JP2018052999A - Rotaxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide rotaxane excellent in self-recovery properties.SOLUTION: The rotaxane is provided, having such a structure that a polymer compound (B) being an axial component penetrates through a ring component formed of cyclic polyether ester (A) represented by at least one general formula (1). In general formula (1), Ris a divalent hydrocarbon group having 2 to 21 carbon atoms in which at least one hydrogen atom may be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group, Ris a divalent hydrocarbon group having 2 to 8 carbon atoms, m is an integer of 1 to 3, n is an integer of 1 to 30, m pieces of Rmay be the same or different, and m×n pieces of Rmay be the same or different.SELECTED DRAWING: None

Description

The present invention relates to rotaxanes. The present invention relates to a rotaxane having a structure in which a polymer component (B) as a shaft component penetrates a ring component composed of at least one cyclic polyether ester (A).

As a novel stimulus-responsive material or viscoelastic material, a (poly) rotaxane having a structure in which a chain polymer is included in a cyclic molecule such as cyclodextrin in a comb-like manner is attracting attention as a novel polymer material ( Patent Document 1).

However, a rotaxane compound using β-cyclodextrin described in Patent Document 1 or the like as a cyclic component has low solubility in a solvent or a chain polymer due to the action of intramolecular hydrogen bonding of cyclodextrin. It was difficult to increase the proportion of β-cyclodextrin penetrating the molecule, and the generated (poly) rotaxane had an insufficient elastic modulus, and there was a problem that a sufficient self-repairing action could not be obtained.

JP 2006-233007 A

An object of this invention is to provide the rotaxane excellent in self-repairing property.

The inventors of the present invention have arrived at the present invention as a result of studies to achieve the above object. That is, the present invention is a rotaxane having a structure in which a polymer component (B) as a shaft component penetrates a ring component composed of at least one cyclic polyether ester (A) represented by the general formula (1).

In general formula (1), R ¹ is a divalent hydrocarbon group having 2 to 21 carbon atoms in which at least ^one of hydrogen atoms may be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group; ² is a divalent hydrocarbon group having 2 to 8 carbon atoms, m is an integer of 1 to 3, n is an integer of 1 to 30, and m R ¹ are the same or different. Alternatively, m × n R ² may be the same or different.

The rotaxane of the present invention is excellent in self-healing properties.

The rotaxane of the present invention has a structure in which a polymer component (B) as an axial component penetrates a ring component composed of at least one cyclic polyether ester (A) represented by the general formula (1).

In the general formula (1), R ¹ is a hydrocarbon group having 2 to 21 carbon atoms in which at least one hydrogen atom may be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group.

Examples of the hydrocarbon group having 2 to 21 carbon atoms include an alkylene group having 2 to 21 carbon atoms, an alkenylene group having 2 to 21 carbon atoms, an arylene group having 6 to 21 carbon atoms, and an aralkylene group having 7 to 21 carbon atoms. It is done.

Examples of the alkylene group having 2 to 21 carbon atoms include linear alkylene groups having 2 to 21 carbon atoms (ethylene group, trimethylene group, tetramethylene group, pentamethylene group and n-henicosanylene group) and branched alkylene groups having 3 to 21 carbon atoms. Groups (1-methylethylene group, 2-methylethylene group, 1-ethylethylene group, 2-ethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethyltrimethylene group, 1 -N-butyltrimethylene group, 1-n-hexyltrimethylene group, 1-n-propyltrimethylene group, 1-n-heptyltrimethylene group, 1-n-octyltrimethylene group, 1-n-heptyltetra Methylene group and 1-n-octylethylene group) and cycloalkylene groups having 4 to 21 carbon atoms (cyclobutylene group, cyclopentylene). Group, 2-methylcyclopentylene group, cyclohexylene group, 1,3-dimethylcyclohexylene group, cycloheptylene group, 1-ethylcyclopentylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, cycloundecylene group, Cyclododecylene group, cyclotridecylene group, cyclotetradecylene group, cyclopentadecylene group, cyclohexadecylene group, cycloheptadecylene group, cyclooctadecylene group, cyclononadecylene group, cycloeicosylene group, norbornylene group , Dicyclopentylene group, isopropylidene dicyclohexylene group, cyclohexane dimethylene group, and the like.

Examples of the alkenylene group having 2 to 21 carbon atoms include straight chain alkenylene groups having 2 to 21 carbon atoms (such as ethenylene group, propenylene group and henicosenylene group) and branched alkenylene groups having 3 to 21 carbon atoms (1-ethylethenylene group, 1, 2-dimethylethenylene group, 1-butylethenylene group, 1-hexylethenylene group, 1-octylethenylene group, etc.).

Examples of the arylene group having 6 to 21 carbon atoms include o-, p- or m-phenylene group, 2,4-naphthylene group, biphenylene group, terphenylene group, anthrylene group, phenanthrylene group, fluorenylene group, pyrenylene group and group. Is mentioned.

Examples of the aralkylene group having 7 to 21 carbon atoms include phenylmethylene group, diphenylmethine group, 1-phenylethylene group, o-phenyleneethyl group and naphthylmethylene group.

Examples of the group in which at least one hydrogen atom of these groups is substituted with a halogeno group, acetyl group, alkoxy group or phenoxy group include 1-bromo-trimethylene group, 1-acetyl-trimethylene group, 1-methoxy-trimethylene group And 1-phenoxy-trimethylene group and the like.

Among these, R ¹ is preferably a linear or branched alkylene group having 3 to 16 carbon atoms, and is an ethylene group, trimethylene group, tetramethylene group, pentamethylene group, tetradecamethylene group, methylethylene group, 1 -N-propyltrimethylene group, 1-n-heptyltrimethylene group, 1-n-octyltrimethylene group, 1-n-heptyltetramethylene group, 1-n-hexyltrimethylene group, 1-n-hexyltetra More preferred are a methylene group, a 1-n-undecyltrimethylene group and a 1-n-undecyltetramethylene group.

In general formula (1), ^{R 2} is a divalent hydrocarbon group having 2 to 8 carbon atoms. Preferred examples of the divalent hydrocarbon group having 2 to 8 carbon atoms include a phenylethylene group and an alkylene group having 2 to 4 carbon atoms, more preferably a linear alkylene group having 2 to 4 carbon atoms (ethylene Group, propylene group and butylene group) and branched alkylene groups having 3 or 4 carbon atoms (such as methylethylene group, ethylethylene group, methylpropylene group and 2-methylpropylene), particularly preferably having 2 to 4 carbon atoms. A linear alkylene group and a branched alkylene group having 3 to 4 carbon atoms, most preferably an ethylene group and a propylene group.

In the above general formula (1), m means the number of repeating units represented by [R ¹ CO (OR ² ) _n O], and n is the number of added moles of the oxyalkylene group represented by (OR ² ). Means.

m is an integer of 1 to 3, and preferably 1.
n is an integer of 1 to 30, and the added mole number (n) of the oxyalkylene group of the cyclic polyether ester (A) is preferably 5 to 5 from the viewpoint of ease of penetration of the polymer compound (B). It is an integer of 20.
When m is 2 or 3, the m R ^{1 s} may be the same or different, and are preferably the same. In addition, when m is 2 or 3, and / or n is an integer of 2 or more, m × n R ² may be the same or different, and the polymer compound (B) can easily penetrate. From the viewpoints of the like, it is preferable that they are the same.

When m × n R ² are different, the composition of m × n R ² is Polym. Chem., 2014, 5, 6905. Can be measured and analyzed by time-of-flight mass spectrometry (also referred to as MALDI-TOF MS) by the matrix-assisted laser desorption ionization method described in 1.

As the cyclic polyether ester (A) contained in the rotaxane of the present invention, the cyclic polyether ester (A) in which m and / or n is a specific value in the general formula (1) may be used alone, m And / or a plurality of cyclic polyether esters (A) having different values of n may be used in combination.
When a plurality of cyclic polyether esters (A) having different m and / or n in the general formula (1) are used in combination, the type and ratio of the cyclic polyether ester (A) to be used are those of the polymer compound (B). It can be adjusted and selected according to the composition, molecular weight, molecular weight distribution, and the like.

Adjustment of the values of m and n in the general formula (1) and adjustment of the content of the cyclic polyether ester (A) having a specific range of n have active hydrogen-containing groups used in the alkoxylation reaction described later. For example, by adjusting the ratio of the lactone and the alkylene oxide having 2 to 8 carbon atoms and changing the addition method of the alkylene oxide, for example, stepping the alkylene oxide that reacts with the lactone having no active hydrogen-containing group Can increase the content of the cyclic polyether ester (A) having a specific value of n, and increase the total proportion of the cyclic polyether ester (A) where n takes a value within a certain range. .
In addition, the value of m of cyclic polyether ester (A) and the value of n are Polym. Chem., 2014, 5, 6905. And can be confirmed by MALDI-TOF MS described in 1.

The number average molecular weight (hereinafter abbreviated as Mn) of the cyclic polyether ester (A) contained in the rotaxane of the present invention can be adjusted according to the molecular weight of the polymer compound (B). From the viewpoint of easiness and the like, 200 to 4000 is preferable.
The Mn of the cyclic polyether ester (A) can be adjusted to a preferred range by adjusting the number of added oxyalkylene groups.

Mn of the cyclic polyether ester (A) can be measured using gel permeation chromatography (hereinafter abbreviated as GPC) under the following conditions.
Apparatus: “Waters Alliance 2695” [manufactured by Waters]
Column: “Guardcolumn Super HL” (1), “TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 each connected one” [all manufactured by Tosoh Corporation]
・ Sample solution: 0.25 wt% tetrahydrofuran solution ・ Solution injection amount: 10 μL
・ Flow rate: 0.6 mL / min ・ Measurement temperature: 40 ° C.
・ Detection device: Refractive index detector ・ Reference material: Standard polyethylene glycol

As the cyclic polyether ester (A) used for the rotaxane of the present invention, R ¹ is a tetradecamethylene group, R ² is an ethylene group and a propylene group, m is 1 to 3, and n is 5 The cyclic polyether ester which is -30 is mentioned.

The cyclic polyether ester (A) used for the rotaxane of the present invention is a lactone having no active hydrogen-containing group by using a lactone having no active hydrogen-containing group and an alkylene oxide having 2 to 8 carbon atoms. It can be obtained by carrying out a reaction (also called an alkoxylation reaction) for inserting an oxyalkylene group between the carbonyl and oxygen atom of the oxycarbonyl group. The alkoxylation reaction is carried out by converting a lactone having no active hydrogen-containing group and an alkylene oxide having 2 to 8 carbon atoms into a catalyst used for the ring-opening addition reaction or alkoxylation reaction of alkylene oxide, etc. It may be used as.
In addition, the said active hydrogen containing group means the functional group which an alkylene oxide can carry out ring-opening addition, and a hydroxyl group, a carboxyl group, a mercapto group, an amino group, etc. are mentioned.

In the alkoxylation reaction, the cyclic polyether ester represented by the other general formula (1) is added to the cyclic polyether ester (A) represented by the general formula (1) generated by the alkoxylation reaction. Side reaction to insert and add occurs.
Therefore, in addition to the cyclic polyether ester (A) in which m = 1 in the general formula (1), the reaction product obtained by the alkoxylation reaction includes [R ¹ CO ( OR ² ) _n O], and a cyclic polyether ester having two units in one molecule (ie, m = 2) and / or a cyclic polyether ester having three units (ie, m = 3). The product becomes a polyether composition mainly composed of a cyclic polyether ester having 1 to 3 units represented by [R ¹ CO (OR ² ) _n O] in the general formula (1), of which m is The weight ratio of the cyclic polyether ester (A) which is 1 to the cyclic polyether ester (A) where m is 2 and the cyclic polyether ester (A) where m is 3 is approximately 6: 3: 1.
The composition of the cyclic polyether contained in the reaction product is Polym. Chem., 2014, 5, 6905. And can be confirmed by MALDI-TOF MS described in 1.

The reaction product of the alkoxylation reaction [that is, the mixture containing the cyclic polyether ester (A)] is further fractionated and purified by a known method such as a gel permeation method and silica gel column chromatography. A cyclic polyether ester (A) having m and n can be obtained. As the cyclic polyether ester (A) contained in the rotaxane of the present invention, m and n obtained by fractionating and purifying the reaction product even if the reaction product of the alkoxylation reaction is used as it is. A cyclic polyether ester (A) having a specific value may be used.

The lactone having no active hydrogen-containing group used for obtaining the cyclic polyether ester (A) has one hydroxyl group and one carboxyl group, and excludes the one hydroxyl group and one carboxyl group. Cyclic esters obtained by intramolecular dehydration of hydroxyl groups and carboxyl groups of monohydroxycarboxylic acids having 4 to 22 carbon atoms that do not have other active hydrogen-containing groups can be used. As a method for synthesizing a lactone by intramolecular dehydration, a method of heat dehydration by a known method, J. Org. S. Nimitz, R.A. H. Wallenberg, Terahedron Lett. Known synthesis methods such as the method described in 1978, 19, 3523 and a method using an enzyme such as lipase can be used.

Examples of the monohydroxycarboxylic acid having 4 to 22 carbon atoms having no other active hydrogen-containing group other than one hydroxyl group and one carboxyl group include linear hydroxycarboxylic acids having 4 to 22 carbon atoms (3-hydroxy Propanoic acid, 4-hydroxybutyric acid, 5-hydroxypentanoic acid, 6-hydroxyhexanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid, 4-hydroxy-2-butenoic acid, etc.) and a branch having 3 to 22 carbon atoms Hydroxycarboxylic acid (3-hydroxybutanoic acid, 5-hydroxytridecanoic acid, 2-methylene-4-hydroxybutyric acid, 4-phenyl-4-hydroxybutyric acid, 2,2-dimethyl-4-hydroxybutyric acid, 4-hexyl- 4-hydroxybutyric acid and 4-hydroxy-2-methyl-2-butenoic acid).

As the lactone having no active hydrogen-containing group, among the hydrogen atoms bonded to the carbon atom of the hydroxycarboxylic acid having 4 to 22 carbon atoms, at least one hydrogen atom is a halogeno group, acetyl group, alkoxy group or phenoxy. A lactone having a structure in which a hydroxycarboxylic acid substituted with a group is dehydrated intramolecularly can also be used.
Among the above-mentioned monohydroxycarboxylic acids having 4 to 22 carbon atoms, examples of the hydroxycarboxylic acid in which at least one hydrogen atom bonded to the carbon atom is substituted with a halogeno group include 2-bromo-4-hydroxybutyric acid. Examples of the hydroxycarboxylic acid substituted with an acetyl group include 2-acetyl-4-hydroxybutanoic acid, and the hydroxycarboxylic acid substituted with an alkoxy group includes 2-methoxy-4-hydroxybutyric acid. Examples of the hydroxycarboxylic acid substituted with a phenoxy group include 2-phenyl-4-hydroxybutyric acid.

Preferable lactones having no active hydrogen-containing group include β-lactone (β-propiolactone, β-butyrolactone, etc.), γ-lactone (γ-butyrolactone, etc.), δ-lactone (δ-valerolactone, etc.). ), Ε-lactone (such as ε-caprolactone), lactone having a long chain alkyl group (such as γ-enanthlactone, γ-undecanolactone, γ-dodecanolactone and δ-dodecanolactone), macrocyclic lactone (15 -Pentadecanolactone) and aromatic lactone (3,4-dihydrocoumarin).
These lactones may be used alone or in combination of two or more.

Examples of the alkylene oxide having 2 to 8 carbon atoms (hereinafter sometimes abbreviated as AO) used in the alkoxylation reaction include ethylene oxide, 1,2-propylene oxide, oxetane, 1,2-, 1,3-, 1 , 4- or 2,3-butylene oxide, styrene oxide, etc., and alkylene oxides having 2 to 3 carbon atoms (ethylene oxide, 1,2-propylene oxide and oxetane) are preferable, ethylene oxide and 1,2-propylene Oxides are more preferred.
An alkylene oxide may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, the coupling | bonding form may be random, a block, or both.
When two or more kinds of alkylene oxides are used in combination, the resulting cyclic polyether ester (A) has different R ² types corresponding to the type of alkylene oxide used as R ² in the general formula (1). It is a cyclic polyether ester having.

The alkoxylation reaction includes metal halides (boron, tin, nickel, zinc, aluminum, etc.), inorganic acids (sulfuric acid, phosphoric acid, etc.), alkali metals (lithium, sodium, potassium, cesium, etc.) hydroxides. , Amine compounds (diethylamine, triethylamine and the like), oxide composites described in JP-A No. 2000-354663, fired products thereof, layered double hydroxides, and the like.
The layered double hydroxide is a divalent metal (Mg, Fe, Zn, Ca, Li, Ni, Co, Cu, etc.) and a trivalent metal (Al, Fe, Mn, etc.) hydroxide. Means an inorganic layered compound in which a laminated structure is formed by composite, and the general formula is [M 2 ⁺ _1-a M ³⁺ _a (OH) ₂ ] [(A ⁿ⁻ ) _{a / n} · mH ₂ O] [here ^{in, M 2+} is a divalent ^{metal, M 3+} is a trivalent ^{metal, a n-n-valent} anion _{^{(HCO 3-, PO 4 3-,}} SO 4 2-, Cl -, NO 2 - and NO ₃ ^- etc.), m> 0. ], And includes hydrotalcite, moscoleite, manacite, stichtite, pyroaulite, tacobite, eardrite, meixenelite, and the like. These layered double hydroxides are known as clay minerals, and may be those contained in naturally occurring minerals, those obtained by synthesis, or used as they are. What baked at 400-950 degreeC (preferably 400-700 degreeC) may be used.

As those available from the market as a layered double hydroxide can be used for the alkoxylation reaction, the layered double hydroxide may be mentioned that represented by the general formula (2), Kyoward _{500 (Mg 6 A l2 (OH} ) ₁₆ CO ₃ / 4H ₂ O) (manufactured by Kyowa Chemical Industry Co., Ltd., “KYOWARD” is a registered trademark of the same company. Hereinafter, the same applies to products with names including “KYOWARD”), KYOWARD 1000 (Mg _{4 .5 A l2 (OH) 13 CO} 3 · 3.5H 2 O) , and the like.

In general formula (2), x and y are 0 <x ≦ 0.5 and 0 <y ≦ 1.0.

The polymer compound (B) that is a shaft component in the rotaxane of the present invention is preferably a hydrophilic polymer compound, preferably a polymer compound having polyacrylic acid and a polyoxyalkylene chain, and more preferably a polymer compound Examples thereof include acrylic acid and polyoxyalkylene (polyethylene glycol, polypropylene glycol, polytetrahydrofuran and copolymers thereof).
Among these, polyoxyalkylene is preferable and polyethylene glycol is more preferable. These polymers may be used alone or in combination of two or more.
In addition, as the polymer compound (B), the polyoxyalkylene and polyisocyanate compound polyurethane and polysiloxane (polydimethylsiloxane etc.) having properties similar to the oxyalkylene chain can be preferably used.

Further, the polymer compound (B) may be a polymer having a reactive functional group introduced, and examples of the reactive functional group to be introduced include an amino group, a thio group, a hydroxyl group, and a maleimide group. Examples of the polymer compound (B) into which these reactive functional groups are introduced include terminal amine-modified polyethylene glycol, terminal thiol-modified polyethylene glycol, terminal maleimide-modified polyethylene glycol, and the like. These are the SUNBRITE series (SUNBRITE is NOF Corporation). It is available from NOF Corporation as a registered trademark of the company. Further, when the polymer compound (B) is a (co) polymer having a (meth) acrylic acid monoester of polyethylene glycol as an essential constituent monomer, a copolymerizable monomer having these reactive functional groups And a method of copolymerizing with a (meth) acrylic acid monoester of polyethylene glycol by a known method and a method of polymerizing by a known method using a radical polymerization initiator having these reactive functional groups.

The number average molecular weight of the polymer compound (B) is preferably 1,000 to 100,000 from the viewpoint of ease of synthesis of the rotaxane.
The number average molecular weight of the polymer compound (B) can be measured under the following conditions using the following GPC.
Apparatus: “Waters Alliance 2695” [manufactured by Waters]
Column: “Guardcolumn Super HL” (1), “TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 each connected one” [all manufactured by Tosoh Corporation]
・ Sample solution: 0.25 wt% tetrahydrofuran solution ・ Solution injection amount: 10 μL
・ Flow rate: 0.6 mL / min ・ Measurement temperature: 40 ° C.
・ Detection device: Refractive index detector ・ Reference material: Standard polyethylene glycol

The rotaxane of the present invention polymerizes the polymer compound (B) by a known method by mixing the cyclic polyether ester (A) and the polymer compound (B) and in the presence of the cyclic polyether ester (A). Although it can manufacture by a method etc., the method of mixing cyclic polyether ester (A) and a high molecular compound (B) from viewpoints, such as the ease of the synthesis | combination of a rotaxane, is preferable.

Examples of the method of mixing the cyclic polyether ester (A) and the polymer compound (B) include a method of stirring and mixing the cyclic polyether ester (A) and the polymer compound (B) in an aqueous medium. The temperature at the time of stirring and mixing is 0 to 100 ° C., preferably 4 to 80 ° C., and the mixing time is 1 second to 1 week, preferably 10 seconds to 3 days. The rotaxane in which the polymer compound (B) penetrates the cyclic polyether ester (A) can be isolated by a known separation method such as reprecipitation, filtration, centrifugation, membrane separation and column chromatography. .

The fact that the complex obtained by mixing the cyclic polyether ester (A) and the polymer compound (B) contains rotaxane means that the powder X-ray diffraction and NMR spectrum measurement and observation with an atomic force microscope are known. You can confirm by doing. In addition, since rotaxane is often obtained as a precipitate in an aqueous medium, the production can be confirmed by visual observation. In the measurement of powder X-ray diffraction, the presence or absence of rotaxane formation can be confirmed by comparing with the diffraction peak shown by a known rotaxane, and by NMR spectrum, one molecule of the polymer compound (B) The number of cyclic polyether ester (A) which penetrates can be calculated.

When the cyclic polyether ester (A) and the polymer compound (B) are mixed, it is preferable to use 1 to 10 parts of the cyclic polyether ester (A) with respect to 100 parts of the polymer compound (B). More preferably, 5 parts are used.

After obtaining the rotaxane (a) in which the polymer compound (B) penetrates the cavity part of the cyclic polyether ester (A), the cyclic polyether ester (A) cannot be further detached from the polymer compound (B). Therefore, it is preferable that the polymer compound (B) has bulky functional groups at both ends, or the rotaxanes (a) are three-dimensionally cross-linked.

The bulky functional group to be added to the end of the rotaxane (a) can be selected according to the size of m and n of the cyclic polyether ester (A) and the type of the polymer compound (B). Any functional group may be used as long as the cyclic polyether ester (A) is not eliminated from the compound (B), such as an N-substituted amino group described in JP2012-172083A, and JP2009-013253A. Functional groups introduced using the described capping agents and bulky groups described in JP-A-2006-233007 can be used.

As the rotaxane in which the rotaxanes (a) are three-dimensionally cross-linked, a reaction product of a compound having at least three functional groups that react with the reactive functional groups of the polymer compound (B) and the rotaxane (a) Is mentioned. When the polymer compound (B) has a hydroxyl group and / or an amino group, a tri- or higher functional polycarboxylic acid (1,3-propanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4 -Cyclohexanetricarboxylic acid, trimellitic acid, aconitic acid, etc.) and / or a reaction product of trifunctional or higher functional polyisocyanate (isocyanurate polyisocyanate etc.) and rotaxane (a). Rotaxane (a), a tri- or higher functional polycarboxylic acid and a reaction product can be obtained by performing a dehydration reaction by a known method, and a reaction product of a taxane (a) and a tri- or higher functional polyisocyanate is a known product. It can be obtained by performing an addition reaction by a method.

Like the conventional rotaxane, the rotaxane of the present invention can be added to a coating agent or the like and used as a self-healing component. Further, a gel in which a solvent such as water is absorbed can be used as a functional material for shock absorbing materials and medical materials.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this.
In addition, the part in an Example shows a weight part.

<Production Example 1>
In a stainless steel autoclave with a stirrer and a temperature control function, 240 parts (1 mol) of 15-pentadecanolactone, “Kyoward 500” [manufactured by Kyowa Chemical Industry Co., Ltd .: Mg ₆ Al ₂ (OH) ₁₆ [CO ₃ .4H ₂ O] 24.2 parts (0.04 mol) and 1 part (0.002 mol) of aluminum perchlorate nonahydrate were sealed and sealed at 160 ° C. under reduced pressure for 3 hours. Heated and dehydrated. Next, the temperature was raised to 180 ° C., and 88 parts (2 mol) of ethylene oxide (hereinafter abbreviated as EO) were introduced into the autoclave while adjusting the gauge pressure to be in the range of 1 to 5 kgf / cm ² at 180 ° C. did. After introducing the total amount of EO, stirring was continued until the pressure reached 0.13 kgf / cm ² G. Thereafter, 0.3 part of potassium hydroxide was added, and 176 parts (4 mol) of EO was further introduced at 180 ° C. so that the gauge pressure was 1 to 5 kgf / cm ² . After the total amount of EO was introduced, stirring was continued until the pressure reached 0.13 kgf / cm ² G to carry out the reaction between 15-pentadecanolactone and EO. The total time required for the EO addition reaction was 8 hours. Thereafter, the catalyst was filtered off from the reaction mixture obtained by the addition reaction of EO to obtain a cyclic polyether ester composition (A1).
The obtained cyclic polyetherester composition (A1) was analyzed by MALDI-TOF MS.
The cyclic polyether ester composition (A1) has a total of 90 weights of the cyclic polyether ester (A1-1) represented by the general formula (1) in which m is 1 to 3 and n is 1 to 30. % Of the cyclic polyether ester, the average value of n of the cyclic polyether ester (A1-1) (that is, the average number of moles of EO added) is 6, and the cyclic polyether ester (A1-1) , N is 5 to 10, the total weight of the cyclic polyether ester is 85% by weight with respect to the total weight of the cyclic polyether ester (A1-1), and among the cyclic polyether ester (A1-1), The cyclic polyether ester with m = 1 was 60% by weight.

<Production Example 2>
In a stainless steel autoclave equipped with a stirrer and a temperature control function, 240 parts (1 mole) of 15-pentadecanolactone, 24.2 parts (Kyoward 500) (0.04 mole), and aluminum perchlorate After 1 part (0.002 mol) of hydrate was added and sealed, it was dehydrated by heating at 160 ° C. for 3 hours under reduced pressure. Next, the temperature was adjusted to 150 ° C., and 61 parts (1.05 mol) of propylene oxide (hereinafter abbreviated as PO) was adjusted in the autoclave while adjusting the gauge pressure to 1 to 3 kgf / cm ² G at 150 ° C. Introduced. After the entire amount of PO was introduced, stirring was continued until the pressure reached 0.13 kgf / cm ² G to carry out the reaction between 15-pentadecanolactone and PO. The time required for the PO addition reaction was 12 hours. Next, the temperature was adjusted to 180 ° C., and 220 parts (5 mol) of EO was introduced into the autoclave while adjusting the gauge pressure to 1 to 3 kgf / cm ² at 180 ° C. After the total amount of EO was introduced, stirring was continued until the pressure became 0.13 kgf / cm ² G, and EO reaction was carried out. The time required for the EO addition reaction was 7 hours. The catalyst was filtered off from the reaction mixture obtained after completion of the EO addition reaction to obtain a cyclic polyether ester composition (A2).
The obtained cyclic polyetherester composition (A1) was analyzed by MALDI-TOF MS.
The cyclic polyether ester composition (A2) is a total of the cyclic polyether esters (A2-1) represented by the general formula (1), wherein m is 1 to 3 and n is 1 to 30 respectively. The average value of n of the cyclic polyether ester (A2) contained in the cyclic polyether ester composition (A2) is 6, and the average added mole number of PO is 1, The average added mole number of EO is 5, and among the cyclic polyether ester (A2-1), the total weight of the cyclic polyether ester represented by the general formula (1) where n is 5 to 10 is It was 90% by weight relative to the total weight of the ether ester (A2-1), and among the cyclic polyether ester (A2-1), the cyclic polyether ester having m = 1 was 60% by weight.

<Production Example 3>
In a stainless steel autoclave equipped with a stirrer and a temperature control function, 240 parts (1 mol) of 15-pentadecanolactone and “Kyoward 500” [manufactured by Kyowa Chemical Industry Co., Ltd .: Mg ₆ Al ₂ (OH)] _[16 CO ₃ .4H ₂ O] 24.2 parts (0.04 mol) was added and sealed, followed by dehydration by heating at 160 ° C. for 3 hours under reduced pressure. Next, the temperature was adjusted to 180 ° C., and 264 parts (6 mol) of EO was introduced into the autoclave while adjusting the gauge pressure to be in the range of 1 to 5 kgf / cm ² at 180 ° C. After the total amount of EO was added, stirring was continued until the pressure reached 0.13 kgf / cm ² G to carry out the reaction between 15-pentadecanolactone and EO. The time required for the EO addition reaction was 10 hours. Thereafter, the catalyst was filtered off from the reaction mixture obtained by the addition reaction of EO to obtain a cyclic polyether ester composition (A3).
The obtained cyclic polyether ester composition (A3) was analyzed by MALDI-TOF MS.
The cyclic polyether ester composition (A3) is a total of the cyclic polyether esters (A3-1) represented by the general formula (1) wherein m is 1 to 3 and n is 1 to 30 respectively. The average value of n of the cyclic polyether ester (A3-1) (that is, the average added mole number of EO) is 6, and among the cyclic polyether ester (A3-1), n 5-10, the total weight of the cyclic polyether ester is 28% by weight with respect to the total weight of the cyclic polyether ester (A3-1), and m is 1 in the cyclic polyether ester (A3-1). The cyclic polyether ester was 60% by weight.

<Production Example 4>
In a stainless steel autoclave with a stirrer and a temperature control function, 240 parts (1 mol) of 15-pentadecanolactone, “Kyoward 500” [manufactured by Kyowa Chemical Industry Co., Ltd .: Mg ₆ Al ₂ (OH) ₁₆ [CO ₃ .4H ₂ O] 24.2 parts (0.04 mol) and 1 part (0.002 mol) of aluminum perchlorate nonahydrate were sealed and sealed at 160 ° C. under reduced pressure for 3 hours. Heated and dehydrated. Next, the temperature was raised to 180 ° C., and 88 parts (2 mol) of ethylene oxide (hereinafter abbreviated as EO) were introduced into the autoclave while adjusting the gauge pressure to be in the range of 1 to 5 kgf / cm ² at 180 ° C. did. After introducing the total amount of EO, stirring was continued until the pressure reached 0.13 kgf / cm ² G. Thereafter, 0.3 part of potassium hydroxide was added, and 352 parts (8 mol) of EO was further introduced at 180 ° C. so that the gauge pressure was 1 to 5 kgf / cm ² . After the total amount of EO was introduced, stirring was continued until the pressure reached 0.13 kgf / cm ² G to carry out the reaction between 15-pentadecanolactone and EO. The total time required for the EO addition reaction was 8 hours. Thereafter, the catalyst was filtered off from the reaction mixture obtained by the addition reaction of EO to obtain a cyclic polyether ester composition (A4).
The obtained cyclic polyetherester composition (A4) was analyzed by MALDI-TOF MS.
The cyclic polyether ester composition (A4) has a total weight of 90 wt% of the cyclic polyether ester (A4-1) represented by the general formula (1) in which m is 1 to 3 and n is 1 to 30. % Of the cyclic polyether ester, and the average value of n of the cyclic polyether ester (A4-1) (that is, the average number of moles of EO added) is 10, of the cyclic polyether ester (A4-1). , N was 8 to 13, and the total weight of the cyclic polyether ester was 85% by weight with respect to the total weight of the cyclic polyether ester (A4-1).

<Production Example 5>
In a stainless steel autoclave with a stirrer and a temperature control function, 240 parts (1 mol) of 15-pentadecanolactone, “Kyoward 500” [manufactured by Kyowa Chemical Industry Co., Ltd .: Mg ₆ Al ₂ (OH) ₁₆ [CO ₃ .4H ₂ O] 24.2 parts (0.04 mol) and 1 part (0.002 mol) of aluminum perchlorate nonahydrate were sealed and sealed at 160 ° C. under reduced pressure for 3 hours. Heated and dehydrated. Next, the temperature was raised to 180 ° C., and 88 parts (2 mol) of ethylene oxide (hereinafter abbreviated as EO) were introduced into the autoclave while adjusting the gauge pressure to be in the range of 1 to 5 kgf / cm ² at 180 ° C. did. After introducing the total amount of EO, stirring was continued until the pressure reached 0.13 kgf / cm ² G. Thereafter, 0.3 part of potassium hydroxide was added, and 1232 parts (28 mol) of EO was further introduced at 180 ° C. so that the gauge pressure was 1 to 5 kgf / cm ² . After the total amount of EO was introduced, stirring was continued until the pressure reached 0.13 kgf / cm ² G to carry out the reaction between 15-pentadecanolactone and EO. The total time required for the EO addition reaction was 8 hours. Thereafter, the catalyst was filtered off from the reaction mixture obtained by the addition reaction of EO to obtain a cyclic polyether ester composition (A5).
The obtained cyclic polyether ester composition (A5) was analyzed by MALDI-TOF MS.
The cyclic polyether ester composition (A5) has a total of 90 weights of the cyclic polyether ester (A5-1) represented by the general formula (1) in which m is 1 to 3 and n is 1 to 30. % Of cyclic polyether ester, and the average value of n of cyclic polyether ester (A5-1) (that is, the average number of moles of EO added) is 30, out of cyclic polyether ester (A5-1). , N was 28 to 33, and the total weight of the cyclic polyether ester was 85% by weight with respect to the total weight of the cyclic polyether ester (A5-1).

<Example 1>
23.7 parts of the cyclic polyether ester composition (A1) obtained in Production Example 1 and both end amino group-modified polyethylene glycols of Mn2000 (SUNBRIGHT DE-020PA, manufactured by NOF Corporation, SUNBRITE is manufactured by NOF Corporation. 200 parts of (registered trademark) was put in a glass container and stirred at room temperature for 1 hour. The obtained composition was washed with water and n-hexane and dried in vacuo at 90 ° C. for 4 hours to obtain a composition (a1).
Similar to Example 1 of JP2009-013253, 3,5-dimethylbenzoic acid (manufactured by Aldrich) was refluxed at the boiling point with a catalytic amount of dimethylformamide in thionyl chloride to give 3,5-dimethylbenzoic acid. An acid chloride was synthesized, and 34 parts of the 3,5-dimethylbenzoic chloride and 34 parts of triethylamine were added to a dimethylformamide dispersion containing 223.7 parts of the composition (a1). Reacted for hours. The obtained reaction solution was poured into diethyl ether and reprecipitated, and the precipitate was collected, washed with water and methanol, and then dried to obtain the rotaxane (R1) of the present invention.
¹ H-NMR of the obtained rotaxane was measured, and it was confirmed that the polyethylene glycol chain penetrated the cyclic polyether ester and 3,5-dimethylbenzoic acid was bonded to both ends of the polyethylene glycol.

<Example 2>
11.85 parts of the cyclic polyether ester composition (A1) obtained in Production Example 1 and both end amino group-modified polyethylene glycols of Mn2000 (SUNBRIGHT DE-020PA, manufactured by NOF Corporation, SUNBRITE is manufactured by NOF Corporation. 200 parts of (registered trademark) was put in a glass container and stirred at room temperature for 1 hour. The obtained composition was washed with water and n-hexane and dried in vacuo at 90 ° C. for 4 hours to obtain a composition (a2).
Similar to Example 1 of JP2009-013253, 3,5-dimethylbenzoic acid (manufactured by Aldrich) was refluxed at the boiling point with a catalytic amount of dimethylformamide in thionyl chloride to give 3,5-dimethylbenzoic acid. An acid chloride was synthesized, and 34 parts of the 3,5-dimethylbenzoic acid chloride and 34 parts of triethylamine were added to a dimethylformamide dispersion containing 211.85 parts of the composition (a2). Reacted for hours. The obtained reaction solution was poured into diethyl ether and reprecipitated, and the precipitate was collected, washed with water and methanol, and then dried to obtain the rotaxane (R2) of the present invention.
¹ H-NMR of the obtained rotaxane was measured, and it was confirmed that the polyethylene glycol chain penetrated the cyclic polyether ester and 3,5-dimethylbenzoic acid was bonded to both ends of the polyethylene glycol.

<Example 3>
2.37 parts of the cyclic polyether ester composition (A1) obtained in Production Example 1 and both end amino group-modified polyethylene glycols of Mn2000 (SUNBRIGHT DE-020PA, manufactured by NOF Corporation, SUNBRITE is manufactured by NOF Corporation. 200 parts of (registered trademark) was put in a glass container and stirred at room temperature for 1 hour. The obtained composition was washed with water and n-hexane and dried in vacuo at 90 ° C. for 4 hours to obtain a composition (a3).
Similar to Example 1 of JP2009-013253, 3,5-dimethylbenzoic acid (manufactured by Aldrich) was refluxed at the boiling point with a catalytic amount of dimethylformamide in thionyl chloride to give 3,5-dimethylbenzoic acid. An acid chloride was synthesized, and 34 parts of the 3,5-dimethylbenzoic chloride and 34 parts of triethylamine were added to a dimethylformamide dispersion containing 202.37 parts of the composition (a3). Reacted for hours. The obtained reaction solution was poured into diethyl ether and reprecipitated, and the precipitate was collected, washed with water and methanol, and then dried to obtain the rotaxane (R3) of the present invention.
¹ H-NMR of the obtained rotaxane was measured, and it was confirmed that the polyethylene glycol chain penetrated the cyclic polyether ester and 3,5-dimethylbenzoic acid was bonded to both ends of the polyethylene glycol.

<Example 4>
11.85 parts of cyclic polyetherester composition (A2) obtained in Production Example 2 and Mn2000-terminated amino group-modified polyethylene glycol (SUNBRIGHT DE-020PA, manufactured by NOF Corporation, SUNBRITE is manufactured by NOF Corporation. 200 parts of (registered trademark) was put in a glass container and stirred at room temperature for 1 hour. The obtained composition was washed with water and n-hexane and dried in vacuo at 90 ° C. for 4 hours to obtain a composition (a4).
Similar to Example 1 of JP2009-013253, 3,5-dimethylbenzoic acid (manufactured by Aldrich) was refluxed at the boiling point with a catalytic amount of dimethylformamide in thionyl chloride to give 3,5-dimethylbenzoic acid. An acid chloride was synthesized, and 34 parts of the 3,5-dimethylbenzoic chloride and 34 parts of triethylamine were added to a dimethylformamide dispersion containing 211.85 parts of the composition (a4). Reacted for hours. The obtained reaction solution was poured into diethyl ether and reprecipitated, and the precipitate was collected, washed with water and methanol, and then dried to obtain the rotaxane (R4) of the present invention.
¹ H-NMR of the obtained rotaxane was measured, and it was confirmed that the polyethylene glycol chain penetrated the cyclic polyether ester and 3,5-dimethylbenzoic acid was bonded to both ends of the polyethylene glycol.

<Example 5>
11.85 parts of the cyclic polyether ester composition (A3) obtained in Production Example 3 and 200 parts of both end amino group-modified polyethylene glycols (SUNBRIGHT DE-020PA, manufactured by NOF Corporation) of Mn2000 in a glass container And stirred at room temperature for 1 hour. The obtained composition was washed with water and n-hexane and dried in vacuo at 90 ° C. for 4 hours to obtain a composition (a5).
Similar to Example 1 of JP2009-013253, 3,5-dimethylbenzoic acid (manufactured by Aldrich) was refluxed at the boiling point with a catalytic amount of dimethylformamide in thionyl chloride to give 3,5-dimethylbenzoic acid. An acid chloride was synthesized, and 34 parts of the 3,5-dimethylbenzoic chloride and 34 parts of triethylamine were added to a dimethylformamide dispersion containing 211.85 parts of the composition (a5). Reacted for hours. The obtained reaction solution was poured into diethyl ether and reprecipitated, and the precipitate was collected, washed with water and methanol, and dried to obtain the rotaxane (R5) of the present invention.
¹ H-NMR of the obtained rotaxane was measured, and it was confirmed that the polyethylene glycol chain penetrated the cyclic polyether ester and 3,5-dimethylbenzoic acid was bonded to both ends of the polyethylene glycol.

<Example 6>
In a glass container, 11.85 parts of the cyclic polyether ester composition (A4) obtained in Production Example 4 and 200 parts of both end amino group-modified polyethylene glycols (SUNBRIGHT DE-020PA, manufactured by NOF Corporation) of Mn2000 are used. And stirred at room temperature for 1 hour. The obtained composition was washed with water and n-hexane and dried in vacuo at 90 ° C. for 4 hours to obtain a composition (a6).
Similar to Example 1 of JP2009-013253, 3,5-dimethylbenzoic acid (manufactured by Aldrich) was refluxed at the boiling point with a catalytic amount of dimethylformamide in thionyl chloride to give 3,5-dimethylbenzoic acid. An acid chloride was synthesized, and 34 parts of the 3,5-dimethylbenzoic chloride and 34 parts of triethylamine were added to a dimethylformamide dispersion containing 211.85 parts of the composition (a6). Reacted for hours. The obtained reaction solution was poured into diethyl ether and reprecipitated, and the precipitate was collected, washed with water and methanol, and then dried to obtain the rotaxane (R6) of the present invention.
¹ H-NMR of the obtained rotaxane was measured, and it was confirmed that the polyethylene glycol chain penetrated the cyclic polyether ester and 3,5-dimethylbenzoic acid was bonded to both ends of the polyethylene glycol.

<Example 7>
11.85 parts of the cyclic polyether ester composition (A5) obtained in Production Example 5 and 200 parts of both end amino group-modified polyethylene glycols (SUNBRIGHT DE-020PA, manufactured by NOF Corporation) of Mn2000 in a glass container. And stirred at room temperature for 1 hour. The obtained composition was washed with water and n-hexane and dried in vacuo at 90 ° C. for 4 hours to obtain a composition (a7).
Similar to Example 1 of JP2009-013253, 3,5-dimethylbenzoic acid (manufactured by Aldrich) was refluxed at the boiling point with a catalytic amount of dimethylformamide in thionyl chloride to give 3,5-dimethylbenzoic acid. An acid chloride was synthesized, and 34 parts of the 3,5-dimethylbenzoic chloride and 34 parts of triethylamine were added to a dimethylformamide dispersion containing 211.85 parts of the composition (a7). Reacted for hours. The obtained reaction solution was poured into diethyl ether and reprecipitated, and the precipitate was collected, washed with water and methanol, and then dried to obtain the rotaxane (R7) of the present invention.
¹ H-NMR of the obtained rotaxane was measured, and it was confirmed that the polyethylene glycol chain penetrated the cyclic polyether ester and 3,5-dimethylbenzoic acid was bonded to both ends of the polyethylene glycol.

<Example 8>
11.12 parts of the cyclic polyether ester composition (A1) obtained in Production Example 1 and 200 parts of both-end hydroxyl group polyethylene glycol (PEG 2000, manufactured by Sanyo Chemical Industries, Ltd.) of Mn2000 are placed in a glass container, and 1 at room temperature. After stirring for a period of time, 22 parts of 1,3-bis (isocyanatomethyl) cyclohexane (Takenate 600, manufactured by Mitsui Chemicals, Inc.) was stirred at 90 ° C. for 24 hours. The obtained composition was washed with water and n-hexane and dried in vacuo at 90 ° C. for 4 hours to obtain a composition (a8).
Similar to Example 1 of JP2009-013253, 3,5-dimethylbenzoic acid (manufactured by Aldrich) was refluxed at the boiling point with a catalytic amount of dimethylformamide in thionyl chloride to give 3,5-dimethylbenzoic acid. An acid chloride was synthesized, and 0.5 part of the 3,5-dimethylbenzoic acid chloride and 0.5 part of triethylamine were added to a dimethylformamide dispersion containing part of the composition (a8), and the mixture was added at 0 ° C. The reaction was performed for 2 hours. The obtained reaction solution was poured into diethyl ether and reprecipitated, and the precipitate was collected, washed with water and methanol, and then dried to obtain the rotaxane (R8) of the present invention.
¹ H-NMR of the obtained rotaxane was measured, and it was confirmed that the polyethylene glycol chain penetrated the cyclic polyether ester and 3,5-dimethylbenzoic acid was bonded to both ends of the polyethylene glycol.

<Example 9>
11.12 parts of the cyclic polyether ester composition (A2) obtained in Production Example 2 and 200 parts of hydroxyl-terminated polyethylene glycol of Mn2000 (PEG 2000, manufactured by Sanyo Chemical Industries, Ltd.) are placed in a glass container, and 1 at room temperature. After stirring for a period of time, 22 parts of 1,3-bis (isocyanatomethyl) cyclohexane (Takenate 600, manufactured by Mitsui Chemicals, Inc.) was stirred at 90 ° C. for 24 hours. The obtained composition was washed with water and n-hexane and dried in vacuo at 90 ° C. for 4 hours to obtain a composition (a9).
Similar to Example 1 of JP2009-013253, 3,5-dimethylbenzoic acid (manufactured by Aldrich) was refluxed at the boiling point with a catalytic amount of dimethylformamide in thionyl chloride to give 3,5-dimethylbenzoic acid. An acid chloride was synthesized, and 0.5 parts of the above 3,5-dimethylbenzoic acid chloride and 0.5 parts of triethylamine were added to a dimethylformamide dispersion containing parts of the composition (a9) at 0 ° C. The reaction was performed for 2 hours. The obtained reaction solution was poured into diethyl ether and reprecipitated, and the precipitate was collected, washed with water and methanol, and then dried to obtain the rotaxane (R9) of the present invention.
¹ H-NMR of the obtained rotaxane was measured, and it was confirmed that the polyethylene glycol chain penetrated the cyclic polyether ester and 3,5-dimethylbenzoic acid was bonded to both ends of the polyethylene glycol.

<Example 10>
11.12 parts of the cyclic polyether ester composition (A3) obtained in Production Example 3 and 200 parts of Mn2000-terminated hydroxyl group polyethylene glycol (PEG 2000, manufactured by Sanyo Chemical Industries, Ltd.) are placed in a glass container, and 1 at room temperature. After stirring for a period of time, 22 parts of 1,3-bis (isocyanatomethyl) cyclohexane (Takenate 600, manufactured by Mitsui Chemicals, Inc.) was stirred at 90 ° C. for 24 hours. The obtained composition was washed with water and n-hexane and dried in vacuo at 90 ° C. for 4 hours to obtain a composition (a10).
Similar to Example 1 of JP2009-013253, 3,5-dimethylbenzoic acid (manufactured by Aldrich) was refluxed at the boiling point with a catalytic amount of dimethylformamide in thionyl chloride to give 3,5-dimethylbenzoic acid. The acid chloride was synthesized, and 0.5 part of the 3,5-dimethylbenzoic acid chloride and 0.5 part of triethylamine were added to the dimethylformamide dispersion containing the part of the composition (a10), and the mixture was added at 0 ° C. The reaction was performed for 2 hours. The obtained reaction solution was poured into diethyl ether and reprecipitated, and the precipitate was collected, washed with water and methanol, and dried to obtain the rotaxane (R10) of the present invention.
¹ H-NMR of the obtained rotaxane was measured, and it was confirmed that the polyethylene glycol chain penetrated the cyclic polyether ester and 3,5-dimethylbenzoic acid was bonded to both ends of the polyethylene glycol.

<Example 11>
11.12 parts of the cyclic polyether ester composition (A4) obtained in Production Example 4 and 200 parts of hydroxyl-terminated polyethylene glycol of Mn2000 (PEG 2000, manufactured by Sanyo Chemical Industries, Ltd.) are placed in a glass container, and 1 at room temperature. After stirring for a period of time, 22 parts of 1,3-bis (isocyanatomethyl) cyclohexane (Takenate 600, manufactured by Mitsui Chemicals, Inc.) was stirred at 90 ° C. for 24 hours. The obtained composition was washed with water and n-hexane and vacuum-dried at 90 ° C. for 4 hours to obtain a composition (a11).
Similar to Example 1 of JP2009-013253, 3,5-dimethylbenzoic acid (manufactured by Aldrich) was refluxed at the boiling point with a catalytic amount of dimethylformamide in thionyl chloride to give 3,5-dimethylbenzoic acid. An acid chloride was synthesized, and 0.5 parts of the 3,5-dimethylbenzoic acid chloride and 0.5 parts of triethylamine were added to a dimethylformamide dispersion containing parts of the composition (a11), and the mixture was added at 0 ° C. The reaction was performed for 2 hours. The obtained reaction solution was poured into diethyl ether and reprecipitated, and the precipitate was collected, washed with water and methanol, and then dried to obtain the rotaxane (R11) of the present invention.
¹ H-NMR of the obtained rotaxane was measured, and it was confirmed that the polyethylene glycol chain penetrated the cyclic polyether ester and 3,5-dimethylbenzoic acid was bonded to both ends of the polyethylene glycol.

<Example 12>
11.12 parts of the cyclic polyether ester composition (A5) obtained in Production Example 5 and 200 parts of both-end hydroxyl group polyethylene glycol (PEG 2000, manufactured by Sanyo Chemical Industries, Ltd.) of Mn2000 are placed in a glass container and 1 at room temperature. After stirring for a period of time, 22 parts of 1,3-bis (isocyanatomethyl) cyclohexane (Takenate 600, manufactured by Mitsui Chemicals, Inc.) was stirred at 90 ° C. for 24 hours. The obtained composition was washed with water and n-hexane and dried in vacuo at 90 ° C. for 4 hours to obtain a composition (a12).
Similar to Example 1 of JP2009-013253, 3,5-dimethylbenzoic acid (manufactured by Aldrich) was refluxed at the boiling point with a catalytic amount of dimethylformamide in thionyl chloride to give 3,5-dimethylbenzoic acid. An acid chloride was synthesized, and 0.5 part of the 3,5-dimethylbenzoic acid chloride and 0.5 part of triethylamine were added to a dimethylformamide dispersion containing part of the composition (a12), and the mixture was added at 0 ° C. The reaction was performed for 2 hours. The obtained reaction solution was poured into diethyl ether and reprecipitated, and the precipitate was collected, washed with water and methanol, and then dried to obtain the rotaxane (R12) of the present invention.
¹ H-NMR of the obtained rotaxane was measured, and it was confirmed that a polyethylene glycol chain penetrated the cyclic polyether ester and 3,5-dimethylbenzoic acid was bonded to both ends of the polyethylene glycol.

<Example 13>
12.53 parts of the cyclic polyether ester composition (A1) obtained in Production Example 1, 250 parts of Mn 25,000 polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 1000 parts of water are placed in a glass container, and 60 ° C. Then, 0.6 parts of ethylenediamine (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed at 60 ° C. for 1 hour, water was removed at 100 ° C., and the mixture was further heated at 110 ° C. for 1 hour. The obtained composition was washed with water and n-hexane and vacuum-dried at 90 ° C. for 4 hours to obtain the rotaxane (R13) of the present invention.
¹ H-NMR of the obtained rotaxane was measured, and it was confirmed that the polyacrylate chain penetrated the cyclic polyether ester.

<Comparative Example 1>
In the same manner as in Synthesis Example 1 of JP-A-2006-233007, 12 g of polypropylene glycol having an alkenyl group at both ends and a molecular weight of 10,000 was placed in a glass container, and 30 mL of water was added. To this, 16 g of β-cyclodextrin (A′1) was added and stirred at room temperature for 6 hours. The obtained precipitate was washed with water and n-hexane and dried in vacuo at 90 ° C. for 4 hours to obtain a cyclic compound (A′1). 10 parts of cyclic compound (A′1) and 200 parts of polyethylene glycol modified with both end amino groups of Mn2000 (SUNBRIGHT DE-020PA, manufactured by NOF Corporation, SUNBRITE is a registered trademark of NOF Corporation) in a glass container. And stirred at room temperature for 1 hour. The obtained composition was washed with water and n-hexane and dried in vacuo at 90 ° C. for 4 hours to obtain a composition (a′1).
Similar to Example 1 of JP2009-013253, 3,5-dimethylbenzoic acid (manufactured by Aldrich) was refluxed at the boiling point with a catalytic amount of dimethylformamide in thionyl chloride to give 3,5-dimethylbenzoic acid. An acid chloride was synthesized, 34 parts of the 3,5-dimethylbenzoic acid chloride and 77 mg of triethylamine were added to a dimethylformamide dispersion containing 11 parts of the composition (a1), and reacted at 0 ° C. for 2 hours. It was. The obtained reaction solution was poured into diethyl ether and reprecipitated, and the precipitate was collected, washed with water and methanol, and then dried to obtain the rotaxane (R′1) of the present invention.
¹ H-NMR of the obtained rotaxane was measured, and it was confirmed that the polyethylene glycol chain penetrated the cyclic polyether ester and 3,5-dimethylbenzoic acid was bonded to both ends of the polyethylene glycol.

<Introduction efficiency of cyclic composition>
¹ H-NMR was measured for each of the rotaxanes (R1) to (R13) and (R′1) obtained in Examples 1 to 13 and Comparative Example 1, and the rotaxanes (R1) to (R12) and ( For each of R′1), the number of cyclic compounds having a rotaxane structure through which a polymer compound penetrated was measured, and Examples 1 to 13 were obtained to obtain rotaxanes (R1) to (R13) and (R′1). Of the cyclic compounds introduced in each of Comparative Examples 1 and Comparative Example 1, the ratio of the cyclic compounds having a rotaxane structure penetrated by the polymer compound (introduction efficiency of the cyclic composition) was calculated and listed in Table 1. The larger this value, the easier the cyclic compound becomes a rotaxane.
Further, the number of cyclic compounds contained in the rotaxane when the Mn of the polymer compound as the shaft component is 1000 based on the number of cyclic compounds penetrated by the polymer compound and the Mn of the polymer compound (polymer compound) The number of ring components per 1000 Mn) was calculated and listed in Table 1. A larger value means a combination of a ring component and a shaft component that are likely to be rotaxanes.

<Self-healing test>
The rotaxanes (R1) to (R13) and (R′1) obtained in Examples 1 to 13 and Comparative Example 1 were dissolved or swollen in water, respectively, and coated on a flat glass plate, respectively, at 100 ° C. for 1 hour. A film having a thickness of 100 μm was produced by drying.
The surface of each film was rubbed with a brass brush (3 rows of bristle material, wire diameter 0.15 mm) under a load of 500 g, and then the time taken to recover the scratch was measured. The results are shown in Table 1.

In the rotaxanes obtained in Examples 1 to 13, the cyclic compound efficiently penetrates the polymer as compared with Comparative Example 1, and the self-healing property was also excellent.

The polyrotaxane of the present invention is useful as a functional material used for viscoelastic materials used for self-healing materials and shock-absorbing materials and medical materials.

Claims (3)

A rotaxane having a structure in which a polymer component (B) as a shaft component penetrates a ring component composed of at least one cyclic polyether ester (A) represented by the general formula (1).
[Wherein, R ¹ is a divalent hydrocarbon group having 2 to 21 carbon atoms in which at least one hydrogen atom may be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group, and R ² is a carbon atom. A divalent hydrocarbon group of 2 to 8, m is an integer of 1 to 3, n is an integer of 1 to 30, and m R ¹ may be the same or different. , M × n R ² may be the same or different. ] The rotaxane according to claim 1, wherein R ¹ in the general formula (1) is a linear or branched alkylene group having 3 to 16 carbon atoms, and R ² is an alkylene group having 2 to 4 carbon atoms. The rotaxane according to claim 1 or 2, wherein the polymer compound (B) is a polymer compound having a polyacrylic acid or polyoxyalkylene chain.