JP7145818B2 - polymer, adsorbent - Google Patents

Description

The present invention relates to polymers and adsorbents.

In recent years, various polymers have been developed. In particular, from the point of view of applications such as adsorbents, polymers with large surface areas are desired. Polymers such as those described above include polymers having spiro carbon atoms.
As a polymer having a spiro carbon atom, for example, Patent Document 1 discloses a polymer represented by the following formula.

U.S. Patent Application Publication No. 4,552,949

When the inventors of the present invention examined the properties of the polymer disclosed in Patent Document 1, they found that it was necessary to further improve the size of the specific surface area. In addition, further improvements were required regarding adsorption of various components such as dichloromethane, acetone, and hexane.

An object of the present invention is to provide a polymer having a large specific surface area and excellent adsorption properties for various components such as dichloromethane, acetone, and hexane.
Another object of the present invention is to provide an adsorbent containing the polymer.

As a result of earnestly examining the above problem, the inventors found that the above problem can be solved by the following configuration.

(1) a compound A having a partial structure represented by formula (A1) described later and having 2 to 3 phenolic hydroxyl groups;
A polymer obtained by reacting at least a compound B having 3 or more groups capable of forming a covalent bond by reacting with a phenolic hydroxyl group.
(2) The polymer according to (1), wherein compound A contains a compound represented by formula (A2) described below.
(3) The polymer according to (1) or (2), wherein compound A contains a compound represented by formula (A3) described below.
(4) The polymer according to any one of (1) to (3), wherein compound A includes any of compounds represented by formulas (A4) to (A7) described below.
(5) A group capable of forming a covalent bond by reacting with a phenolic hydroxyl group is represented by a carboxy group, a carboxylic acid chloride group, a group represented by formula (C), and a leaving group —CH ₂ —. The polymer according to any one of (1) to (4), which is a group selected from the group consisting of groups.
(6) The polymer according to any one of (1) to (5), wherein compound B includes a compound represented by formula (B1) described below.
(7) The polymer according to (6), wherein q1 is an integer of 1 or greater, and ^Yb1 is an electron-withdrawing group.
(8) The polymer according to (6) or (7), wherein the halogen atom is a fluorine atom or a chlorine atom.
(9) The polymer according to any one of claims 1 to 8, wherein compound B includes a compound represented by formula (B4) described later or a compound represented by formula (B5) described later.
(10) An adsorbent containing the polymer according to any one of (1) to (9).

According to the present invention, it is possible to provide a polymer that has a large specific surface area and excellent adsorption properties for various components such as dichloromethane, acetone, and hexane.
Moreover, according to this invention, the adsorbent containing the said polymer can be provided.

The polymers and adsorbents of the invention are described below.
In the present invention, a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.

The bonding direction of the divalent linking group described herein is not particularly limited. For example, in formula (A3), when X ^a1 is —CO—CR ^a9 R ^a10 —, even if —CO— is bound to Y ^a1 side, —CR ^a9 R ^a10 — is bound to Y ^a1 side good too.

A polymer of the present invention is a polymer formed using a compound having a predetermined functional group. More specifically, the polymer of the present invention can be obtained by using a compound A having a predetermined partial structure described later and a compound B that can be a trivalent or higher repeating unit.
Compound A is a compound having a rigid and curved partial structure. Compound B is a compound having three or more reaction points. When compound A and compound B are allowed to react, if compound A tries to close up, it is presumed that due to mutual steric repulsion, close packing is not possible, and as a result, voids at the molecular level are generated. It is thought that the formation of these voids increases the specific surface area and exhibits excellent adsorptivity.
The polymer of the present invention corresponds to a polymer having a so-called crosslinked structure, and it was expected that a polymer having a crosslinked structure would have a small specific surface area and poor adsorptivity. It was found that an excellent effect can be obtained by

The polymer of the present invention is described in detail below.
The polymer of the present invention is a polymer obtained by reacting at least a compound A described later and a compound B described later.
First, the raw materials used for synthesizing the polymer will be described in detail below.

[Compound A]
Compound A is a compound having a partial structure represented by formula (A1) and having 2 to 3 phenolic hydroxyl groups.
Since the partial structure represented by the formula (A1) is a rigid and curved structure, it can form fine and random voids of molecular level size in the polymer.
In addition, a phenolic hydroxyl group means the hydroxyl group substituted by the aromatic ring group. The number of phenolic hydroxyl groups is 2 to 3, and at least one effect of a larger specific surface area and better adsorption of various components can be obtained (hereinafter simply referred to as "the effect of the present invention It is also referred to as "more excellent point".), two is preferable.

In formula (A1), L ^a1 and L ^a2 each independently represent a divalent linking group.
Examples of divalent linking groups include -O-, -CO-, -COO-, -CONH-, -S-, -SO ₂ -, -NR ^A - (R ^A is a hydrogen atom or an alkyl group), divalent hydrocarbon groups (e.g., alkylene groups, alkenylene groups (e.g., -CR ^a7 =CR ^a8 -), alkynylene groups (e.g., -C≡C-), and arylene groups), Alternatively, a group obtained by combining two or more of these may be mentioned. The definitions of R ^a7 and R ^a8 are as described later.
L ^a3 and L ^a4 each independently represent a single bond or —O—.

Compound A may have a substituent other than a hydroxyl group.
The types of substituents other than hydroxyl groups are not particularly limited, and examples thereof include groups exemplified as substituents other than hydroxyl groups for Z ^a1 and Z ^a2 described later.

Among them, the compound represented by the formula (A2) is preferable as the compound A because the effects of the present invention are more excellent.

The definitions of L ^a1 to L ^a4 in formula (A2) are the same as the definitions of L ^a1 to L ^a4 in formula (A1) described above.
Z ^a1 and Z ^a2 each independently represent a substituent other than a hydroxyl group.
The types of substituents represented by Z ^a1 and Z ^a2 are not particularly limited, and examples include halogen atoms (fluorine, chlorine, bromine, iodine, etc.), alkyl groups, cycloalkyl groups, alkenyl groups, Cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclicoxy group, acyloxy group, carbamoyloxy group, amino group (alkylamino and anilino groups), acylamino groups, aminocarbonylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, sulfamoylamino groups, alkyl or arylsulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, hetero ringthio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, Phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, and silyl groups are included.
The above substituent may be further substituted with a substituent.
Among them, the substituent is preferably a hydrocarbon group, and more preferably an alkyl group or an aryl group, from the viewpoint that the effects of the present invention are more excellent.
The number of carbon atoms in the alkyl group is not particularly limited, and is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1, from the viewpoint that the effects of the present invention are more excellent.

m1 and n1 each independently represent 1 or 2, and the sum of n1 and m1 is 2 or 3; That is, if m1 is 1, n1 represents 1 or 2, and if m1 is 2, n1 represents 1.

m2 and n2 each independently represent an integer of 0 to 3; Among them, m2 and n2 are preferably 0 or 1, more preferably 0, from the viewpoint that the effects of the present invention are more excellent.

Furthermore, the compound A is preferably a compound represented by formula (A3) in that the effects of the present invention are more excellent.
The definitions of Z ^a1 , Z ^a2 , m1, n1, m2, and n2 in formula (A3) are the same as the definitions of the groups in formula (A2) described above.

In formula (A3), X ^a1 and X ^a2 are each independently -CR ^a1 R ^a2 -, -CR ^a3 R ^a4 -CR ^a5 R ^a6 -, -CR ^a7 =CR ^a8 -, -CO-, -CO —CR ^a9 R ^a10 — or —O—.
Y ^a1 and Y ^a2 each independently represent —CR ^a11 R ^a12 —, —O—, or a single bond.
R ^a1 to R ^a12 each represent a hydrogen atom or a substituent.
The types of substituents represented by R ^a1 to R ^a12 are not particularly limited, and examples include halogen atoms (fluorine, chlorine, bromine, iodine, etc.), alkyl groups, cycloalkyl groups, alkenyl groups, Cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group ( (including alkylamino groups and anilino groups), acylamino groups, aminocarbonylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, sulfamoylamino groups, alkyl or arylsulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups , heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, and silyl groups.
The above substituent may be further substituted with a substituent.
Among them, the substituent is preferably a hydrocarbon group, and more preferably an alkyl group or an aryl group, from the viewpoint that the effects of the present invention are more excellent.
The number of carbon atoms in the alkyl group is not particularly limited, and is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1, from the viewpoint that the effects of the present invention are more excellent.

R ^a1 and R ^a2 , R ^a3 and R ^a4 , R ^a5 and R ^a6 , R ^a7 and R ^a8 , R ^a9 and R ^a10 , and R ^a11 and R ^a12 each independently bind to each other to form a ring You may have
The type of ring formed is not particularly limited, and may be an aromatic ring or a non-aromatic ring. Aromatic rings include aromatic hydrocarbon rings (eg, benzene and fluorene rings) or aromatic heterocycles. Non-aromatic rings include aliphatic hydrocarbon rings.
When X ^a1 is -O-, Y ^a1 is preferably not -O-, and when X ^a2 is -O-, Y ^a2 is preferably not -O-.

As the compound A, any one of the compounds represented by the formulas (A4) to (A7) is preferable in that the effects of the present invention are more excellent.
The definitions of m1 and n1 in formulas (A4) to (A7) are the same as the definitions of the groups in formula (A2) described above.

Specific examples of compound A are shown below.

[Compound B]
Compound B is a compound having three or more groups capable of forming a covalent bond by reacting with a phenolic hydroxyl group (hereinafter also referred to simply as "specific groups"). That is, the compound B corresponds to a compound having three or more sites that react with the phenolic hydroxyl group of the compound A, and the compound B can be a so-called trivalent or higher repeating unit.

The specific group is a group capable of forming a covalent bond by reacting with the phenolic hydroxyl group of compound A. Among them, the specific group is preferably a group capable of undergoing a substitution reaction with a phenolic hydroxyl group. When a group capable of undergoing a substitution reaction with a phenolic hydroxyl group is used as the specific group, for example, a substitution reaction (nucleophilic substitution reaction) proceeds between the phenolic hydroxyl group and the specific group, leaving a predetermined leaving group. However, there is an embodiment in which an ether bond is formed.
As the specific group, a carboxy group (--COOH), a carboxylic acid chloride group (--COCl), a group represented by the formula (C), and a leaving group --CH ₂ --, are preferred in that the effects of the present invention are more excellent. Groups selected from the group consisting of groups represented by are preferred. In the group represented by the leaving group —CH ₂ —, * represented by the leaving group —CH ₂ —* corresponds to the bonding position.

In formula (C), R ^c represents a leaving group. *1 and *2 represent binding positions.
The group represented by formula (C) corresponds to a group consisting of a leaving group and an sp2 carbon atom directly bonded to the leaving group. The group represented by the above formula (C) is, for example, a partial structure contained in an aromatic hydrocarbon group having a leaving group, or an aromatic heterocyclic group having a leaving group (where the leaving group is an aromatic (bonded to a carbon atom in a group heterocyclic group).

Leaving groups include, for example, halogen atoms and sulfonyloxy groups (eg, alkylsulfonyloxy groups and arylsulfonyloxy groups).
Although the number of specific groups is not particularly limited, it is preferably 3 to 5, more preferably 3 to 4, and even more preferably 4, from the viewpoint that the effects of the present invention are more excellent.
In addition, the compound B may have groups other than the specific group. Other groups include groups not falling under the specific group among the groups exemplified as the substituents represented by R ^a1 to R ^a12 described above.

Examples of compound B include a compound represented by formula (B1), a compound represented by formula (B2), and a compound represented by formula (B3). Among them, the compound represented by the formula (B1) is preferable because the effects of the present invention are more excellent.
Formula (B1) (X ^b1 ) _p1 -Ar ¹ -(Y ^b1 ) _q1
Formula (B2) (X ^b2 ) _p2 -Ar ² -(Y ^b2 ) _q2
Formula (B3) (X ^b3 ) _p3 −L ^b

In formula (B1), X ^b1 represents a halogen atom. A fluorine atom or a chlorine atom is preferable as the halogen atom.
^Yb1 represents a substituent other than a halogen atom. The type of substituent is not particularly limited, and groups other than halogen atoms among the groups exemplified as the substituents represented by R ^a1 to R ^a12 can be mentioned. An electron-withdrawing group can be mentioned because the effects of the present invention are more excellent.
The electron-withdrawing group is a substituent having a Hammett substituent constant σp value (sigma para value) greater than 0, for example, a hydrocarbon group substituted with a halogen atom (e.g., a trifluoromethyl group), cyano group, nitro group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, dialkylsulfamoyl group, dialkylamide group, and heterocyclic group.
These electron-withdrawing groups may be further substituted with a substituent.
Hammett's substituent constant σ value will be described below. Hammett's rule was proposed by L. et al. P. A rule of thumb put forward by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include σp and σm values, and these values can be found in many general books. For example, J. A. Dean, ``Lange's Handbook of Chemistry'', 12th edition, 1979 (Mc Graw-Hill); Rev. , 1991, Vol. 91, pp. 165-195. In the present invention, each substituent is limited or explained by Hammett's substituent constant σp value, but it is said that this is limited only to substituents with values known in the literature, which can be found in the above books. It goes without saying that it includes substituents whose values are unknown in the literature but would fall within the range when measured based on Hammett's rule.

Ar ¹ represents a monocyclic aromatic ring group. Monocyclic aromatic ring groups include monocyclic aromatic hydrocarbon ring groups and monocyclic aromatic heterocyclic groups. The heteroatom contained in the monocyclic aromatic heterocyclic group includes, for example, an oxygen atom, a nitrogen atom and a sulfur atom.
Aromatic hydrocarbon rings include, for example, benzene rings. Examples of aromatic heterocycles include triazine rings.
X ^b1 is preferably bonded to a carbon atom (sp2 carbon atom) in the monocyclic aromatic ring group.

p1 represents an integer of 3 or more. Among them, p1 is preferably 3 to 5, more preferably 3 to 4, and even more preferably 4, from the viewpoint that the effect of the present invention is more excellent.
q1 represents an integer of 0 or more. Among them, q1 is preferably an integer of 1 or more, more preferably 1 or 2, and even more preferably 2, from the viewpoint that the effects of the present invention are more excellent.
The sum of p1 and q1 varies depending on the type of Ar ^1. For example, when Ar ¹ is a benzene ring, the sum of p1 and q1 is 3-6.

In formula ( ^B2 ), Xb2 represents a halogen atom. A fluorine atom or a chlorine atom is preferable as the halogen atom.
Ar ² represents a polycyclic group composed of two or more rings.
The rings constituting the polycyclic group may be condensed, may be connected by a single bond, or may be connected by sharing one carbon atom.
The rings constituting the polycyclic group may be aromatic rings or non-aromatic rings, and are preferably aromatic rings. Aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles, with aromatic hydrocarbon rings being preferred.
When the rings constituting the polycyclic group are aromatic rings, ^Xb2 is preferably bonded to a carbon atom (sp2 carbon atom) in the aromatic ring.

^Yb2 represents a substituent other than a halogen atom. The type of substituent is not particularly limited, and groups other than halogen atoms among the groups exemplified as the substituents represented by R ^a1 to R ^a12 can be mentioned.
p2 represents an integer of 3 or more. Among them, p2 is preferably 3 to 5, more preferably 3 to 4, and even more preferably 4, from the viewpoint that the effect of the present invention is more excellent.
q2 represents an integer of 0 or more. Above all, q2 is preferably from 0 to 2 in that the effect of the present invention is more excellent.

In formula (B3), X ^b3 represents a carboxy group, a carboxylic acid chloride group, a group represented by a halogen atom —CH ₂ —, or a group represented by a sulfonyloxy group —CH ₂ —.
^Lb represents a monocyclic aromatic ring group or a carbon atom.
Monocyclic aromatic ring groups include monocyclic aromatic hydrocarbon ring groups and monocyclic aromatic heterocyclic groups. The heteroatom contained in the monocyclic aromatic heterocyclic group includes, for example, an oxygen atom, a nitrogen atom and a sulfur atom.
p3 represents an integer of 3 to 6 when L ^b is a monocyclic aromatic ring group, and represents 4 when L ^b is a carbon atom.

Among them, as the compound B, the compound represented by the formula (B4) or the compound represented by the formula (B5) is preferable because the effects of the present invention are more excellent.

In formulas (B4) to (B5), each X ^b1 independently represents a halogen atom.

Specific examples of compound B are shown below.

The polymer of the present invention is obtained by using at least the compound A and the compound B described above, but compounds other than the compound A and the compound B (hereinafter simply referred to as "other compounds") may be used in combination.
That is, compound A, compound B, and other compounds may be reacted to obtain the polymer of the present invention.
Other compounds include, for example, compound X which does not have the partial structure represented by formula (A1) and has two or more phenolic hydroxyl groups. Compound X may have groups other than the phenolic hydroxyl group, if necessary.
Further, other compounds include compound Y having one or two specific groups. Compound Y may have groups other than the specific group, if necessary.
When compound X has groups other than phenolic hydroxyl groups, and when compound Y has groups other than the specified groups, other groups can be introduced into the formed polymer, resulting in adsorptive can be controlled.
In addition, the following are mentioned as an example as the compound Y which has other groups other than a specific group.

In addition, as will be described later, a known method can be employed for the reaction of compound A and compound B.
In addition, when the compound A and the compound B are reacted, the reaction conditions can be controlled so that a part of the specific group remains.
For example, when compound B has a carboxyl group and a group represented by formula (C) as specific groups, depending on the reaction conditions of compound A and compound B, some or all of the carboxyl groups remain. In this way, the hydrophilicity of the obtained polymer can be increased, and the ability to adsorb hydrophilic substances and ionic substances can also be increased.
Alternatively, for example, using a compound B having six groups represented by the formula (C) (e.g., hexafluorobenzene), a part (one or two) of the leaving groups may remain. , a polymer can also be obtained.
When the compound A and the compound B are reacted, at least a part of the compound B is preferably reacted with three or more specific groups of the compound B with a phenolic hydroxyl group. That is, it is preferable to react the compound A and the compound B so that the repeating unit derived from the compound B and having a valence of 3 or more is contained in the polymer.

The form of reaction between compound A and compound B is not particularly limited as long as the reaction proceeds between the phenolic hydroxyl group and the specific group to form a covalent bond. (Nucleophilic substitution reaction) is preferred.
Conditions for reacting compound A and compound B are not particularly limited, and known conditions are employed.
The reaction between compound A and compound B may be carried out under heating conditions. The heating temperature is not particularly limited, but is preferably 30 to 200°C, more preferably 50 to 150°C.
Although the reaction time is not particularly limited, it is preferably 0.1 to 96 hours, more preferably 2 to 24 hours.
The reaction may be carried out in the presence of a solvent. Solvents include water and organic solvents. Examples of organic solvents include halogen solvents (eg, dichloromethane, tetrachloroethane, chloroform), ketone solvents (eg, acetone), amide solvents (eg, N,N-dimethylformamide), sulfoxide solvents (eg, dimethyl sulfoxide), alcohol solvents (e.g. methanol), hydrocarbon solvents (e.g. benzene, hexane), ester solvents (e.g. methyl acetate, ethyl acetate, butyl acetate), ketone solvents (e.g. acetone, methyl ethyl ketone ), nitrile solvents (eg, acetonitrile), and ether solvents (eg, tetrahydrofuran, 1,2-dimethoxyethane).

Additives may be used as necessary during the reaction.
For example, the above reaction may be carried out in the presence of a basic compound. Basic compounds include, for example, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, dimethylaminopyridine, triethylamine, and pyridine.

The mixing ratio of compound A and compound B varies depending on the structures of compound A and compound B. The ratio of mol of functional hydroxyl group/mol of specific group in compound B) is preferably 3/1 to 1/3.

After completion of the reaction, if necessary, a treatment for purifying the resulting polymer may be carried out. Purification treatment includes a method of washing the polymer with a predetermined solvent.

The resulting polymer has a compound A-derived repeating unit and a compound B-derived repeating unit.
As described above, compound B can be a trivalent or higher repeating unit, so the resulting polymer has a crosslinked structure. In other words, the polymer has a crosslinked structure with internal voids.
As the repeating unit derived from compound A, for example, a repeating unit represented by the following formula is preferable. The definition of each group in the formula below is the same as the definition of each group in formula (A2) described above.

As the repeating unit derived from compound B, for example, a repeating unit represented by the following formula is preferable. The definition of Y ^1b is the same as the definition of Y ^1b in formula (B1) above.

Specific examples of polymers (1 to 24) are shown below. Below, the polymer has the units listed to the right of each number.

Furthermore, the polymer of the present invention can also control the adsorption capacity using a polymer reaction after the reaction of compound A and compound B. For example, the case of using the following polymer of the present invention will be described.

By causing a polymer reaction at the nitrile group site of the above polymer, it can be converted into, for example, the following polymers (25 to 29), and the adsorption ability can be controlled. Below, the polymer has the units listed to the right of each number.

[Use]
Applications of the polymer of the present invention are not particularly limited, and include various applications (eg, adsorbents, separation materials, and sensors) utilizing high specific surface areas.
More specifically, (1) storage, transport, separation and purification of gases such as hydrogen gas and methane gas, (2) deodorization, (3) removal of poisonous gas, (4) separation and recovery of radioactive waste and Decontamination, (5) Artificial dialysis, (6) Chromatographic carrier, (7) Reaction field, reaction vessel, or catalyst for organic synthesis reaction, (8) Harmful substances from air, water, or blood (9) detection of hazardous substances, hazardous substances (nitro compounds, gasoline, etc.) and biomarker substances, analysis of air or exhaled breath, and diagnosis applying this, ( 10) It can be used as an ion or proton conductor, (11) as a drug delivery system, and the like.

Sensors include resonant sensors, resistive sensors, field effect transistor sensors, and concentration desorption sensors.
In addition, the polymer of the present invention is excellent in adsorbing various components. In particular, it has excellent adsorption properties for various solvents. Examples of solvents include halogen solvents (eg, dichloromethane, tetrachloroethane, chloroform), ketone solvents (eg, acetone), amide solvents (eg, N,N-dimethylformamide), sulfoxide solvents (eg, dimethyl sulfoxide), alcohol solvents (e.g. methanol), hydrocarbon solvents (e.g. benzene, hexane), ester solvents (e.g. methyl acetate, ethyl acetate, butyl acetate), ketone solvents (e.g. acetone, methyl ethyl ketone) , nitrile solvents (eg acetonitrile), and ether solvents (eg tetrahydrofuran, 1,2-dimethoxyethane).

EXAMPLES The present invention will be described in detail below using examples. However, the present invention is not limited to this. Unless otherwise specified, the amount of each component is based on mass.

[Example 1]
2,2′,3,3′-tetrahydro-3,3,3′,3′-tetramethyl-1,1′-spirobi[1H-indene]-6,6′-diol (corresponding to compound A) ( 5.00 g), dimethylformamide (DMF) (65 mL) (super-dehydrated, manufactured by FFWK), and potassium carbonate (8.96 g) (manufactured by FFWK) were placed in a 500 mL three-necked flask and heated to an internal temperature of 70 ° C. under a nitrogen stream. .
After that, tetrafluoroterephthalonitrile (1.62 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in DMF (50 mL), and added dropwise to the flask having an internal temperature of 70° C. over 5 hours.
After the reaction solution gelled, it was diluted with DMF (140 mL) and stirred at 70° C. for 2 hours. After the reaction solution was added to 2 L of water and stirred, the solid obtained by filtration was washed with water (1 L) at 60° C. for 1 hour with stirring. Thereafter, the solid content was recovered by filtration and air-dried at 60° C. for 14 hours to obtain the following polymer P-01 (4.11 g).

[Examples 2-3]
Polymers P-02 and P-03 were synthesized according to the same procedure as in Example 1, except that the raw materials used were changed to the compounds shown in the scheme below.

[Comparative Examples 1 and 2]
Polymer C-01 and polymer C-02 were synthesized according to the following scheme according to a known method (for example, the method described in Patent Document 1).

[evaluation]
<BET specific surface area measurement>
BET specific surface area measurement was performed using the various polymers synthesized above.
The amount of samples used in the measurement was uniformly about 50 mg, and the samples were pretreated by heating at 80° C. for 6 hours in a nitrogen stream using Belprep-flow (manufactured by Microtrack Bell). After that, using Belsorp-miniII (manufactured by Microtrack Bell), N ₂ adsorption isotherms under liquid nitrogen temperature were obtained, and using analysis software Belmaster, the BET specific surface area was determined by the BET method. The pressure range used in the analysis was P/P0=0.05-0.15.
A: 300 m ² /g or more B: 200 m ² /g or more and less than 300 m ² /g C: 100 m ² /g or more and less than 200 m ² /g D: less than 100 m ² /g

<Adsorption>
Adsorptive evaluation was performed using the various polymers synthesized above.
Each sample was exposed to saturated vapor of various solvents for 3 minutes at room temperature in a closed container, and the rate of increase in mass was evaluated. The mass increase rate was determined as "{(mass of sample after adsorption) - (mass of sample before adsorption)}/(mass of sample before adsorption) x 100".
Dichloromethane, acetone, and hexane were used as solvents.
(Evaluation criteria for dichloromethane)
A: 90% by mass or more B: 80% by mass or more and less than 90% by mass C: 70% by mass or more and less than 80% by mass D: less than 70% by mass

(Evaluation criteria for acetone)
A: 50% by mass or more B: 40% by mass or more and less than 50% by mass C: 30% by mass or more and less than 40% by mass D: less than 30% by mass

(Evaluation criteria for hexane)
A: 30% by mass or more B: 25% by mass or more and less than 30% by mass C: 20% by mass or more and less than 25% by mass D: less than 20% by mass

Table 1 shows the results of the above evaluation test.

As shown in Table 1, it was confirmed that the desired effects were obtained when the polymer of the present invention was used.
In particular, a comparison of Examples 1 to 3 confirmed that when compound A contained the compound represented by formula (A3), more excellent effects were obtained.

Claims (6)

Compound A represented by formula (A2) ;
A polymer obtained by reacting at least a compound B having three or more groups capable of forming a covalent bond by reacting with the phenolic hydroxyl group in the compound A ,
A polymer in which the compound B contains a compound represented by formula (B1).
Formula (B1) (X ^b1 ) _p1 -Ar ¹ -(Y ^b1 ) _q1
Xb1 ^represents a halogen atom.
Yb1 ^represents a substituent other than a halogen atom.
Ar ¹ represents a monocyclic aromatic ring group.
p1 represents an integer of 3 or more. q1 represents an integer of 0 or more.

In formula (A2), L ^a1 and L ^a2 each independently represent an alkylene group.
L ^a3 and L ^a4 each independently represent a single bond or —O—.
Z ^a1 and Z ^a2 each independently represent a substituent other than a hydroxyl group.
m1 and n1 each independently represent 1 or 2, and the sum of n1 and m1 is 2 or 3;
m2 and n2 each independently represent an integer of 0 to 2; 2. The polymer of claim 1, wherein m2 and n2 are each independently an integer of 0 or 1. 3. The polymer of claim 1 or 2 , wherein q1 is an integer greater than or equal to 1 and ^Yb1 is an electron-withdrawing group. The polymer according to any one of claims 1 to 3 , wherein said compound B comprises a compound represented by formula (B4) or a compound represented by formula (B5).

In formulas (B4) to (B5), each X ^b1 independently represents a halogen atom. Polymer according to any one of claims 1 to 4, wherein the halogen atom is a fluorine atom or a chlorine atom. An adsorbent comprising the polymer according to any one of claims 1-5 .