JP5806926B2 - Macroazo compound, precursor thereof and production method - Google Patents

Description

  The present invention relates to a novel macroazo compound having a cyclic polymer chain in one molecule, a precursor thereof, and a production method. More specifically, the present invention relates to a novel macroazo compound, a precursor thereof, and a production method thereof that can synthesize a network polymer having a mobile bridge by using it as a polymerization initiator.

In the crosslinked polymer, polymer chains are usually bound to each other by chemical bonds to form a three-dimensional network structure. Conventional crosslinking for forming such a three-dimensional structure is roughly divided into chemical crosslinking and physical crosslinking.
Chemical crosslinking is crosslinking in which polymer chains are linked by a covalent bond, and a network structure is usually formed by a polyfunctional compound added to a polymerization system acting as a crosslinking agent. On the other hand, physical crosslinks are crosslinks that link polymer chains by reversible interactions weaker than covalent bonds, such as hydrophobic interactions, ionic interactions, hydrogen bonds, or coordination interactions, and are linear polymer chains. A network structure is formed by a local regular structure, for example, a crystal structure, a helix structure, or an interaction between a polymer chain and a solvent.

  In recent years, cross-linked structures called transfer cross-links, mechanical cross-links or topological bridges that belong to a new category different from conventional chemical cross-links and physical cross-links have been proposed. In this cross-linking, a backbone polymer is threaded through a cyclic molecule to form a mechanical link, and the polymer chains are constrained to each other so that there is no chemical bond including a covalent bond between the polymer chains. Nevertheless, a three-dimensional network structure is formed.

By introducing such a mobile crosslink into a polymer, it is possible to expect unprecedented physical properties. Therefore, a non-bonding crosslinker for providing a network polymer having a mobile crosslink has been developed.
The crosslinking reaction using a non-bonding crosslinking agent is classified into the following types, for example, depending on the crosslinked structure to be formed.
Type A: In polycondensation with an aromatic diamine, a dicarboxylic acid having a crown ether moiety is allowed to function as a non-bonding cross-linking agent to form a network structure in which the polymer chain segment of the aromatic diamine is threaded through the crown ether moiety. Type B: Polyrotaxane cyclic sites are bonded with a polyfunctional reagent such as cyanuric chloride to form a network structure in which rotaxane chains are constrained by 8-shaped cross-linking points. Type C: Polymerized with macrocyclic sites A cyclic macromonomer having a functional group as a non-bonding type cross-linking agent to form a network structure in which polymer growth chains pass through cyclic sites

Among these, Type C can be expected to be applied with a relatively large number of monomers if a cyclic macromonomer is synthesized.
Cyclic macromonomer in which a polymerizable functional group such as a methacrylamide moiety is introduced into a cyclic polyethylene oxide having a pore size that can be threaded (see Non-Patent Document 1) and polymerization as a non-bonding type crosslinking agent of type C A cyclic polytetrahydrofuran into which a functional functional group is introduced (see Non-Patent Document 2) has been proposed.

Anat Zada, 2 others, `` Monomers for non-bond crosslinking of vinyl polymers II. Cyclic octaethylene glycol 5-methacrylamidoisophthalete '', European Polymer Journal, ELSEVIER, 2000, 36, p.351-357 Hideaki Oike, 2 others, `` A Cyclic Macromonomer Designed for a Novel Polymer Network Architecture Having Both Covalent and Physical Linkages '', Macromolecules, American Chemical Society, 2001, Vol. 34, p.6229-6234

  The present invention relates to a novel macroazo compound having a cyclic polymer chain in one molecule, a precursor thereof and a production method thereof, and more specifically, a network polymer having mobile crosslinking easily and efficiently by using it as a polymerization initiator. It is an object of the present invention to provide a novel macroazo compound, a precursor thereof, and a method for producing the same.

Generally, it is known that a segment of a polymerization initiator is bonded to the end of a polymer chain.
Therefore, even if a cyclic macromonomer described in Non-Patent Document 1 and Non-Patent Document 2 is not used, a macroazo compound having a cyclic polymer chain is used as a polymerization initiator, so that the polymer terminal can be efficiently used. It can be expected that a cyclic polymer chain can be added to the polymer, and at the same time, a threading of a cyclic structure occurs efficiently in the polymerization process, and a network polymer having a mobile bridge can be synthesized.

  The inventors of the present invention consider that it is important for the cyclic polymer portion to form a large inner hole in the reaction system in order for the threading to form a network structure having a mobile bridge efficiently occurs, The present inventors have found a novel macroazo compound of the present invention and have completed the present invention.

Thus, according to the invention, the general formula (I):

(In the formula, X is O or NH, R ₁ and R ₂ are the same or different and are CN or an alkyl group having 1 to 4 carbon atoms, and R ₃ is an alkylene group having 1 to ₃ carbon atoms or 1-imino. -2-azabutylene group, M is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 5 to 100)
In expressed, macroazo compound having a number average molecular weight Mn of 1,500～4,000 and weight average molecular weight Mw is characterized 1,800～5,000 der Rukoto is provided.

According to the invention, the general formula (II):
(In the formula, M and n are as defined in formula (I), and R ₄ is OH or NH ₂ ).
A precursor of the above-mentioned macroazo compound, characterized in that

Furthermore, according to the present invention,
General formula (II):

(In the formula, M and n are as defined in the following general formula (I), and R ₄ is OH or NH ₂ ).
A compound represented by formula (III):
(In the formula, R ₁ , R ₂ and R ₃ have the same meanings as the following general formula (I))
Is reacted with a compound represented by the general formula (I):

(In the formula, X is O or NH, R ₁ and R ₂ are the same or different and are CN or an alkyl group having 1 to 4 carbon atoms, and R ₃ is an alkylene group having 1 to ₃ carbon atoms or 1-imino. -2-azabutylene group, M is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 5 to 100)
In expressed, producing a macroazo compound having a number average molecular weight Mn of 1,500～4,000 a is and a weight average molecular weight Mw is characterized in that it comprises a step of obtaining a 1,800～5,000 der Ru compounds A method is provided.

  According to the present invention, a novel macroazo compound having a cyclic polymer chain in one molecule, a precursor and a production method thereof, and more specifically, a network polymer having a mobile bridge is synthesized by using as a polymerization initiator. It is possible to provide a novel macroazo compound, a precursor thereof, and a production method thereof.

1 is a ¹ H-NMR spectrum of the compound (2) of Example 1. 2 is an IR spectrum of the compound (2) of Example 1. 1 is a ¹ H-NMR spectrum of the compound (3) of Example 1. 3 is an IR spectrum of the compound (3) of Example 1. 1 is a ¹ H-NMR spectrum of the compound (5) of Example 1. 2 is an MS spectrum of the compound (5) of Example 1. 1 is a ¹ H-NMR spectrum of the compound (II) of Example 1. 2 is an MS spectrum of the compound (II) of Example 1. 1 is a ¹ H-NMR spectrum of the compound (I) of Example 1. 2 is an IR spectrum of the compound (I) of Example 1. 3 is GPC data of the compound (I) of Example 1.

The macroazo compound of the present invention has the general formula (I):

(In the formula, X is O or NH, R ₁ and R ₂ are the same or different and are CN or an alkyl group having 1 to 4 carbon atoms, and R ₃ is an alkylene group having 1 to ₃ carbon atoms or 1-imino. -2-azabutylene group, M is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 5 to 100)
It is represented by.

The substituent in general formula (I) is demonstrated.
In the following description, for example, the compound represented by the general formula (A) is also referred to as “compound (A)”.
The substituent X is O or NH, and O is preferable from the viewpoint of ease of synthesis.
The substituents R ₁ and R ₂ are the same or different and are CN or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert Examples include linear or branched alkyl groups such as -butyl and sec-butyl. Among these, a methyl group and CN are particularly preferable from the viewpoint of ease of synthesis.

The substituent R ₃ is an alkylene group having 1 to 3 carbon atoms or a 1-imino-2-azabutylene group (—CH ₂ —CH ₂ —NH—C (═NH) —), and the alkylene group is methylene. , Ethylene, trimethylene and the like. Among these, an ethylene group is particularly preferable from the viewpoint of ease of synthesis.
The substituent M is an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group include ethylene, trimethylene, tetramethylene, and the like. Among these, an ethylene group is particularly preferable from the viewpoint of ease of synthesis.

  The index n is a numerical value particularly related to the molecular weight of the compound (I), is an integer of 5 to 100, and is preferably an integer of 5 to 50, particularly preferably 10 to 35 in terms of ease of synthesis. Is an integer.

  The molecular weight of the macroazo compound of the present invention is usually 500 to 50,000, preferably 1,500 to 4,000 in terms of number average molecular weight Mn, and 600 to 60,000, preferably 1,800 in terms of weight average molecular weight Mw. ~ 5,000.

  Specific examples of the macroazo compound of the present invention include 4,4′-azobis ((3,5-bis (cyclopolyethyleneglycolcarbamoyl) phenyl) 4-cyanopentanoic acid), 4,4′-azobis ((3,5 -Bis (cyclopolyethyleneglycolcarbamoyl) phenyl) N- (2-carboethyl) 2-methylpropion-amidine).

  The macroazo compound of the present invention, for example, reacts a specific azodicarboxylic acid with a specific cyclic polymer using a condensing agent in the presence of a basic catalyst if necessary, as shown below. However, the present invention is not limited to this.

(First step)
General formula (1):

(Wherein R ₄ is OH or NH ₂ )
And a compound represented by general formula (2):

(Wherein R ₅ is (CH ₃ CO) O or (CH ₃ CO) NH)
To obtain a compound represented by:

  Specifically, compound (1) and acetic anhydride are reacted by heating under reflux, and the resulting reaction mixture is poured into, for example, ice water and cooled to precipitate a solid, and the resulting solid is converted into, for example, distilled water / ethanol. Recrystallization from = 1/1 (v / v) gives compound (2).

  The compound (1) is specifically 5-hydroxyisophthalic acid and 5-aminoisophthalic acid, and the compound (2) is specifically 5-acetoxyisophthalic acid and 5-acetamidoisophthalic acid.

The use ratio of compound (1) and acetic anhydride is 1: 3 to 5 in molar ratio.
When acetic anhydride is less than 3 mol with respect to 1 mol of compound (1), the yield of the target compound may be reduced. On the other hand, when acetic anhydride exceeds 5 moles with respect to 1 mole of compound (1), the production cost may increase.

The reaction conditions may be appropriately set depending on the type and amount of raw materials.
The reaction temperature is usually 20 to 150 ° C, preferably 100 to 140 ° C.
When reaction temperature is less than 20 degreeC, there exists a possibility that reaction efficiency may fall. On the other hand, when reaction temperature exceeds 150 degreeC, there exists a possibility that the yield of a target compound may fall and manufacturing cost may become high.
Moreover, reaction time is 5 to 24 hours normally, Preferably it is 10 to 15 hours.
When reaction time is less than 5 hours, there exists a possibility that reaction may become inadequate. On the other hand, when reaction time exceeds 24 hours, there exists a possibility that manufacturing cost may become high.
Furthermore, the reaction pressure is not particularly limited, and examples thereof include atmospheric pressure.
The atmosphere is not particularly limited, and examples thereof include air and a nitrogen atmosphere.

(Second step)
The compound represented by the general formula (2) obtained in the first step is reacted with 2-mercaptothiazoline to give a general formula (3):

(Wherein R ₅ has the same meaning as in formula (2))
To obtain a compound represented by:

Specifically, the compound (2) obtained in the first step and thionyl chloride as the chlorinating agent are heated to reflux in the presence of the solvent A and dimethylformamide, the solvent A is distilled off, and 2-mercapto is distilled off. Thiazoline and solvent B are added, and further triethylamine is added and reacted. Next, the obtained reaction mixture is washed, dried and crystallized in a solvent by a known method to obtain a compound (3).
As described above, in this reaction, it is preferable to react the compound (2) with 2-mercaptothiazoline in the presence of a chlorinating agent such as thionyl chloride or phosphorus oxychloride.

The use ratio of the compound (2) and triethylamine is 1: 2 to 4 in molar ratio.
When the amount of triethylamine is less than 2 moles relative to 1 mole of compound (2), the yield of the target compound may be reduced. On the other hand, when the amount of triethylamine exceeds 4 mol per 1 mol of compound (2), the production cost may increase.

  Specifically, the compound (3) includes 5- (acetoxy) -1,3-phenylene) bis ((2-thioxathiazolin-3-yl) methine and 5- (diacetylamino) -1,3-phenylene. ) Bis ((2-thioxathiazolin-3-yl) methine.

The use ratio of compound (2) and thionyl chloride is 1: 3-5 in molar ratio.
When the amount of thionyl chloride is less than 3 mol relative to 1 mol of compound (2), the yield of the target compound may be reduced. On the other hand, when the amount of thionyl chloride exceeds 5 mol with respect to 1 mol of compound (2), the production cost may increase.

The solvent A is not particularly limited as long as it does not adversely affect the raw material compound and the reaction compound and can be easily distilled off, and examples thereof include benzene, toluene, hexane, and cyclohexane.
The amount used is about 5 to 50 times the capacity of the raw material compound.

The reaction conditions may be appropriately set depending on the type and amount of raw materials.
The reaction temperature is usually 20-100 ° C, preferably 60-80 ° C.
When reaction temperature is less than 20 degreeC, there exists a possibility that reaction efficiency may fall. On the other hand, when reaction temperature exceeds 100 degreeC, there exists a possibility that the yield of a target compound may fall and manufacturing cost may become high.
Moreover, reaction time is 1 to 10 hours normally, Preferably it is 3 to 5 hours.
When reaction time is less than 1 hour, there exists a possibility that reaction may become inadequate. On the other hand, when reaction time exceeds 10 hours, there exists a possibility that manufacturing cost may become high.
Furthermore, the reaction pressure is not particularly limited, and examples thereof include atmospheric pressure.
The atmosphere is not particularly limited, and examples thereof include air and a nitrogen atmosphere.

The ratio of the compound (2) to 2-mercaptothiazoline used is 1: 2 to 2.5 in terms of molar ratio.
When the amount of 2-mercaptothiazoline is less than 2 moles relative to 1 mole of compound (2), the yield of the target compound may be reduced. On the other hand, when the amount of 2-mercaptothiazoline exceeds 2.5 mol with respect to 1 mol of compound (2), the production cost may increase.

The solvent B is not particularly limited as long as it does not adversely affect the raw material compound and the reaction compound and can be easily distilled off, and examples thereof include tetrahydrofuran, diethyl ether, diisopropyl ether, dioxane, ethyl acetate and the like.
The amount used is about 5 to 100 times the capacity of the raw material compound.

The reaction conditions may be appropriately set depending on the type and amount of raw materials.
The reaction temperature is usually 5 to 50 ° C., preferably 10 to 30 ° C.
When reaction temperature is less than 5 degreeC, there exists a possibility that reaction efficiency may fall. On the other hand, when reaction temperature exceeds 50 degreeC, there exists a possibility that the yield of a target compound may fall and manufacturing cost may become high.
Moreover, reaction time is 1 to 30 hours normally, Preferably it is 5 to 20 hours.
When reaction time is less than 1 hour, there exists a possibility that reaction may become inadequate. On the other hand, when reaction time exceeds 30 hours, there exists a possibility that manufacturing cost may become high.
Furthermore, the reaction pressure is not particularly limited, and examples thereof include atmospheric pressure.
The atmosphere is not particularly limited, and examples thereof include air and a nitrogen atmosphere.

(Third step)
The compound represented by the general formula (3) obtained in the second step, and the general formula (4):

(In the formula, M and n have the same meaning as in formula (I))
Is reacted with a compound represented by the general formula (5):

(In the formula, M and n have the same meaning as in general formula (I), and R ₅ has the same meaning as in formula (2)).
To obtain a compound represented by:

Examples of the alkylene in the amino group-terminated polyalkylene glycol of the compound (4) include ethylene, propylene, and butylene.
Examples of the compound (4) include aminoethyl-terminated polyoxyethylene glycol, aminoethyl-terminated polyoxytrimethylene glycol, and aminoethyl-terminated polyoxytetramethylene glycol.

  Compound (4) is a method for preparing available compounds such as M. Yuan, et al., “Synthesis and Characterization of Poly (ethylene glycol) -block-poly (amino acid) Copolymer”, European Polymer Journal, Elsevier, 2001, 37, p. 1907-1912, or K. Kugo, 3 others, `` Synthesis and Conformation of ABA Tri-Block Copolymers with Hydrophobic Poly (g-benzyl L-glutamate) and Hydrophilic Poly (ethylene oxide) ”, Polymer Journal, Japan Society for Polymer Science, 1987, Vol. 19, p.375-381, and commercially available products can also be used.

Specifically, the compound (3) obtained in the second step and the compound (4) are reacted in the presence of a solvent. Next, the obtained reaction mixture is washed, dried and purified by a known method to obtain compound (5). In this reaction, it is preferable to dilute both in a solvent at a low concentration (highly dilute), for example, to gradually react both diluted solutions dropwise over time, and then react under stirring.
The solvent is not particularly limited as long as it does not adversely affect the raw material compound and the reaction compound and can be easily distilled off, and examples thereof include halogenated solvents such as dichloromethane, chloroform, dichloroethane and the like.
The dilution rate is about 500 to 1000 times the total amount of the compound (3) and the compound (4).

The use ratio of compound (3) and compound (4) is 1: 0.95 to 1.05 in molar ratio.
When the compound (4) is less than 0.95 mol relative to 1 mol of the compound (3), the yield of the target compound may be reduced. On the other hand, when compound (4) exceeds 1.05 mol with respect to 1 mol of compound (3), there exists a possibility that manufacturing cost may become high.

The reaction conditions may be appropriately set depending on the type and amount of raw materials.
The reaction temperature is usually 10 to 30 ° C, preferably 20 to 25 ° C.
When reaction temperature is less than 10 degreeC, there exists a possibility that reaction efficiency may fall. On the other hand, when reaction temperature exceeds 30 degreeC, there exists a possibility that the yield of a target compound may fall and manufacturing cost may become high.
Moreover, reaction time is 12 to 72 hours normally, Preferably it is 24 to 48 hours.
When reaction time is less than 12 hours, there exists a possibility that reaction may become inadequate. On the other hand, when reaction time exceeds 72 hours, there exists a possibility that manufacturing cost may become high.
Furthermore, the reaction pressure is not particularly limited, and examples thereof include atmospheric pressure.
The atmosphere is not particularly limited, and examples thereof include air and a nitrogen atmosphere.

(4th process)
By reacting the compound represented by the general formula (5) obtained in the third step with an alkali, the general formula (II):

(In the formula, M and n have the same meaning as in general formula (I), and R ₄ has the same meaning as in formula (1)).
To obtain a compound represented by:

  Specifically, the compound (5) obtained in the third step and the alkali are reacted by heating under reflux in the presence of a solvent, and then washed and dried by a known method to obtain the compound (II).

Examples of the alkali include sodium hydroxide, potassium hydroxide, magnesium hydroxide, lithium hydroxide and the like.
The amount of alkali used varies depending on the type of compound (5) and alkali, so that stoichiometrically, the hydroxyl group in the alkali becomes 1 equivalent with respect to 1 equivalent of the (CH ₃ CO) group in compound (5). As long as it is a sufficient amount, it is preferably 2 to 25 equivalents.
When the hydroxyl group in the alkali is less than 1 equivalent with respect to 1 equivalent of the (CH ₃ CO) group in the compound (5), the yield of the target compound may be reduced. On the other hand, when the hydroxyl group in the alkali exceeds 20 equivalents with respect to the (CH ₃ CO) group in the compound (5), the production cost may increase.

The reaction conditions may be appropriately set depending on the type and amount of raw materials.
The reaction temperature is usually 40 to 120 ° C, preferably 60 to 100 ° C.
When reaction temperature is less than 40 degreeC, there exists a possibility that reaction efficiency may fall. On the other hand, when reaction temperature exceeds 120 degreeC, there exists a possibility that the yield of a target compound may fall and manufacturing cost may become high.
Moreover, reaction time is 5 to 48 hours normally, Preferably it is 12 to 24 hours.
When reaction time is less than 5 hours, there exists a possibility that reaction may become inadequate. On the other hand, when reaction time exceeds 48 hours, there exists a possibility that manufacturing cost may become high.
Furthermore, the reaction pressure is not particularly limited, and examples thereof include atmospheric pressure.
The atmosphere is not particularly limited, and examples thereof include air and a nitrogen atmosphere.

(5th process)
The compound represented by the general formula (II) obtained in the fourth step, and the general formula (III):

(Wherein R ₁ , R ₂ and R ₃ have the same meanings as in general formula (I))
To obtain a compound represented by the general formula (I).

  Specifically, the compound (II) and the compound (III) are reacted in the presence of a solvent, and if necessary, a condensing agent and a condensing aid, and washed and dried by a known method to obtain a compound (I )

Compound (III) is an available compound manufacturing method, for example, BV Tamhankar, 4 others, "Oxidation of alkylcyanohydrazines to azo-bis nitriles using oxone-potassium bromide in aqueous medium", Synthetic Communications, Marcel Dekker, 2002, It can be produced according to the production method described in Vol. 32, p.3643-3646, and commercially available products can also be used.
Specific examples of the compound (III) include 3,3′-azobis (3-cyanobutanoic acid), 3,3′-azobis (3-methylbutanoic acid), 4,4′-azobis (4-cyanopentanoic acid), 4,4'-azobis (4-methylpentanoic acid), 2,2'-azobis {2-methyl-N- (2-carboxyethyl) -2-methylpropyne amidine} hydrate, and the like.

The use ratio of compound (II) and compound (III) is 1: 0.45-0.55 in molar ratio.
When the compound (III) is less than 0.45 mol relative to 1 mol of the compound (II), the yield of the target compound may be reduced. On the other hand, when compound (III) exceeds 0.55 mol with respect to 1 mol of compound (II), there exists a possibility that manufacturing cost may become high.

In the fifth step, a condensing agent and a condensing aid may be added as necessary.
The condensing agent is not particularly limited and those conventionally used in esterification reactions can be used. Specifically, carbodiimides such as N, N′-dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, diisopropylcarbodiimide; 2,4,6-triisopropylbenzenesulfonyl chloride, p-toluene Arylsulfonyl chlorides such as sulfonyl chloride; arylsulfonamides such as 2,4,6-triisopropylbenzenesulfonylimidazolide and 2,4,6-triisopropylbenzenesulfonyltriazolide; azodicarboxylic acid esters; halogenated organics Sulfonyl; diphenylphosphoryl azide, diethoxyphosphonyl chloride, diethoxyphosphonyl azide, propylphosphonic anhydride, diphenylphosphonyl chloride; magnesium dimethoxide, magnesium diethoxide, aluminum diisopropoxy Metal alkoxides such as aluminum tri-t-butoxide; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; oxidation Alkaline earth metal oxides such as calcium and magnesium oxide; alkali metal amides such as lithium amide; potassium carbonate; zinc chloride, aluminum trichloride, phosphorus oxychloride, tetramethylammonium chloride, concentrated sulfuric acid, pentaacidic niline, polyphosphoric acid , Acetic anhydride, carbonyldiimidazole, p-toluenesulfonyl chloride, basic ion exchange resin and the like. Among these, hydrochloride of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide is particularly preferable from the viewpoints of availability and synthesis.

  Examples of the condensation assistant include organic bases such as triethylamine, pyridine, benzylamine, benzylmethylamine, 4-dimethylaminopyridine, dimethylaniline, tributylamine, and 4-piperidinopyridine. Among these, 4-dimethylaminopyridine is particularly preferable from the viewpoint of easy availability and synthesis.

The amount of the condensing agent to be used is 1 to 4 mol, more preferably 1.5 to 2 mol, per 1 mol of compound (II).
When the amount of the condensing agent used is less than 1 mole relative to 1 mole of compound (II), the yield of the target compound may be reduced. On the other hand, when the usage-amount of a condensing agent exceeds 4 mol with respect to 1 mol of compound (II), there exists a possibility that manufacturing cost may become high.

The usage-amount of a condensation adjuvant is 0.01-0.5 mol with respect to 1 mol of compound (II), More preferably, it is 0.05-0.2 mol.
When the usage-amount of a condensation adjuvant is less than 0.01 mol with respect to 1 mol of compound (II), there exists a possibility that the yield of a target compound may fall. On the other hand, when the usage-amount of a condensation adjuvant exceeds 0.5 mol with respect to 1 mol of compounds (II), there exists a possibility that manufacturing cost may become high.

The reaction conditions may be appropriately set depending on the type and amount of raw materials.
The reaction temperature is usually 5 to 30 ° C, preferably 20 to 25 ° C.
When reaction temperature is less than 5 degreeC, there exists a possibility that reaction efficiency may fall. On the other hand, when reaction temperature exceeds 30 degreeC, there exists a possibility that manufacturing cost may become high.
Moreover, reaction time is 12 to 72 hours normally, Preferably it is 24 to 48 hours.
When reaction time is less than 12 hours, there exists a possibility that reaction may become inadequate. On the other hand, when reaction time exceeds 72 hours, there exists a possibility that manufacturing cost may become high.
Furthermore, the reaction pressure is not particularly limited, and examples thereof include atmospheric pressure.
The atmosphere is not particularly limited, and examples thereof include air and a nitrogen atmosphere.

The present invention will be described more specifically with reference to the following examples and reference examples, but the scope of the present invention is not limited thereby.
The compounds obtained in each step of the examples were identified by analyzing with the following equipment and conditions, and their physical properties were evaluated.

⁽¹ H-NMR)
An EX-270 type superconducting nuclear magnetic resonance absorber manufactured by JEOL Ltd. was used. As the solvent, deuterated chloroform or deuterated dimethyl sulfoxide was used. As a reference substance, tetramethylsilane was used and measured at room temperature.

(MALDI-TOF MS)
A KOMPACT-2 type matrix-assisted laser ionization time-of-flight mass spectrometer manufactured by Shimadzu Corporation was used. As the matrix and ionization aid, α-cyano-4-hydroxycinnamic acid and sodium iodide were used, respectively.
A sample solution was prepared by dissolving 1 mg of a sample in 1 mL of tetrahydrofuran (THF). The matrix solution was prepared by dissolving 17 mg of α-cyano-4-hydroxycinnamic acid in 1 mL of THF. Thereafter, the matrix solution and the sample solution were mixed at a ratio of 1: 1. Spot 0.5 L of 0.1 mmol / mL sodium iodide solution on the sample plate, let dry for several minutes at room temperature, then spot 0.5-1.0 μL of sample / matrix mixed solution on it. The measurement was performed after the solvent was volatilized with dry air.

(IR)
An FT / IR4100 type Fourier transform infrared spectrophotometer manufactured by JASCO Corporation was used.
The sample was mixed well with potassium bromide and measured after molding into a disk-shaped pellet having a diameter of about 5 mm and a thickness of about 0.1 to 0.2 mm with a pressurizer.

(Elemental analysis)
A YANACO CHN coder MT-5 type was used.
Measurements were performed at least twice using approximately 2.5 mg of sample per measurement. Element content was calculated | required as an average value of the obtained value.

(Gel permeation chromatography: GPC)
A PU-2080 pump manufactured by JASCO Corporation and a UV / visible detector UV-8020 manufactured by Tosoh Corporation were used. As the column, Tosoh TSK gel G2500H / G3000H was used. Tetrahydrofuran was used as a solvent, and measurement was performed at a flow rate of 1.0 mL / min.

(Melting point)
An MP-S3 melting point measuring device manufactured by Yanaco was used.

Example 1
(First Step) Synthesis of 5-acetoxyisophthalic acid In a 100 mL eggplant flask equipped with a magnetic stirrer, 5-hydroxyisophthalic acid (10.0 g, 55 mmol) as compound (1) and acetic anhydride (22.0 g, 215 mmol) was added, and the mixture was refluxed with heating at 140 ° C. for 12 hours in air at atmospheric pressure.
Thereafter, the reaction mixture was poured into ice water to be cooled, and the precipitated solid was collected by filtration. The obtained solid was recrystallized from distilled water / ethanol = 1/1 (v / v) to obtain 9.3 g of a white solid.
The following analysis confirmed that the obtained white solid was 5-acetoxyisophthalic acid as compound (2). The yield was 76%.

¹ H-NMR (DMSO-d ₆ ) δ ppm (see Fig. 1)
8.35 (s, 1H), 7.90 (s, 2H), 2.32 (s, 3H)
IR (KBr) cm ^-1 (See Fig. 2)
3452, 1760, 1687, 1292, 1207
Elemental analysis Value: C 53.47%, H 3.56%
Calculated as C ₈ H ₈ O ₆ : C 53.38%, H 3.60%

(Second Step) Synthesis of (5- (acetoxy) -1,3-phenylene) bis ((2-thioxathiazolin-3-yl) methine) In a 200 mL eggplant flask equipped with a Dimroth condenser and a magnetic stirrer 5-acetoxyisophthalic acid (2.2 g, 10 mmol) as compound (2) obtained in the first step, thionyl chloride (3.6 g, 30 mmol) as chlorinating agent, benzene (40 mL) as solvent, and Dimethylformamide (DMF, 1 mL) as an activator was added, and the mixture was refluxed by heating at 80 ° C. for 3 hours in air at atmospheric pressure. After allowing to cool, the solvent was distilled off under reduced pressure, 2-mercaptothiazoline (2.4 g, 20 mmol) and tetrahydrofuran (THF, 70 mL) as a solvent were added, and triethylamine (4.1 mL, 30 mmol) as a base was further added. The solution was added dropwise and stirred in air at atmospheric pressure at a temperature of 25 ° C. for 20 hours.
Thereafter, the reaction mixture was diluted to about 5 times volume with dichloromethane and washed with 5% aqueous sodium hydroxide and distilled water. Next, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was dissolved in about 5 mL of dichloromethane and crystallized by adding isopropyl ether to obtain 2.6 g of a yellow solid.
The following analysis confirmed that the obtained yellow solid was 5- (acetoxy) -1,3-phenylene) bis ((2-thioxathiazolin-3-yl) methine as compound (3). The yield was 61%.

¹ H-NMR (CDCl ₃ ) δ ppm (see Figure 3)
7.85 (s, 1H), 7.57 (s, 2H), 4.53 (t, J = 7.0 Hz, 4H), 3.49 (t, J = 7.0 Hz, 4H), 2.31 (s, 3H)
IR (KBr) cm ^-1 (See Fig. 4)
3469, 1722, 1707, 1282, 1209
Elemental analysis Value: C 44.87%, H 3.36%, N 6.39%
Calculated as C ₁₆ H ₁₄ N ₂ O ₄ S ₄ : C 45.06%, H 3.31%, N 6.57%

(Third step) Synthesis of cyclic polyethylene glycol (5- (acetoxy) -1,3 as compound (3) obtained in the second step was added to a 3000 mL three-necked flask equipped with a mechanical stirrer and a metall pump. -Phenylene) bis ((2-thioxathiazolin-3-yl) methine) (0.43 g, 1.0 mmol) in dichloromethane (300 mL) and amino group-terminated polyethylene glycol (polyoxyethylene as compound (4)) Diethylamine, Mn = 1,000) (1.0 g, 1.0 mmol) in dichloromethane (300 mL) was slowly and dropwise added simultaneously in air at atmospheric pressure at a temperature of 25 ° C. for 12 hours.

After completion of the dropwise addition, the mixture was further stirred for 12 hours, concentrated until the total amount of dichloromethane was about 200 mL, and then washed with dilute hydrochloric acid (1%), a saturated aqueous sodium hydrogen carbonate solution, and distilled water. Next, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting yellow viscous liquid was purified by a silica gel column (methylene chloride → ethyl acetate → methylene chloride / methanol = 8/2).
The obtained product was dissolved in a small amount (about 5 mL) of dichloromethane, and diethyl ether was poured to remove the polycyclic cyclized product as a precipitate. Subsequently, the solvent was distilled off under reduced pressure to obtain 0.6 g of a pale yellow viscous liquid.
The following analysis confirmed that the obtained pale yellow viscous liquid was cyclic polyethylene glycol as the compound (5). The yield was 50%.

¹ H-NMR (CDCl ₃ ) δ ppm (see Fig. 5)
8.23 (s, 1H), 7.79 (s, 2H), 7.64 (br, 2H), 2.31 (s, 3H)
MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid, NaI) (see Fig. 6)

(Fourth Step) Synthesis of Cyclic Polyethylene Glycol Cyclic Polyethylene Glycol (1.0 g, 0.84 mmol) as Compound (5) obtained in the third step was added to a 200 mL eggplant flask equipped with a Dimroth cooler and a magnetic stirrer. ), Sodium hydroxide (0.7 g, 18 mmol) as an alkali and methanol (50 mL) as a solvent were added, and the mixture was heated to reflux at 60 ° C. for 18 hours in air at atmospheric pressure. Thereafter, the solvent was distilled off from the reaction mixture under reduced pressure, and 50 mL of dichloromethane was added, followed by washing with dilute hydrochloric acid (1%) and distilled water. Next, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 0.9 g of a colorless transparent viscous liquid.
The following analysis confirmed that the obtained colorless transparent viscous liquid was cyclic polyethylene glycol as compound (II). The yield was 93%.

¹ H-NMR (CDCl ₃ ) δ ppm (see Fig. 7)
7.81 (s, 1H), 7.51 (s, 2H), 7.41 (br, 2H)
MALDI-TOF MS (α-cyano-4-hydroxycinnamic acid, NaI) (see Fig. 8)

(Step 5) Synthesis of cyclic macroazo compound In a 100 mL eggplant flask equipped with a magnetic stirrer and a calcium chloride tube, cyclic polyethylene glycol (0.9 g, 0.78 mmol) as compound (II) and compound (III) 4,4'-azobis (4-cyanopentanoic acid) (0.11 g, 0.39 mmol), dichloromethane (30 mL) as solvent, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide as condensing agent Hydrochloride (WSCI, 0.29 g, 1.5 mmol) and 4-dimethylaminopyridine (DMAP, 10 mg, 0.08 mmol) as a condensation assistant were added, and the mixture was stirred at 25 ° C. for 48 hours.

The reaction mixture was then diluted to about 2 volumes with dichloromethane and washed with dilute hydrochloric acid (1%), saturated aqueous sodium bicarbonate and distilled water. Next, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was dissolved in a small amount (about 5 mL) of dichloromethane, reprecipitated with diethyl ether, and then freeze-dried with benzene to obtain 0.45 g of a white solid.
According to the following analysis, the obtained white solid was obtained from the compound (I) (X in the general formula (I) was O, and R ₁ and R ₂ bonded to the same carbon atom were each a combination of CN and a methyl group. A cyclic macroazo compound (4,4′-azobis (3,5-bis (cyclopolyethyleneglycolcarbamoyl) phenyl) 4 corresponding to R ₃ and M is an ethylene group, and n is an integer of 5 to 100) 4 -Cyanopentanoic acid). The yield was 45%.
Moreover, it was Mn = 2,600, Mw = 2,800, Mw / Mn = 1.06 from the result of GPC measurement.

¹ H-NMR (CDCl ₃ ) δ ppm (see Fig. 9)
8.24 (s, 1H), 7.81 (s, 2H), 7.60 (br, 2H), 2.54-2.94 (m, 4H), 1.78 (d, J = 20 Hz, 3H)
IR (KBr) cm ^-1 (See Fig. 10)
2869, 1762, 1661, 1108
GPC (see Figure 11)

(Reference Example 1)
Using the macroazo compound obtained in Example 1 as a polymerization initiator, a butyl acrylate polymer was obtained and its physical properties were evaluated.
40 mg (0.016 mmol) of macroazo initiator (I) was dissolved in n-butyl acrylate (1.0 g, 7.8 mmol) purified by distillation under reduced pressure immediately before, and after deaeration and sealing, irradiation with a 100 W mercury lamp for 15 minutes. As a result, the reaction system solidified, and a colorless and transparent rubber-like substance that swells insoluble in an organic solvent was obtained.
In addition, when a polymer azo polymerization initiator having a conventional polyethylene glycol unit was used in place of the cyclic macroazo compound as a polymerization initiator and irradiated in the same manner, a polymer soluble in an organic solvent (polyethylene glycol and polymer) was obtained. A block copolymer with n-butyl acrylate) was obtained.

  From the above results, a butyl acrylate polymer using the macroazo compound of the present invention as a polymerization initiator is formed by threading a cyclic polyethylene glycol moiety in which a polymer growth chain is contained in an initiator fragment during polymerization. It can be seen that this is a three-dimensional polymer having a movable cross-linked structure.

Since the macroazo compound of the present invention has a cyclic polymer chain in one molecule, it can be used as a polymerization initiator to synthesize a three-dimensional network polymer having mobile crosslinking.
In the three-dimensional structure, the crosslinking point can move and the mobility of the polymer chain segment becomes high. Therefore, such a network polymer can be expected as a material having good swelling property and excellent impact resistance. For example, it can be expected to be applied to a coating material having resilience against impact and having excellent scratch resistance. Moreover, application to highly functional soft materials such as smart gels (intelligent gels) that respond to external stimuli such as temperature, pH, solvent composition, and magnetic field can also be expected.

Claims (5)

Formula (I):
(In the formula, X is O or NH, R ₁ and R ₂ are the same or different and are CN or an alkyl group having 1 to 4 carbon atoms, and R ₃ is an alkylene group having 1 to ₃ carbon atoms or 1-imino. -2-azabutylene group, M is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 5 to 100)
In represented, macroazo compound number average molecular weight Mn of a 1,500～4,000 and weight average molecular weight Mw is characterized 1,800～5,000 der Rukoto. X in the general formula (I) is O, R ₁ and R ₂ bonded to the same carbon atom are each a combination of CN and a methyl group, R ₃ is an ethylene group, M is an ethylene group, The macroazo compound according to claim 1, wherein n is an integer of 5 to 100. General formula (II):
(In the formula, M and n are as defined in formula (I), and R ₄ is OH or NH ₂ ).
The precursor of a macroazo compound according to claim 1 or 2, characterized by: The precursor of a macroazo compound according to claim 3, wherein R ₄ in the general formula (II) is OH. General formula (II):
(In the formula, M and n are as defined in the following general formula (I), and R ₄ is OH or NH ₂ ).
A compound represented by formula (III):
(In the formula, R ₁ , R ₂ and R ₃ have the same meanings as the following general formula (I))
Is reacted with a compound represented by the general formula (I):
(In the formula, X is O or NH, R ₁ and R ₂ are the same or different and are CN or an alkyl group having 1 to 4 carbon atoms, and R ₃ is an alkylene group having 1 to ₃ carbon atoms or 1-imino. -2-azabutylene group, M is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 5 to 100)
In expressed, producing a macroazo compound having a number average molecular weight Mn of 1,500～4,000 a is and a weight average molecular weight Mw is characterized in that it comprises a step of obtaining a 1,800～5,000 der Ru compounds Method.