JP4783098B2 - Pseudopolyrotaxane and method for producing polyrotaxane - Google Patents

Description

  The present invention relates to a method for producing a pseudopolyrotaxane and a polyrotaxane, and particularly to a method for producing a pseudopolyrotaxane and a polyrotaxane that can be carried out in a solid phase without using a solvent.

  In recent years, polyrotaxane has attracted attention because of its specificity in molecular structure and various properties. In this polyrotaxane, the molecular chain of the chain compound (axial molecule) penetrates through the pores of the molecular ring of the cyclic compound (ring molecule), and has bulky end-capping groups at both ends of the molecular chain of the chain compound. Of structure. For example, polyrotaxane formed using α-cyclodextrin as a ring molecule and polyethylene glycol as an axis molecule is used for soft materials such as contact lenses, molecular devices such as molecular switches and molecular gates, sensors for metal ions, etc. Is also expected.

  As a method for producing this polyrotaxane, conventionally, a pseudopolyrotaxane which is an intermediate in which a shaft molecule penetrates a ring molecule is produced, and then a bulky substituent is added to both ends of the shaft molecule of this pseudopolyrotaxane. Various methods such as a method of winding a ring molecule around an axial molecule having groups at both ends are known. Moreover, as shown in FIG. 5, the product which precipitates by mixing polytetrahydrofuran which becomes an axis molecule and α-cyclodextrin (α-CD) which becomes a ring molecule in an aqueous solvent while irradiating ultrasonic waves. A method for producing a polyrotaxane is known by treating the pseudopolyrotaxane with an appropriate end-capping agent in an organic solvent after obtaining the pseudopolyrotaxane. Furthermore, recently, when a mixture of polyethylene glycol and cyclodextrin is allowed to stand at room temperature without using a solvent, the reaction occurs very slowly, and a pseudopolyrotaxane having a structure in which polyethylene glycol penetrates the molecular ring of cyclodextrin is generated. (Non-Patent Document 1).

  However, these methods have problems such as a low yield of pseudopolyrotaxane or polyrotaxane or a very slow reaction rate. Therefore, the conventional method can be used in the laboratory as a method for producing pseudo-polyrotaxane and polyrotaxane, but is not practical as a method for producing pseudo-polyrotaxane or polyrotaxane that is actually used in large quantities by commercialization or the like. It was.

By the way, in general, a solvent-free synthesis / production method (or solid-phase synthesis or solid-phase production) that does not use a solvent (solvent) in methods such as chemical reaction and substance synthesis is expected from the viewpoint of environmental protection and green chemistry. Has been. Therefore, a method for producing a pseudopolyrotaxane as a raw material of polyrotaxane without using a solvent in a solid phase is useful from this viewpoint.
A. Harada, M .; Okada, Y. Kawaguchi, Chem. Lett. , 34, 542 (2005)

  Accordingly, an object of the present invention is to provide a method for producing a pseudopolyrotaxane that can produce a pseudopolyrotaxane in a solid phase without using a solvent, and a method for producing a polyrotaxane from the pseudopolyrotaxane. is there.

In order to solve the above-described problem, the method for producing a pseudopolyrotaxane according to the first aspect of the present invention is a structure in which the chain portion of the compound B having a chain molecular structure penetrates the molecular ring of the compound A having a cyclic molecular structure. a method of manufacturing a pseudopolyrotaxane with the compound a, both compounds in the solid phase by pressure mixing viewing including the step (1) for generating said pseudo-polyrotaxane comprising said compound B, the compound B is characterized by having a methylsulfonyl group or a toluenesulfonyl group at both ends .

  In this pseudopolyrotaxane production method, both compounds are pressurized and mixed in a solid phase containing Compound A and Compound B, so that a chain molecular structure is formed in the molecular ring of Compound A without using a solvent. A pseudopolyrotaxane having a structure in which the chain portion of the compound B having a penetrating structure can be obtained.

  The invention according to claim 2 is the method for producing a pseudopolyrotaxane according to claim 1, wherein the pressure mixing is performed by sandwiching a mixture containing the compound A and the compound B between two surfaces. And pressure kneading.

  In this method for producing a pseudopolyrotaxane, a mixture containing Compound A and Compound B is sandwiched between two surfaces and subjected to pressure kneading, whereby the molecular ring of Compound A is chained without using a solvent. A pseudopolyrotaxane having a structure in which a chain portion of compound B having a molecular structure is penetrated can be obtained.

  The invention according to claim 3 is the method for producing a pseudopolyrotaxane according to claim 2, wherein the pressure mixing is performed by adding a mixture containing the compound A and the compound B using a pestle in a mortar. It is the process of pressure kneading.

  In this pseudopolyrotaxane production method, a compound having a chain molecular structure is formed in the molecular ring of compound A by subjecting a mixture containing compound A and compound B to pressure kneading using a pestle in a mortar. A pseudopolyrotaxane having a structure in which the chain portion of B penetrates can be produced in a solid phase without using a solvent.

  The invention according to claim 4 is the method for producing a pseudopolyrotaxane according to any one of claims 1 to 3, wherein the compound B is polyethylene glycol or polytetrahydrofuran.

  In this method for producing a pseudopolyrotaxane, a pseudopolyrotaxane having a structure in which the chain portion of polyethylene glycol or polytetrahydrofuran as the compound B penetrates the molecular ring of the compound A is produced in a solid phase without using a solvent. Can do.

  The invention according to claim 5 is the method for producing a pseudopolyrotaxane according to any one of claims 1 to 4, wherein the compound A is cyclodextrin.

  In this method for producing a pseudopolyrotaxane, a pseudopolyrotaxane having a structure in which the chain portion of the compound B having a chain molecular structure penetrates in the molecular ring of cyclodextrin is produced in a solid state without using a solvent. Can do.

  The invention according to claim 6 includes a pseudopolyrotaxane obtained by the method for producing a pseudopolyrotaxane according to any one of claims 1 to 5 and a substituent bulky than the pore size of the molecular ring of the compound A. It is a method for producing a polyrotaxane, comprising a step of reacting with a terminal blocking agent having a terminal block of the pseudopolyrotaxane.

  In this polyrotaxane production method, the pseudopolyrotaxane obtained by the production method of the pseudopolyrotaxane is reacted with an endblocker having a substituent bulkier than the pore size of the molecular ring of the compound A to endblock the pseudopolyrotaxane. By performing this, a polyrotaxane can be produced.

  In the present invention, the polyrotaxane means that the molecular chain of the chain compound (axial molecule) penetrates through the pores of the molecular ring of the cyclic compound (ring molecule), and bulky end-capping at both ends of the molecular chain of the axial molecule. A polymer having a supramolecular structure having a group and a pseudopolyrotaxane refers to a polymer in which both ends of an axial molecule are not blocked by a terminal blocking group.

  According to the method for producing a pseudopolyrotaxane of the present invention, a pseudopolyrotaxane can be produced in a solid phase without using a solvent. Therefore, the production method of the pseudo polyrotaxane of the present invention is a solvent-free synthesis / production method (or solid phase) in which a pseudo polyrotaxane used as a raw material of a polyrotaxane expected to be used in various fields is not used. Synthesis and solid phase production), which are useful from the viewpoint of environmental protection and green chemistry. Moreover, the reaction of penetrating the shaft molecule through the molecular ring of the ring molecule to produce a pseudopolyrotaxane can be performed easily and dramatically at a high rate and in a high yield by a physical method called pressure mixing. Because it can, it has high practical value.

  Moreover, according to the method for producing a polyrotaxane of the present invention, the polyrotaxane can be synthesized by end-capping the axial molecular terminal of the pseudo-polyrotaxane obtained by the above method with a bulky end-blocking group.

Next, embodiments of the present invention will be described in detail with reference to the drawings as appropriate.
The method for producing a pseudopolyrotaxane according to the present invention comprises reacting a compound A having a cyclic molecular structure with a compound B having a chain molecular structure to cause a chain molecular structure in the molecular ring of the compound A having a cyclic molecular structure. This is a method comprising the step (1) of producing a pseudopolyrotaxane having a structure in which the chain portion of the compound B having a penetrating structure.

  Compound A has a cyclic molecular structure, and has a molecular ring through which the chain portion of compound B having a chain molecular structure penetrates. As this compound A, for example, a cyclodextrin having a structure in which a plurality of α-glucopyranose groups are linked in a cyclic manner by α-1,4-glycoside bonds to form a molecular ring, or the like can be used. Examples of the cyclodextrin include α-cyclodextrin (hole diameter: 4.5 mm), β-cyclodextrin (hole diameter: 7.0 mm), γ-cyclodextrin (hole diameter: 8.5 mm), and the like. These cyclodextrins may be those in which some or all of the functional groups of cyclodextrin are substituted, for example, those in which some or all of the hydroxyl groups are substituted with substituents. The substituent is not particularly limited, and examples thereof include alkoxy groups such as methoxy group and ethoxy group.

  After the formation of the pseudopolyrotaxane, this substituent is a group that does not react with the terminal reactive group that the compound B as the axial molecule has at the molecular end and does not react with the terminal blocking group of the terminal blocking agent to be used. This is advantageous from the viewpoint of the yield, purity and properties of the obtained pseudopolyrotaxane. For example, when the terminal reactive group of compound B is end-capped using isocyanate or acyl halide which is a terminal blocking agent, the groups that do not react with the terminal blocking agent include alkoxy groups, acyl groups, alkoxycarbonyl groups, carbamoyl groups. Group, siloxy group, sulfonyl group, phosphonyl group and the like. Among these, an alkoxy group is preferable. Examples of alkoxy groups include methoxy, ethoxy, benzyloxy, diphenylmethoxy, trityloxy, 4-methoxybenzyloxy, methoxymethoxy, 1-ethoxyethoxy, benzyloxymethoxy, 2-trimethylsilylethoxy, A 2-trimethylsilylethoxymethoxy group, a phenoxy group, a 4-methoxyphenoxy group, and the like can be mentioned. Among these, a methoxy group is particularly preferable because it can be easily obtained.

  In these compounds A, the pore size R1 of the molecular ring has a size in a direction perpendicular to the chain length direction of the chain portion (molecular chain) of the compound B penetrating the molecular ring, that is, the molecular axis diameter R2. On the other hand, R1 <R2 is selected.

  The compound B has a chain molecular structure and has a chain portion (molecular chain) C penetrating the molecular ring of the compound A. Specific examples of this compound B include polypropylene glycol, polytetrahydrofuran, polyethylene glycol, polyoxetane, polytrioxane, poly (1,3-dioxolane), poly (1,3-dioxepane), polysiloxane, terminal hydroxylated polybutadiene and the like. Examples thereof include linear polymers and polymerized (oligomerized) products of these linear polymers. Compound B has a chain portion (molecular chain) C penetrating through the molecular ring of compound A to form a pseudopolyrotaxane. Therefore, at both ends of the molecular chain, the bulk is larger than the pore diameter R1 of the molecular ring of compound A. It is preferable that the structure is not high. Among these, when producing a pseudopolyrotaxane having cyclodextrin as a ring molecule, polytetrahydrofuran (PTHF) and polyethylene glycol are suitable for forming a pseudopolyrotaxane through the molecular ring of cyclodextrin. The compound B having a number average molecular weight (Mn) of about 1000 to 30000 is preferable because the structure penetrating the pores of the molecular ring of the compound A is stable.

In the method of the present invention, in order to produce a pseudopolyrotaxane having a structure in which the chain portion (molecular chain) C of compound B penetrates the molecular ring of compound A, a mixture containing compound A and compound B is mixed under pressure. It is a method to do.
In the mixture to be mixed under pressure, the mixing ratio of compound A and compound B is preferably a ratio of 3 to 20 in terms of a molar ratio of compound A / compound B, particularly preferably a ratio of 5 to 10. By adjusting this mixing ratio, the number n of compound A (ring molecule) penetrated by compound B (axial molecule) in the obtained pseudopolyrotaxane and the coverage θ of compound B by compound A can be adjusted. .

  As shown in FIG. 1, this pressure mixing is performed by sandwiching a mixture M containing the compound A and the compound B between two surfaces S1 and S2 and applying pressure from one side or both sides. It is preferable to carry out by adding a kneading action. Here, the shape of the two surfaces S1 and S2 is not particularly limited, and a mixture in which one surface is flat and the other surface is a curved surface (spherical, roll, or planar surface), or both surfaces are flat and both surfaces are curved. Any form may be used as long as it can pressurize from one side or both sides and can add a kneading action to the mixture.

  Specific examples of this pressure mixing include a method of pressure kneading a mixture containing the compound A and the compound B with a pestle in a mortar made of straw, alumina or the like, a ball mill, a kneader, a stone mill, a calendar. Examples thereof include a method using a roller such as a roll, a screw, a grinder, a mixer, a kneader and the like.

The pressure during the pressure mixing is not particularly limited, but it is preferable to apply a pressure exceeding atmospheric pressure to the mixture. Further, the reaction temperature during the pressure mixing is not particularly limited, but is preferably room temperature or higher. By heating, the yield and coverage of the pseudopolyrotaxane can be improved.
The pressure mixing time is not particularly limited, but about 30 minutes to 2 hours is sufficient.

In the method of the present invention, a specific example of a reaction for obtaining a pseudopolyrotaxane using α-CD as compound A and PTHF as compound B is shown in the following formula for the reaction in which a mixture of compound A and compound B is mixed under pressure.

  In the present invention, the pseudopolyrotaxane obtained by pressure mixing a mixture of compound A and compound B can be obtained by purifying the reaction mixture after pressure mixing. Purification is not particularly limited, and can be performed by appropriately adopting methods such as column chromatography, HPLC, recrystallization, solvent washing, water washing, and reprecipitation.

  In the method of the present invention, depending on the pressure mixing conditions (mixing ratio of compound A and compound B, pressure during pressure mixing, temperature, pressure method, time, apparatus, etc.), one molecule of pseudopolyrotaxane The number n of the compound A (ring molecule) penetrated by the compound B (axial molecule) and the ratio of the length of the portion covered by the compound A (ring molecule) in the molecular chain of the compound B (axial molecule) Pseudopolyrotaxanes having various structures with different coverages θ can be obtained. For example, when a 10-fold equivalent of a ring molecule is added to an axial molecule having a molecular weight of about 1000 to 2000 and mixed under pressure at 80 ° C. for 30 minutes to 2 hours, a pseudo-polyrotaxane (θ = 107%: Since the ring enters beyond the end of the shaft, it becomes 100% or more).

  Further, in the present invention, the pseudopolyrotaxane axial molecule (compound B) obtained by the above-described method is reacted with a terminal blocker having a substituent bulkier than the pore diameter R1 of the molecular ring of the ring molecule (compound A). Then, the polyrotaxane can be obtained by end-capping the pseudopolyrotaxane.

  The endblocking of the pseudopolyrotaxane may be performed by any method as long as the endblocking agent can be reacted with the functional groups at both ends of the pseudopolyrotaxane shaft molecule (compound B) and the endblocking agent. For example, it can be carried out by any method such as a method in which both ends of the pseudopolyrotaxane axial molecule are reacted with a terminal blocking agent in a solvent, and a method in which end blocking is performed by a solid-phase reaction between the pseudopolyrotaxane and the terminal blocking agent. Also good.

As the method for subjecting the pseudopolyrotaxane and the end-capping agent to a solid phase reaction, it is preferable to pressure-mix a mixture of the pseudopolyrotaxane and the end-capping agent. As a mixing means, in addition to mixing while grinding in a mortar, a ball mill, a kneader, a stone mortar, a roller, a screw, a grinding machine, a mixer, a kneader, or the like can be used. Although it does not specifically limit as a pressure, It is preferable to add the pressure exceeding atmospheric pressure to the mixture of pseudo polyrotaxane and a terminal blocker.
The reaction temperature during the pressure mixing is not particularly limited, but is preferably room temperature or higher. By heating, the yield of polyrotaxane and the coverage of the substituted cyclodextrin with respect to the polymer can be improved.

  As the end-capping agent, a compound that selectively reacts with the end of the axial molecule (compound B) and has a group (R1 <R2) that is bulkier than the pore diameter R1 of the ring molecule (compound A) can be used. For example, isocyanate, acyl halide, acid anhydride and the like can be mentioned. As the bulky group, 3,5-di-t-butylphenylmethyl group, 3,5-dimethylphenylmethyl group, 3,5-dinitrophenylmethyl group, 4-t-butylphenylmethyl group, tritylmethyl group, 4-tritylphenyl group, 3,5-dimethylphenyl group and the like can be mentioned.

  Specific examples of the isocyanate used as the end-capping agent include 4-tritylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, 4-ferrocenylphenyl isocyanate, 3,5-di-tert-butylphenyl isocyanate and the like. Among these, 4-tritylphenyl isocyanate is particularly preferable. Examples of the acyl halide include 3,5-dimethylbenzoic acid chloride, triphenylacetic acid chloride, diphenylacetic acid chloride, 4-tritylbenzoic acid chloride, 3,5-di-tert-butylbenzoic acid chloride, ferrocenecarbonyl chloride and the like. Is mentioned. Examples of the acid anhydride include acid anhydrides corresponding to the compounds exemplified as the acyl halide. Specifically, 3,5-dimethylbenzoic anhydride, triphenylacetic anhydride, diphenylacetic anhydride. Products, 4-tritylbenzoic acid anhydride, 3,5-di-tert-butylbenzoic acid anhydride, ferrocenecarboxylic acid anhydride and the like. The amount of the end-capping agent used is preferably in the range of 5 to 30 equivalents relative to the end group of the axial molecule (compound B).

  When using isocyanate as a terminal blocking agent, it is preferable to carry out addition reaction of isocyanate and the said pseudo poly rotaxane in presence of a catalyst. Catalysts used include n-dibutyltin dilaurate (DBTDL), tetrabutyltin, tributyltin hydride, tributyltin chloride, triphenyltin chloride, bis (tributyltin) oxide, tributyltin alkoxide, dibutyltin maleate, dibutyltin oxide , Dibutyltin dichloride, imidazole, cyanamide, triethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine and the like. These catalysts may be used alone or in combination of two or more. Among these catalysts, n-dibutyltin dilaurate is preferable. It is preferable to use the catalyst in an amount of 0.01 to 0.1 mol with respect to 1 mol of the pseudopolyrotaxane.

  When acyl halide is used as the end-capping agent, it is preferable to react acyl halide and pseudopolyrotaxane in the presence of a catalyst. Examples of the catalyst used include 4-dimethylaminopyridine (DMAP), triethylamine, triethylenediamine, tributylamine, imidazole, pyridine, picoline, and lutidine. Among these catalysts, it is preferable to use 4-dimethylaminopyridine and triethylamine in combination. The amount of the catalyst used is preferably 3 to 15 equivalents, more preferably 5 to 10 equivalents, based on the pseudopolyrotaxane.

In the method of the present invention, a specific example of a reaction for obtaining a polyrotaxane by end-capping pseudopolyrotaxane is shown in the following formula.

  The polyrotaxane obtained as described above utilizes the characteristics resulting from its unique structure, making use of soft materials such as contact lenses, molecular devices such as molecular switches and molecular gates, sensors for metal ions, biosensors, cartilage, etc. It is expected to be used in a wide range of fields, such as materials for alternative tissues of biological tissues such as tissues, drug delivery systems, and polyfunctional crosslinking agents.

  Note that the present invention is not limited to the production of pseudopolyrotaxane or polyrotaxane, and may be applicable to the synthesis of various substances. For example, it can be applied to the usual chemical reaction, urethane synthesis by addition reaction of alcohol and isocyanate, Diels-Alder reaction, and ring-opening polymerization of epoxy. As expected.

  Next, examples of the present invention will be described, but the present invention is not limited to the following examples.

Example 1
PM-α-CD 490 mg (0.360 mmol) and PTHF (Mn = 1400) 42.0 mg (0.0300 mmol) were placed in an agate mortar and added at room temperature for 2 hours by crushing the reaction mixture with a pestle. Pressure kneading (step A).

  Thereafter, 217 mg (0.600 mmol) of 4-tritylphenyl isocyanate and 18.0 mL (0.0300 mmol) of di-n-butyltin dilaurate were added to the reaction mixture, followed by pressure kneading for 1 hour (step) B).

  Next, the reaction mixture was purified by high performance liquid chromatography (HPLC) to obtain 107 mg of a solid reaction product (yield: 43.9% (based on PTHF)).

The identification result by ¹ H NMR of the obtained reaction product is shown below. From this result, it was found that polyrotaxane was obtained.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 7.26 (m, 38H, end group ArH), 4.98 (s, 6H × 4.9, TM (α) -CD-C (1) H) , 4.22 (t, 4H, —NHCOOOCH ₂ CH ₂ CH ₂ CH ₂ —), 3.86-3.12 (m, TM (α-CD) C (2-6) H and O (2,3 _{, 6) CH 3, PTHF -CH} 2 CH 2 CH 2 CH 2 O of _{-), 1.56 (s, -CH} 2 CH 2 CH 2 CH 2 O-) ppm

Examples 2-7
By using pressure-kneading in an agate mortar in the same manner as in Example 1 except that PTHF having the number average molecular weight shown in Table 1 below was used and the mixing ratio of PM-α-CD / PTHF shown in Table 1 was used. The reaction was performed.
About the obtained reaction product, the yield of the reaction product, the number n of PM-α-CD penetrated by one PTHF molecule (average number of wheels introduced), and the axial molecule PTHF are covered by the ring molecule PM-α-CD. The coverage θ, which is the ratio of the length of the cracked portion, was determined. The results are shown in Table 1.

Example 8
1.57 g (0.10 mmol) of the pseudopolyrotaxane obtained in Example 1, 1.09 g (3.0 mmol) of 4-tritylphenyl isocyanate and 3.0 μL (5.1 × 10 ⁻³ mmol) of dibutyltin dilaurate In a mortar, pressure mixing was performed at room temperature for 90 minutes. Next, the mixture was dissolved in chloroform, and the hardly soluble component was filtered off and then reprecipitated once in ether and once in methanol to obtain 242 mg (yield: 22%) of a white solid product. The product identification results are shown below. The reaction scheme is shown in FIG.
¹ H NMR (270 MHz, CDCl ₃ , VT60 ° C.): δ = 7.28-7.04 (m, 38H, end group ArH), 4.91 (s, 7.2 × 6H, PMα-CD C (1) H), 3.92- 3.05 (m, PMα-CD C (2-6) H and O (2,3,6) CH ₃ , PTHF -CH ₂ CH ₂ CH ₂ CH ₂ O-), 1.53 (s, 77H, PTHF -CH ₂ CH ₂ CH ₂ CH ₂ O-) ppm.
¹³ C NMR (CDCl ₃ ): δ = 130.7, 127.3, 127.1, 100.2, 82.5, 82.2, 81.3, 71.2, 71.0, 61.7, 58.9, 57.7, 26.7, 26.4 ppm.
IR (KBr): 1736, 1596, 1527 cm ⁻¹ .
GPC (polystyrene standard, eluent: chloroform, UV): Mw / Mn = 1.3, Mn = 10100 (theoretical value 10935)
DSC: Tg = 20.9 ° C., Td = 238 ° C.

Peaks derived from PTHF and PMα-CD are present in the ¹ H NMR spectrum of the product, aromatic carbon peaks derived from 4-tritylphenyl isocyanate are observed in the ¹³ C NMR spectrum, and urethane bonds are derived from the IR spectrum. Absorption was observed. Moreover, since Mn measured by GPC almost coincided with the theoretical value, it was confirmed that polyrotaxane was produced. From the integration ratio of ¹ H NMR, n = 7.2 and θ = 70%.

Example 9
As shown in FIG. 3, polytetrahydrofuran (MeSO ₂ PTHF) having a methylsulfonyl group at both ends of the axial molecule and α-CD were subjected to solid phase reaction by pressure kneading in the same manner as in Example 1. the pseudo-poly rotaxane was produced.

The ¹ H NMR spectrum before and after this solid-phase reaction was measured, and the ¹ H NMR spectrum of the pseudopolyrotaxane after the solid-phase reaction is shown in FIG. 3A, and the ¹ H NMR spectrum of MeSO ₂ PTHF before the solid-phase reaction is shown in FIG. This is shown in 3 (b).

Example 10
As shown in FIG. 4, polytetrahydrofuran (Ts-PTHF) having a toluenesulfonyl group at both ends of the axial molecule and α-CD were pressure-kneaded and subjected to solid phase reaction in the same manner as in Example 1. the pseudo-poly rotaxane was produced.

The ¹ H NMR spectrum before and after the solid-phase reaction was measured, and the ¹ H NMR spectrum of the pseudopolyrotaxane after the solid-phase reaction is shown in FIG. 4 (a), and the ¹ H NMR spectrum of Ts-PTHF before the solid-phase reaction is shown. Shown in 4 (b).

It is a conceptual diagram explaining the manufacturing process of the pseudo polyrotaxane by the pressurization mixing in the method of this invention. 10 is a view showing a reaction scheme of a production process of polyrotaxane in Example 8. FIG. It is a figure which shows the manufacturing process of the pseudo polyrotaxane in Example 9, and the < ¹ > H NMR spectrum before and behind reaction. Is a diagram showing the ^{1 H} NMR spectrum before and after the manufacturing process and the reaction of the pseudopolyrotaxane in Example 10. It is a figure explaining the conventional manufacturing method of a pseudo polyrotaxane.

Claims (6)

A method for producing a pseudopolyrotaxane having a structure in which a chain portion of a compound B having a chain molecular structure penetrates a molecular ring of the compound A having a cyclic molecular structure,
See containing the compound A, the step (1) of the compound B and a double compound with the solid phase comprising by pressure mixed to generate the pseudo-polyrotaxane,
The compound B has a methylsulfonyl group or a toluenesulfonyl group at both ends, and a method for producing a pseudopolyrotaxane,   The pseudo-polyrotaxane according to claim 1, wherein the pressure mixing is a process in which a mixture containing the compound A and the compound B is sandwiched between two surfaces and pressure-kneaded. Method.   3. The production of pseudopolyrotaxane according to claim 2, wherein the pressure mixing is a process of pressure kneading a mixture containing the compound A and the compound B in a mortar using a pestle. Method.   The said compound B is polyethyleneglycol or polytetrahydrofuran, The manufacturing method of the pseudo polyrotaxane of any one of Claims 1-3 characterized by the above-mentioned.   The said compound A is cyclodextrin, The manufacturing method of the pseudo polyrotaxane of any one of Claims 1-4 characterized by the above-mentioned.   A pseudopolyrotaxane obtained by the method for producing a pseudopolyrotaxane according to any one of claims 1 to 5 is reacted with a terminal blocking agent having a substituent bulkier than the pore size of the molecular ring of the compound A. And a step of capping the pseudopolyrotaxane. The method for producing a polyrotaxane is characterized by comprising:

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