JP2002293828A - Polymer supported type halogenating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel halogenating agent which can change its solubility to a solvent or the like with maintaining the ability as a halogenating agent and which is recovered and recycled easily. SOLUTION: A specific partial structure capable of supporting a halogen such as (N-methyl-N'-methacryloyl ethylimidazolidinone) or the like is fixed as a side chain within a high polymer compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polymer-supported halogenating agent.

[0002]

2. Description of the Related Art Conventionally, various compounds have been known as halogenating agents. In recent years, haloiminium salts and difluoroimidazolidines (JP-A-2000-38370) have attracted attention. A typical example of the haloiminium salt is 2-chloro-1,3-dimethylimidazolinium chloride (hereinafter abbreviated as CDC), and a difluorooimidazolidine compound is 2,2-difluoro-1,3-dimethyl-imidazolidin ( DFI) is typical. All of the halogenating agents have extremely high reactivity of a halogen atom bonded to the 2-position or an ion-bonded halogen anion, and easily react with various functional groups. Therefore, application research to new organic synthesis has been promoted. I have. In addition, CDC and DFI have an advantage that they can be recovered and reused as 1,3-dimethylimidazolidin-2-one (hereinafter abbreviated as DMI) as a raw material after contributing to the reaction.

[0003] However, DMI is characterized by
It has a high boiling point and often mixes well with water, solvents, raw materials, reaction products, by-products, catalysts, and various polymers, etc. Conversely, in the recovery of DMI itself and the purification of the resulting product, However, there is a problem that the method is complicated and may not be easy. As a method for solving this problem, a method has been proposed in which the haloiminium salt skeleton is immobilized in a polymer compound (Japanese Patent Application Laid-open No.
00-154155). This method is an excellent method that can change the solubility in a solvent or the like and can provide a halogenating agent that is easy to recover and reuse. However, also in this excellent method, since the haloiminium salt skeleton is incorporated in the main chain, steric hindrance, for example, the desired halogenation reaction does not easily proceed, or a decomposition reaction occurs due to an excess reaction temperature. In some cases, the reaction at a higher temperature was required in the process of producing the haloiminium salt. That is, the reactivity may be hindered, and strictly speaking, there is still room for improvement.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel halogenating agent which has solved the conventional disadvantages and is easy to recover and reuse.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a polymer compound having the following partial structural formulas (1) to (4) as side chains If it is immobilized inside, the problem of steric hindrance will be improved, the solubility in solvents etc. can be changed while maintaining the ability as a halogenating agent, and thus a new halogenation that is easy to recover and reuse They have found that an agent can be provided, and have reached the present invention.

[0006]

DETAILED DESCRIPTION OF THE INVENTION That is, the present invention relates to a compound of the formula (1)

[0007]

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(Wherein R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or a residue having 1 to 10 carbon atoms, and R ₂ and R ₃ may be bonded to each other. X ₁ And X ₂ each independently represent a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, provided that X ₁ and X ₂ are not both fluorine atoms.) (2) [Formula 6]

[0009]

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(Wherein R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or a residue having 1 to 10 carbon atoms, and R ₂ and R ₃ may be bonded). The partial structure represented or the formula (3)

[0011]

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(Wherein R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are
Each independently represents a hydrogen atom or a residue having 1 to 10 carbon atoms. Further, R ₄ and R ₅ , R ₆ and R ₇ , R ₄ and R ₆ , R ₄ and R ₇ ,
R ₅ and R ₆ , R ₅ and R ₇ , R ₆ and R ₈ , or R ₇ and R ₈ may be bonded. X ₁ and X ₂ each independently represent a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. However,
X ₁ and X ₂ exclude the case where both are fluorine atoms. Or a partial structure represented by formula (4):

[0013]

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Wherein R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are
Each independently represents a hydrogen atom or a residue having 1 to 10 carbon atoms. Further, R ₄ and R ₅ , R ₆ and R ₇ , R ₄ and R ₆ , R ₄ and R ₇ ,
R ₅ and R ₆ , R ₅ and R ₇ , R ₆ and R ₈ , or R ₇ and R ₈ may be bonded. A) a reactive oligomer or polymer having at least one of one or more selected from the partial structures represented by the following, or a reactive composition containing them, and further using them as a reactant. It is a reaction method. Hereinafter, the present invention will be described in detail.

R _{1 to} R ₈ represented by the formulas (1) to (4) are
Each independently represents a hydrogen atom, a residue having 1 to 10 carbon atoms, or a residue having 1 to 10 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms. Further, R ₂ and R ₃ , R ₄ and R ₅ ,
R ₆ and R _7, R ₄ and R _6, R ₄ and R _7, R ₅ and R _6, R ₅ and R _7,
R ₆ and R ₈ , or R ₇ and R ₈ may be bonded. The residue according to the present invention represents a substituted or unsubstituted saturated or unsaturated alkyl group or a substituted and unsubstituted aryl group, unless otherwise specified.In addition to carbon and hydrogen atoms, for example,
It may contain a hetero atom such as an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom, a boron atom, a phosphorus atom, and furthermore, a part or all of the hydrogen atoms constituting the residue are a fluorine atom, a chlorine atom, a bromine atom And an iodine atom or the like. R _{1 to} R ₈ when the residues are not bonded to each other are preferably C ₁ to C 6 residues,
If the residue has 1 to 4 carbon atoms, more preferable results may be obtained.

R ₂ and R ₃ , R ₄ and R ₅ , R ₆ and R ₇ , R ₄ and R ₆ , R ₄ and R ₇ , R ₅ and R ₆ , R ₅ and R ₇ , R ₆ and R ₈ Or when R ₇ and R ₈ are bonded, the number of carbon atoms constituting the ring is relatively preferably 4 to 18, more preferably 4 to 12, and still more preferably 4 to 6, when the number of carbon atoms constituting the ring is 4 to 6. You. Further, the formed ring structure is represented by the formulas (1) to (4).
May be formed in the partial structural formula represented by, furthermore, a saturated or unsaturated alicyclic structure, even an aromatic ring structure, other than carbon and hydrogen atoms, for example, an oxygen atom, It may have a heterocyclic structure containing a hetero atom such as a sulfur atom, a selenium atom, a nitrogen atom, a boron atom, and a phosphorus atom. A part or all of the hydrogen atoms constituting the ring may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, or a residue having 1 to 6 carbon atoms.

[0017] formula (1), X ₁ and X ₂ described in Formula (3) is independently a fluorine atom, respectively, a chlorine atom, a bromine atom, or represents a iodine atom, X ₁ and X ₂ Except when both are fluorine atoms.

If the partial structure represented by the formula (1) is more specifically described, for example, N, N, N'-trimethyl-chloro-formamidium-chloride, N, N,
N'-trimethyl-bromo-formamidium-chloride, N, N, N'-trimethyl-bromo-formamidium-bromide, N, N, N'-trimethyl-iodo-formamidium-iodide, N, N , N'-Trimethyl-
Chloro-formamidium-bromide, N, N, N'-
Trimethyl-chloro-formamidium-iodide,
N, N, N'-trimethyl-fluoro-formamidium-
Chloride, N, N, N'-trimethyl-fluoro-formamidium-bromide, N, N, N'-trimethyl-
Fluoro-formamidium-iodide, N, N, N '
-Tris (trifluoromethyl) -chloro-formamidium-chloride, N, N, N'-triethyl-chloro-formamidium-chloride, N, N, N'-tris (trifluoroethyl) -chloro-form Amidium chloride, N, N, N'-tripropyl-chloro-formamidium chloride, N, N, N'-tributyl-chloro-
Formamidium-chloride, N, N, N'-trihexyl-chloro-formamidium-chloride, N, N,
N'-tricyclohexyl-chloro-formamidium-chloride, N, N, N'-triphenyl-chloro-formamidium-chloride, N, N, N'-tribenzyl-
Chloro-formamidium-chloride, N, N, N'-
Trinaphthyl-chloro-formamidium-chloride,
N, N, N'-Trinaphthyl-chloro-formamidium-
Chloride and the like.

If the partial structure represented by the formula (2) is more specifically described, for example, N, N, -dimethyl-
N'-methyl-difluoromethane, N, N, -di (trifluoromethyl) -N '-(trifluoromethyl) -difluoromethane, N, N, -diethyl-N'-methyl-
Difluoromethane, N, N, -di (trifluoroethyl) -N '-(trifluoroethyl) -difluoromethane, N, N, -dibutyl-N'-butyl-difluoromethane, N, N, -dihexyl-N '-Hexyl-difluoromethane, N, N, -dicyclohexyl-N'-cyclohexyl-difluoromethane, N, N, -diphenyl-N'-phenyl-difluoromethane, N, N, -dibenzyl-N'-benzyl-difluoro Methane, N, N,
-Dinaphthyl-N'-naphthyl-difluoromethane and the like.

If the partial structure represented by the formula (3) is more specifically described, for example, N-methyl-chloro-imidazolidium-chloride, N, -methyl-bromo-imidazolidium-chloride, N -Methyl-bromo-imidazolidium-bromide, N, -methyl-iodo-imidazolidium-iodide, N-methyl-chloro-imidazolidium-bromide, N-methyl-chloro-imidazolidium-iodide, N-methyl-fluoro- Imidazolidium-chloride, N-methyl-fluoro-imidazolidium-bromide, N-methyl-fluoro-imidazolidium-iodide, N- (trifluoromethyl) -chloro-imidazolidium-chloride, N-ethyl-chloro-
Imidazolidium chloride, N- (trifluoroethyl) -chloro-imidazolidium chloride, N-propyl-chloro-imidazolidium chloride, N-butyl-chloro-imidazolidium chloride, N-hexyl-chloro-imidazolidium chloride -Chloride, N-cyclohexyl-chloro-imidazolidium-chloride, N
-Phenyl-chloro-imidazolidium-chloride, N-
Benzyl-chloro-imidazolidium-chloride, N-
Naphthyl-chloro-imidazolidium-chloride, N-
Methyl-2-chloro-benzimidazolidium-chloride and the like.

If the partial structure represented by the formula (4) is more specifically described, for example, N-methyl-2,2-difluoro-imidazolidine, N- (trifluoromethyl) -2,2 -Difluoro-imidazolidine, N-ethyl-2,2-difluoro-imidazolidine, N- (trifluoroethyl) -2,2-difluoro-imidazolidine, N-butyl-2,2-difluoro-imidazolidine, N -Hexyl-2,2-difluoro-imidazolidine, N-cyclohexyl-2,2-difluoro-imidazolidine, N-phenyl-2,2-difluoro-imidazolidine, N-benzyl-2,2-difluoro-imidazolidine , N-naphthyl-2,2-difluoro-imidazolidin, N-methyl-2,2-difluoro-benzimidazole, and the like. Is not limited only to the partial structure described above.

In the reactive oligomer or polymer of the present invention, at least one of the partial structures represented by the formulas (1) to (4) is immobilized as a side chain in a polymer compound. Things. Therefore, Equations (1) to (4)
The partial structure represented by may be fixed by only one type, two or more types may be fixed by combining several types, or all types may be fixed. It is more preferable that the partial structures represented by the formulas (1) to (4) are immobilized in the polymer compound as a side chain. Immobilization with the main chain may inhibit the reactivity.

Examples of the method of immobilization in a polymer compound include a method of polymerizing a polymerizable compound having a partial structure represented by formulas (1) to (4), a method of formulas (1) to (4) A) a method of copolymerizing a polymerizable compound having a partial structure represented by formula (1) with another polymerizable compound, a method of bonding a partial structure represented by formulas (1) to (4) to an oligomer or a polymer, Various methods such as a method of synthesizing a desired reactive oligomer or polymer using an oligomer or a polymer having a partial structure that is a precursor of the partial structure represented by 1) to (4) as a raw material can be given. However, the present invention is not limited by the immobilization method described above.
The polymer compound according to the present invention in which the partial structures represented by the formulas (1) to (4) are immobilized has at least one kind or two or more kinds of arbitrary repeating structural units. Represents an organic polymer compound having two or more repeating structural units. In order to facilitate the recovery and reuse by changing the solubility in a solvent or the like, the effect is exhibited even if any one of the repeating structural units is 2, but one or more of the repeating structural units are effective. More preferably, the total of the units is 5 or more,
If it is 10 or more, more preferable results may be obtained.

The reactive composition of the present invention essentially contains at least one kind of the above-mentioned reactive oligomer or polymer. Therefore, if you meet this requirement,
Any other compound may be contained as long as no problem occurs. For example, solvents, reactive compounds, polymerizable compounds, other oligomers / polymers, binders, inorganic and organic acids, stabilizers, dehydrating agents, antioxidants, unreacted raw materials, by-products, additives and the like can be mentioned.

The reaction method of the present invention using a reactive oligomer or polymer having a partial structure represented by the formulas (1) to (4), or a composition containing them as a reactant,
For example, phosphorus tribromide, thionyl chloride, N, N'-dimethyl-chloro-imidazolidium chloride, diethylaminosulfur trifluoride, N, N, -dimethyl-
It can be used in almost the same reactions as ordinary halogenating agents such as 2,2-difluoro-imidazolidin. Specific examples of the reaction use include, for example, halogenation of alcohol, acid halide formation of carboxylic acid, esterification of hydroxycarboxylic acid, dihalogenation of ketone, and unsaturated monohalogenation. The invention is not limited to only these use examples.

The method for producing the reactive polymer of the present invention will be described below with reference to an example, but the present invention is not limited to this method. For example,
Poly (N-methyl-N′-methacryloylethylimidazolidinone) is obtained by reacting bishalogenoethylamines with an alkali metal hydrogencarbonate such as sodium hydrogencarbonate or an alkali metal carbonate such as sodium carbonate.
An alkylamine is reacted with halogenoethyl-2-oxazolidone to synthesize N-alkyl-N′-hydroxyalkylimidazolidinone. Then, N-alkyl-
A methacrylate is obtained by reacting N'-hydroxyalkylimidazolidinone with methacrylic acid chloride. The reaction temperature at this time is approximately -50 to 200 ° C and 0 to 150.
C. is preferable, and 0-100 C. is more preferable.

Next, the monomer is polymerized to be polymerized. Polymerization methods include, for example, a photopolymerization method performed by adding a photocatalyst or a photoinitiator as necessary, a radical polymerization method, an anion catalyst, a thermal polymerization method performed by adding a cation catalyst, and the like, if necessary. There are various methods such as a solution polymerization method performed in a solution, and in the present invention, these polymerization methods are arbitrarily selected according to the purpose. Furthermore, copolymerization with a polymerizable compound such as methyl methacrylate, styrene, (poly) ethylene glycol di {(meth) acrylate}, bisphenol A-bis {(meth) acryloyl (poly) oxyalkylene} may be performed.

Here, the case of solution polymerization will be described by way of example, but the present invention is not limited by these polymerization methods. For example, it can be obtained by mixing N-methyl-N′-methacryloylethylimidazolidinone and methyl methacrylate with a solvent such as cyclohexane, adding a catalyst such as AIBN, and heating. The poly (N-methyl-N′-methacryloylethylimidazolidinone) -methyl methacrylate copolymer thus obtained is halogenated with a halogenating agent to give the poly (N-methyl-N′-) of the present invention.
A methacryloylethyl-2-chloro-imidazolidium-chloride) -methyl methacrylate copolymer is synthesized. As the halogenating agent used in this case, for example, thionyl halide, oxalyl halide, phosphorus trihalide, phosphorus pentahalide, phosphorus oxyhalide, halogenated carbonyl, halomethyl haloformate and the like. Can be

When it is desired to synthesize a polymer in which X1 and X2 of the partial structure represented by the formula (1) or (3) are fluorine, bromine, or iodine, the halogenation is carried out directly using the corresponding halogenating agent. The chlorinated product may be synthesized by a halogen exchange reaction using a corresponding halogen exchange agent such as an alkali metal halide. Furthermore, the poly (N-methyl-N'-methacryloylethyl-2,2-difluoro-imidazolidin) -methyl methacrylate copolymer of the present invention having a partial structure represented by the formula (2) or (4) Is synthesized, the resulting poly (N-methyl-N′-methacryloylethyl-2-chloro-
It can be synthesized by adding a halogen exchange agent to the imidazolidium-chloride) -methyl methacrylate copolymer and exchanging the halogen. Examples of the halogen exchange agent used herein include fluoro salts such as cesium fluoride, silver fluoride, potassium fluoride, and sodium fluoride.

The temperature at which the above-mentioned halogenation reaction or halogen exchange reaction is carried out is from -20 to 200 ° C., preferably from 0 to 200 ° C.
To 180 ° C, more preferably 20 to 150 ° C.
If the temperature is lower than −20 ° C., the reaction takes a long time,
If the temperature is higher than ° C., the generated target product may be decomposed, which may not be preferable. The molar ratio of the halogenating agent or halogen exchanging agent used is stoichiometric or more, for example, poly (N-methyl-N'-methacryloylethylimidazolidinone)-
In the case of the methyl methacrylate copolymer, the amount is preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents, and still more preferably 1 to 3 equivalents to the imidazolidinone structure. Use of more than 10 equivalents of halogenating agent may be economically disadvantageous. The reaction solvent is not particularly limited as long as it does not react with the raw material, the halogenating agent, and the target substance. For example, benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, dichloromethane, 1,
2-dichloroethane, acetonyl, N, N-dimethylformamide, N, N-dimethylimidazolidinone, sulfolane, tetrahydrofuran and the like.

After completion of the reaction, filtration or decantation of the solvent, and evaporation of the solvent and excess halogenating agent are carried out to obtain the poly (meth) acrylate having a partial structure represented by the formula (1) or (3) of the present invention. Halloyminium salt or formula (2) of the present invention
Alternatively, polydifluoromethines having a partial structure represented by the formula (4) can be obtained. The polyhaloiminium salts, polydifluoromethines, and the reactive oligomers, reactive polymers, and reactive compositions containing them of the present invention often have high water absorption, and the halogen moiety reacts with water. In some cases, it may be possible to return to the raw material, and therefore it is preferable that the handling is performed in a dry atmosphere.

[0032]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 {Synthesis of chloroethyl oxazolidone (hereinafter abbreviated as CEAZ)} 173.2 g of 97% sodium hydroxide (4.20)
Mol), 378.0 g (4.50 mol) of sodium hydrogen carbonate and 1500 ml of water were mixed to form a homogeneous solution. Next, 750.0 g (4.20 mol) of bis (2-chloroethyl) amine hydrochloride was separately charged into the solution at an internal temperature of 30 to 35 ° C over 0.5 hour, and the mixture was aged at 40 ° C for 4 hours. . 0.5 l of chloroform was charged into the obtained reaction solution and stirred, and a lower organic layer was collected. The upper aqueous layer was extracted with 0.5 l of chloroform three times (1.5 l in total) to extract organic components. The chloroform layers were combined and the solvent was removed to obtain 569.8 g (3.55 mol, pure conversion yield = 84.5%) of CEAZ having a purity of 93.2%.

Example 2 Synthesis of N-methyl-N'-hydroxyethylimidazolidinone (hereinafter abbreviated as HEMI) In a 500 ml Hastelloy C autoclave, 140 g (1.80 mol) of a 40% aqueous solution of methylamine and a purity of 9 were prepared.
95.5 g (0.60 mol) of 3.2% CEOZ was charged and reacted at 120 ° C. for 2 hours. After cooling, the reaction solution was extracted, and 24.0 g of sodium hydroxide was used at an internal temperature of 20 to 35 ° C.
(0.6 mol) was added for neutralization, and the precipitated salt was removed by filtration. Then, after evaporating water with an evaporator,
After dissolving in chloroform, the precipitated salt was filtered and chloroform was distilled off by an evaporator. The concentrated residue is purified by silica gel column chromatography, and the purity is 99%.
Of HEMI was 67.1 g (0.47 mol, purification yield = 7)
7%).

Example 3 Synthesis of N-methyl-N'-methacryloylethylimidazolidinone (hereinafter abbreviated as MMEU) 40.0 g (0.275 mol) of 99% pure HEMI,
To a mixture of 28.3 g (0.280 mol) of triethylamine and 80 g of chloroform, 29.2 g (0.280 mol) of methacrylic acid chloride was added dropwise at an internal temperature of 0 to 10 ° C over 1 hour. Aged for hours. Chloroform and water were added to the reaction solution to separate it, and the upper aqueous layer was discarded. The obtained organic layer was concentrated under reduced pressure by an evaporator, and the residue was purified by silica gel column chromatography. As a result, 38.2 g of 92% pure MMEU was obtained.
(0.166 mol, pure conversion yield = 60.2%).

Example 4 Synthesis of poly (N-methyl-N'-methacryloylethylimidazolidinone) (hereinafter abbreviated as PMMU) 120 m of cyclohexane subjected to nitrogen bubbling at room temperature
azobisisobutyronitrile (AIBN) 300m
g was added and nitrogen bubbling was performed. Then, 38.0 g of the MMEU of Example 3 was charged therein, and the temperature was increased to carry out heat polymerization at 70 ° C. for 4 hours. After completion of the polymerization, the solvent cyclohexane was decanted, and 60 ml of methanol was added to the remaining white solid.
Was added and dissolved, and the mixture was added dropwise with stirring to 500 ml of diethyl ether spread in advance, and the precipitated white solid was taken out and dried under reduced pressure. As a result, 18.1 g of an MMEU polymer having an average molecular weight of 120,000 (in terms of polystyrene) as determined by GPC analysis was obtained. As a result of DSC measurement of this polymer, neither Tg nor Tm was observed in the range of −180 to 250 ° C. (1st-Heat, 1st-Cool,
2nd-Heat).

Example 5 Poly (2-chloro-1-methyl-3-methacryloylethylimidazolidinium chloride) (hereinafter abbreviated as PMMC)
To 30 g of PMMU, 300 g of dichloroethane was added, dissolved with stirring, heated to 50 ° C., and 53.9 g (0.425 mol) of oxalyl chloride was added dropwise over 30 minutes. The temperature was raised to 70 ° C. and aging was performed for 9 hours. PMMC generated from about 4 hours of aging precipitates as an oily substance,
The reaction liquid became a suspension. After ripening, the mixture was cooled to room temperature and allowed to stand, and then separated into two layers, and PMMC became a lower layer. The supernatant dichloroethane was discarded, and the PMMC layer was dropped into 500 ml of ether while stirring. Since a dark brown solid precipitated, ether was decanted and the solid was dried under reduced pressure to obtain 31.8 g of PMMC. The chlorine content in the obtained PMMC was 14.6% as determined by silver nitrate titration. The obtained PMMC and 1-octanol were mixed at room temperature, and the solution was analyzed by GC-MS.
A chlorooctane peak was observed. From this, P
It was confirmed that MMC had a chlorination ability.

Example 6 Synthesis of poly (2,2-difluoro-1-methyl-3-methacryloylethyl imidazolidine) While stirring 100 g of acetonitrile, 21 g of PMMC obtained in Example 5 was dissolved and heated to 40 ° C. After warming, 12 g of silver fluoride was added thereto. Some time after the addition, white turbidity, which was considered to be silver chloride, occurred, and the amount increased with time. After stirring at the same temperature for 2 hours, the mixture was cooled to room temperature, and the suspension was centrifuged to remove solids (silver chloride). The silver chloride that could not be removed was filtered through a membrane filter, and the filtrate was dropped into 500 ml of diethyl ether to precipitate a polymer. The precipitated polymer was dried under reduced pressure at 30 ° C. to obtain 17.3 g of PMMF. The obtained PMMF and 1-octanol were mixed at room temperature, and the solution was analyzed by GC-MS. As a result, a peak of 1-fluorooctane was confirmed. From this, PMMF
Was confirmed to have fluorination ability.

[0038]

According to the present invention, it is possible to provide a novel halogenating agent in which a haloiminium salt skeleton is immobilized in a polymer compound and which can be recovered and reused.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Naoki Asashige 580-32 Nagaura, Sodegaura-shi, Chiba F-term in Mitsui Chemicals, Inc. (reference) 4J100 AB02Q AL03Q AL08P AL66Q BA08Q BC43Q BC73P CA04 JA15

Claims (4)

[Claims] 1. A compound represented by the formula (1): (Wherein R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom or a residue having 1 to 10 carbon atoms, and R ₂ and R ₃ may be bonded to each other. X ₁ and X ₂ Each independently represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, provided that X is
₁ and X ₂ exclude the case where both are fluorine atoms. Or a partial structure represented by the formula (2): (Wherein R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom or a residue having 1 to 10 carbon atoms, and R ₂ and R ₃ may be bonded to each other). Partial structure or formula (3) (In the formula, R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ each independently represent a hydrogen atom or a residue having 1 to 10 carbon atoms.
₄ and R ₅ , R ₆ and R ₇ , R ₄ and R ₆ , R ₄ and R ₇ , R ₅ and R ₆ , R
₅ and R ₇ , R ₆ and R ₈ , or R ₇ and R ₈ may be bonded. X ₁ and X ₂ each independently represent a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. However, X ₁ and X ₂
Excludes the case where both are fluorine atoms. ) Or a partial structure represented by the formula (4): (In the formula, R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ each independently represent a hydrogen atom or a residue having 1 to 10 carbon atoms.
₄ and R ₅ , R ₆ and R ₇ , R ₄ and R ₆ , R ₄ and R ₇ , R ₅ and R ₆ , R
₅ and R ₇ , R ₆ and R ₈ , or R ₇ and R ₈ may be bonded. A) a reactive oligomer or polymer having at least one of one or more selected from the partial structures represented by 2. The reactive oligomer or polymer according to claim 1, wherein the repeating structural unit has at least two or more moieties. 3. A reactive composition comprising at least one reactive oligomer or polymer according to claim 1 or 2. 4. The reactive oligomer according to claim 1, wherein
A reaction method using a reactive polymer or a reactive composition as a reactant.