Introduction reaction of 4- (4′-sulfonylphenylthio) benzenesulfonyl chloride [the above formula (55)] to polyether ether sulfone [the following formula (58)] Synthesis of

Polyether ether sulfone (manufactured by Aldrich) (3.0 g) and nitrobenzene (60 ml) were placed in a reaction vessel, and the system was replaced with dry nitrogen while heating and dissolving at 60 ° C. In this polymer solution, 3.50 g (37 mmol) of 4- (4′-sulfonylphenylthio) benzenesulfonyl chloride [the above formula (55)] was added and dissolved. To this reaction solution, 5.44 g (40.8 mmol) of aluminum chloride was added little by little and stirred at 90 ° C. for 40 hours. The reaction solution was added to 500 ml of a mixed solution of methanol: hydrochloric acid = 10: 1, and the precipitated solid was stirred while being pulverized. The solid was filtered, washed several times with methanol, and vacuum dried at 80 ° C. to obtain a polymer (formula (58)) with a yield of 4.36 g.
(2) Sulfonation was carried out using the same method as in Reference Example 1 except that the polymer obtained above (Formula (58) above) was used.
(3) Oxidation reaction [synthesis of the following formula (59)]
An oxidation reaction was carried out in the same manner as described in Reference Example 1- (3) to obtain a polymer catalyst 7. It was confirmed that 1.6 sulfonic acid groups were introduced into the side chain per side chain.

[Reference Example 8] Production of polymer catalyst 8 (1) Synthesis of bis (thiophenoxy) benzenesulfonyl chloride (the following formula (60)) 1,4-dibromo in a three-necked flask equipped with a thermometer, a dropping funnel and a three-way cock 50 g (212 mmol) of benzene and 16 ml of chloroform were added, and the inside of the system was replaced with dry nitrogen. To this was slowly added dropwise 27.2 g (233 mmol) of chlorosulfuric acid dissolved in 100 ml of chloroform at room temperature. A reaction tube was attached for 4 hours at room temperature, and a reaction was performed for 10 hours under reflux of chloroform. After confirming that all 1,4-dibromobenzene had reacted by thin layer chromatography, chloroform and chlorosulfuric acid were distilled off under reduced pressure for purification to obtain 56.9 g (180 mmol) of dibromobenzenesulfonic acid ( Yield 85%). Next, 3.5 g (79 mmol) of thiophenol was put into a three-necked flask equipped with a Dean-Stark tube, a condenser tube, and a thermometer, and 4.5 g of potassium hydroxide, 25 ml of N, N-dimethylacetamide and 25 ml of toluene were added and stirred with a stirrer. did. The temperature was raised to 150 ° C., and water produced was removed while heating under reflux. To this, 7.1 g (23 mmol) of dibromobenzenesulfonic acid was added and reacted at 160 ° C. for 4 hours. After confirming the completion of the reaction by thin layer chromatography, the organic substance was separated from the mixture solution and purified by recrystallization to obtain 7.2 g of bis (thiophenoxy) benzenesulfonic acid (yield 84%). ). This is put into a three-necked flask equipped with a thermometer, a dropping funnel and a three-way cock, and 100 ml of chloroform is added and dissolved. After slowly dropping 2.1 g (21.2 mmol) of thionyl chloride with a dropping funnel and refluxing for 90 minutes, chloroform was distilled off and dried under vacuum to obtain bis (thiophenoxy) benzenesulfonyl chloride (following formula (60)) 6 0.4 g was obtained (yield 85%).

(2) Introduction reaction of bis (thiophenoxy) benzenesulfonyl chloride (the above formula (60)) to polyethersulfone [Synthesis polyethersulfone of the following formula (61)] (Radel A-200, manufactured by Solvay Advanced Polymers) 2.0 g and 30 ml of nitrobenzene were placed in a reaction vessel, and the inside of the system was replaced with dry nitrogen while heating and dissolving at 60 ° C. To this polymer solution, 6.70 g (17.08 mmol) of bis (thiophenoxy) benzenesulfonyl chloride (the above formula (60)) was added and dissolved. To this solution, 2.54 g (18.96 mmol) of aluminum chloride was added little by little and stirred at 80 ° C. for 20 hours. The reaction solution was added to 500 ml of a mixed solution of methanol: hydrochloric acid = 10: 1, and the precipitated solid was stirred while being pulverized. After filtering this solid, it was washed several times with methanol, and vacuum-dried at 80 ° C. to obtain a polyethersulfone having the side chain introduced (the following formula (61)). The yield was 2.31 g.

(3) Sulfonation thermometer of side chain group, dripping funnel, three-necked flask equipped with a three-way cock was charged with 2.00 g of the polymer described in the above formula (61) and 16 ml of chloroform, and the system was filled with dry nitrogen. Replaced. To this, 4.0 g (40 mmol) of chlorosulfuric acid dissolved in 100 ml of chloroform at room temperature was slowly added dropwise. A reaction tube was attached for 4 hours at room temperature, and a reaction was performed for 10 hours under reflux of chloroform. After confirming that all the starting polymers had reacted by thin layer chromatography, chloroform and chlorosulfuric acid were distilled off under reduced pressure and purified to effect side chain introduction reaction (sulfone sulfonate of the following formula (62)) 2.03 g was obtained.

(4) Oxidation reaction A two-necked flask equipped with a thermometer was charged with 1.0 g of a polymer described in the above formula (62) and 20 ml of acetic acid, which had been side chain introduced and sulfonated. To this mixture, 1000 mg (9 mmol) of 30% aqueous hydrogen peroxide was added and refluxed for 3 hours. The solid in the system was suction filtered, washed with water, and vacuum dried at 100 ° C. to obtain the final polymer catalyst 8 (the following formula (63)). From NMR and IR, it was confirmed that the side chain sulfide was converted to sulfone. The yield was 0.87g. It was confirmed that a plurality of sulfonic acid groups were introduced per side chain.

[Reference Example 9] Production of polymer catalyst 9 (1) Synthesis of 4-thiophenoxybenzene sulfide Thermometer, dripping funnel, 3-bromo-1-fluorobenzene 50.0 g (286 mmol) in a three-necked flask equipped with a three-way cock , 300 ml of N, N-dimethylformamide was added, and 22.0 g (314 mmol) of sodium thiomethylate dissolved in 100 ml of N, N-dimethylformamide was slowly dropped with a dropping funnel and stirred at 20 ° C. for 100 hours to react. I let you. After confirming that all of the 3-bromo-1-fluorobenzene had reacted by thin layer chromatography, the organic substance was separated from the mixture solution and purified by recrystallization to give 4-bromophenylmethyl sulfide 49. 3 g (243 mmol) were obtained. Next, 45.0 g (222 mmol) of 4-bromophenyl methyl sulfide, 15.5 g of copper oxide and 240 ml of pyridine 60 ml of quinoline were placed in a three-necked flask equipped with a thermometer, a dropping funnel and a three-way cock, and 26.8 g (244 mmol) of thiophenol. Was dissolved and dispersed in 20 ml of pyridine in 80 ml of quinoline and added with a dropping funnel, and the mixture was reacted at 150 ° C. for 40 hours. After confirming the completion of the reaction by thin layer chromatography, the organic substance was separated from the mixture solution and purified by recrystallization to obtain 43.8 g (189 mmol) of 4-thiophenoxyphenyl methyl sulfide. Subsequently, 40.0 g (172 mmol) of 4-thiophenoxyphenyl methyl sulfide obtained and 300 ml of N, N-dimethylformamide were placed in a three-necked flask equipped with a thermometer and a condenser tube, and 21.3 g (190 mmol) of sodium thio t-butylate was added. After confirming that the reaction was completed with N and N, the organic substance was separated from the mixture solution, and dissolved in 300 ml of purified dimethylformamide by recrystallization was added by a dropping funnel and reacted at 150 ° C. for 4 hours. . Thin-layer chromatography was performed to obtain 32.2 g (148 mmol) of 4-thiophenoxybenzene sulfide (yield 86%).
(2) Synthesis of long-branched sulfide In the same manner as in (1), except that 30.0 g (138 mmol) of 4-thiophenoxybenzene sulfide obtained in (1) was used instead of thiophenol, long-branched sulfide (see below) 31.0 g of the formula (64)) was obtained (yield 83%).

(3) 31.0 g (57.2 mmol) of a long-branched sulfide (formula (64)) and 200 ml of chloroform were placed in a three-necked flask equipped with a sulfonation reaction thermometer, a dropping funnel and a three-way cock, and the inside of the system was filled with dry nitrogen. Replaced. To this was slowly added dropwise 7.34 g (63.0 mmol) of chlorosulfuric acid dissolved in 100 ml of chloroform at room temperature. A reaction tube was attached for 4 hours at room temperature, and the reaction was carried out for 10 hours under reflux of chloroform. After confirming that all the starting polymers had reacted by thin layer chromatography, chloroform and chlorosulfuric acid were distilled off under reduced pressure for purification to obtain 36.1 g of a sulfonated product of long branched sulfide (the following formula (65)). (Yield 90%).

(4) Oxidation reaction A two-necked flask equipped with a thermometer was charged with 36.0 g (51.3 mmol) of a sulfonated product of a long-branched sulfide and 200 ml of acetic acid. To this mixture, 116 g (1.03 mmol) of 30% aqueous hydrogen peroxide was added and refluxed for 3 hours. The solid in the system was suction filtered, washed with water, and vacuum dried at 100 ° C. to obtain 42.8 g of a sulfonated product of long-branched sulfone (formula (66) below) (yield 95%).

(5) Chlorination 30.0 g (34.2 mmol) of a sulfonated product of long-branched sulfone (formula (66)) is placed in a three-necked flask equipped with a thermometer, a dropping funnel and a three-way cock, and 100 ml of chloroform is added and dissolved. Let Then, 3.74 g (37.6 mmol) of thionyl chloride was slowly added dropwise with a dropping funnel and refluxed for 90 minutes, after which chloroform was distilled off and vacuum-dried, and sulfonyl chloride of a long-branched sulfone (the following formula (67)) 27. 0 g was obtained (88% yield).

(6) Reaction of introduction of sulfonyl chloride of long-branched sulfone into polyethersulfone In the same manner as in Reference Example 8 (2), except that sulfonyl chloride of long-branched sulfone is used instead of bis (thiophenoxy) benzenesulfonyl chloride. Thus, polyethersulfone having the side chain of the long branched sulfone (the following formula (68)) was obtained as the polymer catalyst 9. The yield was 2.05g.

[Reference Example 10] Production of polymer catalyst 10 (1) Synthesis thermometer of bis (3,5-thiophenoxy) benzene sulfide, dripping funnel, and 3,5-dibromo-1-fluoro in a three-necked flask equipped with a three-way cock Benzene (50.0 g, 197 mmol) and N, N-dimethylformamide (300 ml) were added, sodium thiomethylate (15.2 g, 217 mmol) dissolved in N, N-dimethylformamide (100 ml) was slowly added dropwise with a dropping funnel at 20 ° C. For 4.5 days with stirring. After confirming that all 3,5-dibromo-1-fluorobenzene had reacted by thin layer chromatography, the organic substance was separated from the mixture solution, purified by recrystallization, and 3,5-dibromophenyl 48.3 g (171 mol) of methyl sulfide was obtained (yield 87%). Next, 45 g (160 mmol) of 3,5-dibromophenylmethyl sulfide, 22.4 g of copper oxide, and 240 ml of quinoline 240 ml of pyridine were put into a three-necked flask equipped with a thermometer, a dropping funnel and a three-way cock, and 38.7 g (352 mmol) of thiophenol. Was dissolved and dispersed in 20 ml of pyridine in 80 ml of quinoline and added with a dropping funnel, and the mixture was reacted at 150 ° C. for 40 hours. After confirming the completion of the reaction by thin layer chromatography, the organic substance was separated from the mixture solution and purified by recrystallization to obtain 45.7 g (134 mmol) of bis (3,5-thiophenoxy) phenyl methyl sulfide. Obtained. Subsequently, 40.0 g (118 mmol) of the obtained bis (3,5-thiophenoxy) phenylmethyl sulfide was placed in a three-necked flask equipped with a thermometer and a condenser, and 14.5 g (129 mmol) of sodium thio t-butylate was added to N , N-dimethylformamide dissolved in 300 ml was added with a dropping funnel and reacted at 150 ° C. for 4 hours. After confirming the completion of the reaction by thin layer chromatography, the organic substance was separated from the mixture solution and purified by recrystallization to obtain 33.1 g (101 mmol) of bis (3,5-thiophenoxy) benzene sulfide. (Yield 86%).
(2) Synthesis of multi-branched sulfide (the following formula (69)) 1) Instead of thiophenol, 30.0 g (92.0 mmol) of bis (3,5-thiophenoxy) benzene sulfide obtained in 1) is used. In the same manner, 31.4 g of a hyperbranched sulfide (the following formula (69)) was obtained. (Yield 90%)

(3) Sulfonation reaction 30.0 g (39.6 mmol) of multi-branched sulfide (the above formula (69)) and 200 ml of chloroform were placed in a three-necked flask equipped with a thermometer, a dropping funnel and a three-way cock, and the system was filled with dry nitrogen Was replaced. To this, 5.07 g (43.5 mmol) of chlorosulfuric acid dissolved in 100 ml of chloroform at room temperature was slowly added dropwise. A reaction tube was attached for 4 hours at room temperature, and a reaction was performed for 10 hours under reflux of chloroform. After confirming that all raw material sulfides were reacted by thin layer chromatography, chloroform and chlorosulfuric acid were distilled off under reduced pressure for purification to obtain 36.3 g of a sulfonated product of the multi-branched sulfide (the following formula (70)). Obtained (yield 85%).

(4) Oxidation reaction A two-necked flask equipped with a thermometer was charged with 36.0 g (33.4 mmol) of a sulfonated product of multi-branched sulfide and 200 ml of acetic acid. To this mixture, 114 g (1.00 mol) of 30% aqueous hydrogen peroxide was added and refluxed for 3 hours. The solid in the system was suction filtered, washed with water, and vacuum dried at 100 ° C. to obtain 39.6 g of a sulfonated product of a multi-branched sulfone (the following formula (71)) (yield 90%).

(5) Chlorination 30.0 g (22.8 mol) of the sulfonated product of the multi-branched sulfone (formula (71)) is put into a three-necked flask equipped with a thermometer, a dropping funnel and a three-way cock, and 100 ml of chloroform is added and dissolved. Let After slowly dropping 2.49 g (25.0 mmol) of thionyl chloride with a dropping funnel and refluxing for 90 minutes, chloroform was distilled off and vacuum drying to obtain a sulfonyl chloride of a multi-branched sulfone (the following formula (72)) 27. 1 g was obtained (89% yield).

(6) Reaction of introducing a sulfonyl chloride of a multi-branched sulfone into a polyethersulfone In the same manner as in Reference Example 8- (2), except that a sulfonyl chloride of a multi-branched sulfone is used instead of bis (thiophenoxy) benzenesulfonyl chloride. Thus, polyethersulfone having the side chain of the multi-branched sulfone (the following formula (73)) was obtained as the polymer catalyst 10. The yield was 2.10g.

Reference Example 11 Production of Polymer Catalyst 11 (1) Synthesis of TTBS3 50.0 g of 1,3,5-tris (phenylthio) -benzene (TTB) in a three-necked flask equipped with a thermometer, a dropping funnel and a three-way cock 124 mmol) and 120 ml of sulfolane were added, and the inside of the system was replaced with dry nitrogen. The liquid temperature was kept at 70 ° C., and 15.9 g (136 mmol) of chlorosulfuric acid was slowly added dropwise, followed by stirring for 1.5 hours. The reaction was confirmed by liquid chromatography [Agilent 100 series, column: GL Science, Intersil ODS-3, mobile phase: 10 M ammonium formate / acetonitrile, UV detection wavelength: 254 nm]. A mixture containing 53 g of TTB trisulfonate [TTBS3, the following formula (74)] was obtained (yield 67%).

(2) Synthesis of TTBS3C The above mixture containing TTBS3 was placed in a three-necked flask equipped with a thermometer, a dropping funnel and a three-way cock. The liquid temperature was kept at 70 ° C., and 12.4 g (124 mmol) of thionyl chloride was slowly dropped from the dropping funnel, followed by stirring for 2 hours. The reaction was confirmed by liquid chromatography. A mixture containing 18.5 g of sulfonyl chloride [TTBS3C, the following formula (75)] of a TTB trisulfonate was obtained (34% yield).

(3) Side chain introduction reaction to polyethersulfone In Reference Example 8- (2), instead of bis (thiophenoxy) benzenesulfonyl chloride, 11.3 g (17.1 mmol) of the above TTBS3C [formula (75)] was added. A side-chain sulfonic acid polyethersulfone [Formula (76) below] was obtained as the polymer catalyst 11 in the same manner except that the mixture containing was used. The yield was 2.30 g.

[Examples] In Examples, GC-7A manufactured by Shimadzu Corporation was used as the gas chromatograph, and silicon DC-550 was used as the column filler.
[Example 1]
<Friedel crafts acylation reaction>
Using the polymer catalyst 1 synthesized in Reference Example 1 as a catalyst, acetylation of anisole with acetic anhydride was performed.
To a 50 ml three-necked flask equipped with a condenser, 2.16 g of anisole, 4.12 g of acetic anhydride, and 20 ml of acetonitrile as a solvent were added and placed in an oil bath with a stirrer. When the oil bath was heated and reached a predetermined temperature, 0.1 g of catalyst was added to carry out an acetylation reaction. The reaction solution after the reaction for a predetermined time was analyzed using a gas chromatograph. The results are shown in Table 2.

[Examples 2 to 11]
The reaction was carried out under the same conditions as in Example 1 except that the polymer catalyst produced in Reference Examples 2 to 11 was used as the catalyst. The results are shown in Table 2.
[Comparative Example 2]
The reaction was carried out under the same conditions as in Example 1 except that 10% by weight of anhydrous aluminum chloride conventionally used as a catalyst was used and the reaction was carried out at a reaction temperature of 70 ° C. for 10 hours. The results are shown in Table 2. Despite severer reaction conditions and a larger amount of catalyst than Example 1, the conversion rate of anisole is as low as 4%.

[Example 12]
The catalyst used in Example 11 was filtered and washed, and used as a catalyst under the same conditions as in Example 11. This operation was repeated 10 times. The results of the tenth reaction are shown in Table 2. When this result is compared with the first reaction (Example 11), it can be seen that neither the conversion rate nor the selectivity is decreased. Furthermore, when aluminum chloride is used as a catalyst, it is extremely difficult to reuse, but in the method of the present invention, since the catalyst can be used repeatedly, the amount of catalyst used can be reduced and the generated waste is reduced. I understand that there are few.

[Example 13]
<Esterification reaction>
Using the polymer catalyst 5 synthesized in Reference Example 5 as a catalyst, propyl acetate was produced from propylene and acetic acid by a fixed bed continuous flow reaction using the reaction apparatus shown in FIG. A reactor (length 100 cm, inner diameter 2.3 cm) filled with a pellet-shaped catalyst was placed in a thermostatic bath (not shown) and heated to 80 ° C. Acetic acid / propylene mixture (molar ratio 1.4) is fed from feed stream 1 to LHSV1.
Is supplied at 0, passed through the catalyst layer 3 in the reactor 2, and through a circulation pump and a heat exchanger, a quarter of the reaction liquid is partially extracted from the reaction mixture outlet 5, and the remainder of the reaction liquid is Recycled again from the circulation flow inlet 4 to the reactor. The effluent reaction mixture was periodically analyzed by gas chromatography. Table 3 shows the reaction conditions and the results 10 hours after the start of the reaction.

[Examples 14 to 16]
The same reaction as in Example 13 was performed except that the catalysts 8, 10, and 11 obtained in Reference Examples 8, 10, and 11 were used. The results are shown in Table 3.
[Comparative Example 3]
The same reaction as in Example 13 was performed except that Amberlite R120B (manufactured by Organo Corporation, sulfonated product of styrene / divinylbenzene copolymer) was used as the catalyst. The results are shown in Table 3.

[Example 17]
Example 16 was carried out continuously for 300 hours. There was no decrease in catalyst activity.
[Comparative Example 4]
Comparative Example 3 was carried out continuously for 300 hours. The catalytic activity was 70% of the initial activity (reaction time 10 hours), showing a significant decrease in activity.

  INDUSTRIAL APPLICABILITY The present invention is widely and effectively used as an acid catalyst useful for an acid-catalyzed conversion reaction of an organic compound and is useful as an environmentally friendly catalyst.

FIG. 1 is a process diagram including reactors used in Examples 13 to 17 and Comparative Examples 3 and 4.

Explanation of symbols

1 Feed stream 2 Reactor 3 Catalyst layer 4 Circulation flow inlet 5 Reaction mixture outlet

Claims (7)

A polymer catalyst used for an acid-catalyzed conversion reaction of an organic compound having at least a repeating unit (A) represented by the following general formula (1).

(Y represents a (k + 2) -valent aromatic residue, and P represents —CO—, —O—, —S—, —SO—, —SO ₂ —, —CONH—, —C (CF ₃ ) ₂ —. , A linking group selected from single bonds, k is an integer of 1 to 4, and the side chain portion Z in the formula is represented by the following general formula (2).
^{Z = - (X 1 Ar 1} (B 1)) - (X 2 Ar 2 (B 2)) - ··· - (X n-1 Ar n-1 (B n-1)) - (X n Ar ⁿ ) (2)
^{B 1 ~B n-1} in the general formula (2) in means a branched chain in the side chain moiety Z, is expressed by the following equation.
B ¹ = - ^{[(X 2 Ar 2 (B 2} )) - (X 3 Ar 3 (B 3)) - ··· - (X n-1 Ar n-1 (B n-1)) - (X ⁿ Ar ⁿ )] _f
B ² = - ^{[(X 3 Ar 3 (B 3} )) - ··· - (X n-1 Ar n-1 (B n-1)) - (X n Ar n) ] _f
・
・
・
B ⁿ⁻¹ = − [X ⁿ Ar ⁿ ] _f
In said general formula (2), n is an integer of 2-5 each independently,
f is each independently an integer of 0 to 5;
Ar ^{1 to} Ar ⁿ are each independently an aromatic residue,
X ^{1 to} X ⁿ are each independently —CO—, —CONH—, — (CF ₂ ) _p — (p is an integer of 1 to 10), —C (CF ₃ ) ₂ —, —COO—, —SO—. , —SO ₂ —.
Then, Z is a number greater than 1.0 of the -SO ₃ H group. ) P is -CO -, - O -, - S -, - SO 2 -, - C (CF 3) 2 - claim 1, wherein the polymeric catalyst which is a linking group selected from.   The polymer catalyst according to claim 1 or 2, wherein k is an integer of 1 to 2, and f is an integer of 0 to 2 each independently.   4. The polymer catalyst according to claim 3, wherein at least one f is 1 or 2.   The polymer catalyst according to claim 3, wherein f is 0 or 1, and at least one f is 1.   The polymer catalyst according to any one of claims 1 to 5, wherein the acid-catalyzed conversion reaction is a Friedel-Crafts reaction.   The polymer catalyst according to any one of claims 1 to 5, wherein the acid-catalyzed conversion reaction is an esterification reaction or a transesterification reaction.

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