JP5463541B2 - Modified pseudopolyrotaxane and modified polyrotaxane, and methods for producing them - Google Patents

Description

  The present invention relates to a modified pseudopolyrotaxane and a modified polyrotaxane having a modified cyclodextrin as a ring component, and a method for producing them.

  Modified polyrotaxanes using a modified cyclodextrin as a ring component and a high molecular weight polymer as an axial molecule are known to exhibit interesting physical properties such as sol-gel transition and lower critical solution temperature (LCST). (Non-Patent Documents 1 and 2).

  To synthesize a modified polyrotaxane containing a modified cyclodextrin as a ring component, a method of modifying a hydroxyl group of cyclodextrin after synthesizing a polyrotaxane using cyclodextrin as a starting material (Patent Document 1) or a modified cyclodextrin Only a method for synthesizing a polyrotaxane in a solid phase starting from the above (Patent Documents 2 and 3) has been known.

  In contrast, in recent years, a method for synthesizing polyrotaxane in a solvent using a modified cyclodextrin as a starting material has been proposed (Patent Document 4).

JP 2007-63412 A JP 2005-75979 A JP 2007-70553 A JP 2008-19371 A

Chemical Communication (Chem. Commun.), 2006, 4102 Journal of Physical Chemistry B (J. Phys. Chem. B), 2006, 110, 24377

  In the method of modifying the hydroxyl group of cyclodextrin after the synthesis of the polyrotaxane, a complicated operation and a lot of time are spent to obtain the modified polyrotaxane, which is not efficient. Furthermore, with this method, it is difficult to obtain a polyrotaxane having a high modification rate. Also, the synthesis of polyrotaxane in the solid phase has a low yield and poor production efficiency. On the other hand, Patent Document 4 does not describe the case where the axial molecule has a high molecular weight.

  The present invention has been made in view of such a situation, and provides a modified pseudo-polyrotaxane and a modified polyrotaxane having a high production efficiency and a high yield, and a novel modified pseudo-polyrotaxane and a modified polyrotaxane. Objective.

  In order to achieve the above object, first, the present invention relates to a method for producing a modified pseudopolyrotaxane by a reaction in which an axial molecule is passed through a hole of a cyclic molecule of a modified cyclodextrin to form an inclusion complex. A method for producing a modified pseudopolyrotaxane having a number average molecular weight of 1500 or more and a covering ratio of the modified cyclodextrin to the axial molecule of 80% or less is provided (Invention 1).

  According to the said invention (invention 1), a modified pseudo polyrotaxane can be manufactured efficiently and the yield of the obtained modified pseudo polyrotaxane is also high.

  In the above invention (Invention 1), the modified cyclodextrin may be a (partially) methylated cyclodextrin (Invention 2).

  In the above invention (Invention 2), the (partial) methylated cyclodextrin may be a permethylated cyclodextrin (Invention 3).

  Secondly, the present invention provides a modified pseudopolyrotaxane by a reaction in which an axial molecule penetrates through a hole of a cyclic molecule of a modified cyclodextrin to form an inclusion complex, and then the obtained modified pseudopolyrotaxane has a shaft molecule and a capping agent. In the method for producing a modified polyrotaxane in which a blocking group is added to both ends of the shaft molecule, the number average molecular weight of the shaft molecule is 1500 or more. Provided is a method for producing a modified polyrotaxane having a dextrin coverage of 80% or less (Invention 4).

  According to the said invention (invention 4), a modified polyrotaxane can be manufactured efficiently and the yield of the obtained modified polyrotaxane is also high.

  In the above invention (Invention 4), the modified cyclodextrin may be a (partially) methylated cyclodextrin (Invention 5).

  In the above invention (Invention 5), the (partial) methylated cyclodextrin may be a permethylated cyclodextrin (Invention 6).

  In the said invention (invention 4-6), it is preferable to make the said axial molecule | numerator and the said capping agent react with the combination of an isocyanate group and an amino group (invention 7).

  Third, the present invention provides a modified pseudopolyrotaxane in which an axial molecule penetrates through a hole of a cyclic molecule of a modified cyclodextrin, wherein the number average molecular weight of the axial molecule is 1500 or more, Provided is a modified pseudopolyrotaxane characterized in that the covering ratio to axial molecules is 80% or less, and the modified cyclodextrin is a permethylated cyclodextrin (Invention 8).

  The modified pseudopolyrotaxane according to the above invention (Invention 8) is a novel modified pseudopolyrotaxane.

  Fourth, the present invention is a modified polyrotaxane in which a shaft molecule penetrates through a hole of a cyclic molecule of a modified cyclodextrin and has blocking groups at both ends of the shaft molecule, and the number average molecular weight of the shaft molecule is 1500 or more. A modified polyrotaxane is characterized in that the covering ratio of the modified cyclodextrin to the axial molecule is 80% or less, and the modified cyclodextrin is a permethylated cyclodextrin (Invention 9).

  The modified polyrotaxane according to the above invention (Invention 9) is a novel modified polyrotaxane.

  According to the method for producing a modified pseudopolyrotaxane or the method for producing a modified polyrotaxane according to the present invention, the production efficiency is good and the yield is remarkably high. In addition, according to the present invention, a novel modified pseudopolyrotaxane or modified polyrotaxane is obtained.

2 is a ¹ H-NMR chart of the polyrotaxane synthesized in Example 1. FIG. 2 is a ¹ H-NMR chart of a polyrotaxane synthesized in Example 2. FIG. 2 is a ¹ H-NMR chart of a polyrotaxane synthesized in Example 3. FIG. 2 is a ¹ H-NMR chart of a polyrotaxane synthesized in Example 4. FIG.

Hereinafter, embodiments of the present invention will be described.
In this embodiment, a pseudo polyrotaxane is produced, and then a polyrotaxane is produced from the obtained pseudo polyrotaxane.

  The pseudopolyrotaxane produced in the present embodiment is one in which a linear molecule (axial molecule) having a functional group at the end penetrates through a hole of a cyclic molecule of a modified cyclodextrin that is a ring component. In this embodiment, first, a linear molecule having a functional group at the terminal and a modified cyclodextrin are prepared. As the linear molecule having a functional group at the terminal, a commercially available one can be used, and it can also be produced as follows.

  The linear molecule is preferably a molecule that dissolves in the reaction solvent. Examples of such molecules include polyethers, polyesters, polyorganosiloxanes, and specific examples include polytetrahydrofuran, polycaprolactone, polyacrylic acid ester, polyethylene glycol, polydimethylsiloxane, and the like. Among these, it is particularly preferable to use polytetrahydrofuran in terms of excellent complex formation with the modified cyclodextrin.

  In the present specification, “linear” of “linear molecule” means substantially “linear”. That is, the linear molecule may have a branched chain as long as the cyclic molecule can move on the linear molecule.

  The number average molecular weight of the linear molecule needs to be 1500 or more, preferably 3000 to 1000000, particularly preferably 5000 to 100,000.

  In the production of a (pseudo) polyrotaxane using a modified cyclodextrin as a starting material, the use of an axial molecule having a number average molecular weight of 1500 or more is less than that using an axial molecule having a number average molecular weight of less than 1500. The rate rises dramatically. Usually, in the production of polyrotaxane using unmodified cyclodextrin as a starting material, it is considered that the yield decreases as the molecular weight of the axial molecule increases, and synthesis using a modified cyclodextrin with low complexing ability as a starting material As such, the above results are completely contrary to those skilled in the art. In addition, when the number average molecular weight of a linear molecule exceeds 1,000,000, there exists a possibility that solubility may fall and control of the penetration number of a ring component may become difficult.

  The terminal functional group of the linear molecule is not particularly limited as long as it can react with the block group described later to block the end of the linear molecule, but is preferably an amino group, a hydroxyl group, an isocyanate group, At least one selected from the group consisting of a carboxyl group, a vinyl group and an epoxy group is used, and an amino group is particularly preferably used. The terminal functional groups may be the same at both ends, or may be different.

  When the linear molecule has the functional group at the end, the functional group may be used, but it is necessary even when the linear molecule does not have the functional group at the end or has the functional group. Accordingly, the functional group is added to the end of the linear molecule. The addition of the functional group to the end of the linear molecule can be performed by a conventionally known method such as the method described in Nature, 356, 325-327 (1992).

  For example, when the linear molecule is polytetrahydrofuran, it has a hydroxyl group at the end, so the hydroxyl group can be used as it is, or the hydroxyl group can be substituted with an amino group or the like. You can also.

  On the other hand, in this embodiment, a modified cyclodextrin is used as a ring component. Cyclodextrin has a plurality of hydroxyl groups (for example, α-cyclodextrin has 18 hydroxyl groups), and some or all of these hydroxyl groups are substituted with other functional groups. Gives a modified cyclodextrin. Examples of other functional groups include alkoxy groups such as methoxy group and ethoxy group, acyl groups such as acetyl group, hydroxyalkyl groups such as trityl group, nitro group, trimethylsilyl group, and hydroxypropyl group. Among them, the methoxy group is particularly preferable because the methoxy group is small as a functional group and does not inhibit modification of the adjacent hydroxyl group.

  For example, a cyclodextrin in which all hydroxyl groups are substituted with methoxy groups is a permethylated cyclodextrin, and a cyclodextrin in which other hydroxyl groups are substituted with methoxy groups, leaving one or more hydroxyl groups, Partially methylated cyclodextrin. In this specification, both are collectively referred to as “(partial) methylated cyclodextrin”.

  Here, the above partially methylated cyclodextrin is cyclodextrin from the viewpoint of improving the affinity with the axial molecule in order to exert the effect of improving the yield by using the axial molecule having a large molecular weight. In general, 10% or more of all the hydroxyl groups are preferably substituted with methoxy groups, more preferably 20% or more are substituted with methoxy groups, and 30% or more are substituted with methoxy groups. It is particularly preferred.

  In the present embodiment, the modified cyclodextrin is effective when it is a (partially) methylated cyclodextrin, particularly permethylated cyclodextrin, and is further effective when the cyclodextrin is α-cyclodextrin. The modified cyclodextrin can be produced by a conventional method.

  If a linear molecule having a functional group at the end as an axial molecule as described above and a modified cyclodextrin as a ring component are prepared, an inclusion complex is formed by penetrating the axial molecule through the hole of the cyclic molecule of the modified cyclodextrin. To obtain a pseudopolyrotaxane.

  Water, an organic solvent, or a water-organic mixed solvent can be used as a solvent for the reaction of penetrating a shaft molecule into a hole of a cyclic molecule of a modified cyclodextrin to form an inclusion complex, and among them, an organic solvent is used. It is preferable. In general, when an organic solvent is used as a solvent, it is considered that the ring component cannot exhibit the inclusion ability, and this method is used even though a modified cyclodextrin having a low complexing ability is used as the ring component. Then, (pseudo) polyrotaxane is obtained with high yield.

  The organic solvent is preferably at least one selected from the group consisting of aliphatic hydrocarbons, alcohols, amides, sulfoxides, ethers, nitriles and derivatives thereof, among which aliphatic hydrocarbons are more preferable, in particular carbon It is preferable that it is an alkane of several 5-12. The organic solvent may be a hydrophilic solvent or a hydrophobic solvent.

  Specific examples of organic solvents include, as hydrophobic solvents, alkanes such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, and isooctane; alkane derivatives such as 2,2-dimethylbutane and 2-methylpentane. Is preferred. On the other hand, as hydrophilic solvents, alcohols such as methanol, ethanol, propanol, butanol and isopropanol; polyols such as ethylene glycol and diethylene glycol; amides such as dimethylformamide (DMF) and dimethylacetamide; dimethyl sulfoxide (DMSO) and diethyl sulfoxide Examples thereof include sulfoxides; ethers such as diethyl ether and dipropyl ether; nitriles such as acetonitrile and propanenitrile. These organic solvents can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The pseudopolyrotaxane can be produced by dissolving a linear molecule having a functional group at the terminal and a modified cyclodextrin in a solvent and stirring the solution.

  There is no restriction | limiting in particular about the stirring method, It can stir by methods, such as a mechanical stirring process and an ultrasonic treatment, at normal temperature or the temperature controlled appropriately. In particular, in order to obtain a modified pseudopolyrotaxane in a short time, stirring by ultrasonic treatment is efficient and preferable. The stirring time is preferably performed under conditions of several minutes to 1 hour. Although there is no restriction | limiting in particular about the irradiation conditions of an ultrasonic wave, It is preferable to carry out with a frequency of 20-40 kHz.

  After producing the modified pseudopolyrotaxane as described above, the modified pseudopolyrotaxane and the capping agent are mixed to react the modified pseudopolyrotaxane with the capping agent, and the blocking group of the capping agent is reacted at both ends of the axial molecule. Is added (capping) to obtain a modified polyrotaxane.

  The blocking group is not particularly limited as long as the modified cyclodextrin as a ring component can maintain a form skewered by a linear molecule, but preferably a dialkylphenyl group, a dinitrophenyl group, Cyclodextrins, adamantane groups, trityl groups, fluoresceins, pyrenes, anthracenes and the like are appropriately selected.

  The axial molecule and the capping agent may be reacted with each other having functional groups that react with each other, but it is particularly preferable to react with a combination of an isocyanate group and an amino group. That is, as a capping agent, when an amino group having a terminal functional group is selected as an axial molecule, a capping agent having an isocyanate group is selected. It is preferred to use a capping agent having a group. Thereby, even if it does not use other reagents, such as a catalyst, and it does not heat, reaction advances efficiently and for a short time, and the yield of the modification polyrotaxane obtained is also high.

  Examples of the capping agent having an isocyanate group include monoisocyanates such as 3,5-dimethylphenyl isocyanate and 4-tritylphenyl isocyanate. Examples of the capping agent having an amino group include 3,5-dimethylaniline and 4-tritylaniline.

  The amount of capping agent used is preferably equivalent to 30 times, more preferably 2 to 10 times the molar amount of the terminal functional group of the axial molecule.

  In order to react the pseudopolyrotaxane and the capping agent, it is only necessary to stir the mixture of the pseudopolyrotaxane and the capping agent. The pseudopolyrotaxane and the capping agent may be stirred in a solvent or in a solid phase. . For stirring in the solvent, mechanical stirring treatment using a stirring bar, a stirring blade or the like is sufficient. Moreover, it is good to use a mortar, a ball mill, a mixer etc. for the stirring in a solid phase.

  As the solvent, water, an organic solvent, or a water-organic mixed solvent can be used, and among these, it is preferable to use an organic solvent. As the organic solvent, various organic solvents such as tetrahydrofuran, chloroform, and acetone can be used in addition to the organic solvent described above. For example, an isocyanate group used in a capping agent or the like easily reacts with water but does not react with an organic solvent. Therefore, when an organic solvent is used as a solvent, the choice of the capping agent is greatly expanded.

  Further, as the solvent, it is particularly preferable to use the solvent used in the production of the pseudopolyrotaxane as it is. Thereby, the synthesis | combination of a pseudo polyrotaxane and the synthesis | combination of a polyrotaxane can be performed by one pot, Therefore, a polyrotaxane can be manufactured very efficiently.

  Since the modified cyclodextrin has low reactivity with the capping agent, the temperature of the solvent is not particularly limited, and may be room temperature or an appropriately controlled temperature. The reaction time is preferably about 0.1 to 5 hours, particularly 0.5 to 3 hours. Thus, according to this method, a polyrotaxane can be produced in a short time and in a high yield. The purification may be performed by a conventional method.

  Here, the coverage with respect to the axial molecule of the modified cyclodextrin in the present embodiment is 80% or less, preferably 10 to 70%, particularly preferably 30 to 60%. When the coverage is 80% or less, the modified cyclodextrin having an interlock structure can freely move on the axial molecule. For example, those obtained by crosslinking with the obtained polyrotaxane can exhibit extremely excellent flexibility. . In addition, the coverage as used in this specification represents the ratio of the chain | strand part covered with the cyclodextrin among the whole chain | strands of the axial molecule | numerator which comprises a pseudo polyrotaxane or a polyrotaxane.

  The coverage of the modified cyclodextrin with respect to the axial molecule can be adjusted, for example, by changing the reaction temperature during preparation of the pseudopolyrotaxane, the charging ratio of the modified cyclodextrin and the axial polymer, the concentration, and the like. In addition, the calculation method of a coverage is shown in the Example mentioned later.

  As described above, according to the method according to the present embodiment, the production efficiency is good, and the pseudopolyrotaxane and the polyrotaxane can be produced with a significantly high yield. The specific yield is less than 20% in the conventional manufacturing method, but according to the method according to the present embodiment, the yield is dramatically improved to about 60 to 70%.

  Among the modified pseudopolyrotaxanes or modified polyrotaxanes obtained by the above method, in particular, those in which the modified cyclodextrin is a permethylated cyclodextrin are novel modified pseudopolyrotaxanes or modified polyrotaxanes. That is, a modified pseudopolyrotaxane in which a shaft molecule penetrates into a hole of a cyclic molecule of a modified cyclodextrin, the number average molecular weight of the shaft molecule is 1500 or more, and the coverage of the modified cyclodextrin on the shaft molecule is 80%. The modified pseudo-polyrotaxane, in which the modified cyclodextrin is a permethylated cyclodextrin, is a novel modified pseudo-polyrotaxane, and the shaft molecule penetrates through the hole of the cyclic molecule of the modified cyclodextrin, and is attached to both ends of the shaft molecule. A modified polyrotaxane having a blocking group, wherein the number average molecular weight of the axial molecule is 1500 or more, the coverage of the modified cyclodextrin to the axial molecule is 80% or less, and the modified cyclodextrin is a permethylated cyclodextrin Polyrotaxane is a novel modified polyrotaxane.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

[Example 1]
(1) Preparation of linear molecule Polytetrahydrofuran having a hydroxyl group at the end (manufactured by Aldrich, number average molecular weight Mn: 2100) is dissolved in chloroform, tosyl chloride is added, and the catalyst is stirred overnight using pyridine. Went. Thereafter, liquid separation washing with dilute hydrochloric acid and drying under reduced pressure were performed, and the obtained liquid was poured into diethyl ether to cause precipitation. The precipitated solid was collected and dried to obtain tosylated polytetrahydrofuran.

  Next, the tosylated polytetrahydrofuran obtained was dissolved in dimethylformamide, potassium phthalimide was added, and boiling point reflux was performed for 5 hours. The filtrate obtained by filtering the reaction solution was poured into diethyl ether and precipitated, and the precipitated solid was collected and dried to obtain phthalimidized polytetrahydrofuran.

The obtained phthalimidized polytetrahydrofuran was dissolved in ethanol, hydrazine was added, and boiling point reflux was performed for 20 hours. The filtrate obtained by filtering the reaction solution was poured into diethyl ether and precipitated, and the precipitated solid was collected to obtain polytetrahydrofuran having a terminal amino group. As a result of ¹ H-NMR measurement of the resulting polytetrahydrofuran of the terminal amino group, the number average molecular weight Mn was 4100.

(2) Synthesis of modified cyclodextrin Permethylated α-cyclodextrin was obtained by reacting α-cyclodextrin (manufactured by Nacalai Tesque) with sodium hydride and methyl iodide in dimethylformamide.

(3) Synthesis of pseudopolyrotaxane In a solution obtained by dissolving 0.8 g of the permethylated α-cyclodextrin as a ring component obtained above in 2 ml of water, the terminal amino group polytetrahydrofuran obtained as an axial molecule ( 47 mg of number average molecular weight Mn: 4100) was added, ultrasonic waves (frequency: 35 kHz) were irradiated for 20 minutes, and the mixture was allowed to stand overnight at room temperature.

(4) Synthesis of polyrotaxane Thereafter, 58 μl of 3,5-dimethylphenyl isocyanate (manufactured by Aldrich) was added as a capping agent to the above solution, and the mixture was stirred and allowed to react for 1 hour. The obtained reaction solution was poured into diethyl ether and precipitated, and the precipitate was collected. Subsequently, the high molecular weight material was recovered by preparative gel permeation chromatography (developing solvent: CHCl ₃ ) and dried to obtain a modified polyrotaxane. Yield (mg) is shown in Table 1. In addition, FIG. 1 shows a ¹ H-NMR chart of the obtained modified polyrotaxane.

[Example 2]
In the same manner as in Example 1 except that polytetrahydrofuran (Aldrich, number average molecular weight Mn: 2900) is used instead of polytetrahydrofuran (Aldrich, number average molecular weight Mn: 2100) in Example 1, a linear form is used. Molecules were prepared. As a result of ¹ H-NMR measurement of the resulting polytetrahydrofuran of the terminal amino group, the number average molecular weight Mn was 7700.

A modified polyrotaxane was produced in the same manner as in Example 1, except that the terminal amino group polytetrahydrofuran (number average molecular weight Mn: 7700) obtained above was used as the axial molecule. Yield (mg) is shown in Table 1. Moreover, the ¹ H-NMR chart of the obtained modified polyrotaxane is shown in FIG.

Example 3
Under an argon atmosphere, 0.05 ml of trifluoromethanesulfonic anhydride as a polymerization initiator was added to 25 ml of anhydrous tetrahydrofuran and stirred for 15 minutes. Thereafter, the reaction solution was poured into water and precipitated to collect a solid, which was then dried to obtain 2.1 g of polytetrahydrofuran as a white solid. As a result of ¹ H-NMR measurement of the obtained polytetrahydrofuran, the number average molecular weight Mn was 11,000.

Instead of polytetrahydrofuran in Example 1 (manufactured by Aldrich, number average molecular weight Mn: 2100), the same procedure as in Example 1 was used except that polytetrahydrofuran having the number average molecular weight Mn of 11000 obtained above was used. A molecule-like molecule was prepared. As a result of ¹ H-NMR measurement of the resulting polytetrahydrofuran of the terminal amino group, the number average molecular weight Mn was 12000.

A modified polyrotaxane was produced in the same manner as in Example 1, except that the terminal amino group polytetrahydrofuran (number average molecular weight Mn: 12000) obtained above was used as the axial molecule. Yield (mg) is shown in Table 1. Moreover, the ¹ H-NMR chart of the obtained modified polyrotaxane is shown in FIG.

Example 4
A modified polyrotaxane was produced in the same manner as in Example 2 except that isooctane was used in place of water as a solvent. Yield (mg) is shown in Table 1. Further, FIG. 4 shows a ¹ H-NMR chart of the obtained modified polyrotaxane.

[Comparative Example 1]
A modified polyrotaxane was produced in the same manner as in Example 1 except that polytetrahydrofuran having a terminal amino group (Aldrich, Polytetrahydrofuran bis (3-aminopropyl) terminated, number average molecular weight Mn: 1100) was used as the axial molecule. Yield (mg) is shown in Table 1.

[Test Example 1]
From the result of ¹ H-NMR measurement ( ¹ H-NMR chart) of the modified polyrotaxane obtained in Examples and Comparative Examples, 5 ppm of signal A (from protons attached to the first carbon of the glucose ring of cyclodextrin) ) And 1.55 ppm of signal B (derived from polytetrahydrofuran alkyl chain), and the length of about 12 mm of methylated cyclodextrin calculated by the CPK model corresponds to two monomer units of polytetrahydrofuran. Therefore, the coverage θ (%) was calculated by the following formula. The results are shown in Table 1.
Coverage θ (%) = 2 / {(B / 4) / (A / 6)} × 100
A: Integration value of signal A B: Integration value of signal B

[Test Example 2]
The weight of the shaft molecule in the yield (mg) of the modified polyrotaxane is calculated from the integral ratio of the signal derived from the cyclodextrin of ¹ H-NMR and the signal derived from the shaft molecule, and from the ratio with the amount of the charged shaft molecule. The yield (%) based on the axial molecule was calculated. The results are shown in Table 1.

  As can be seen from Table 1, the modified polyrotaxanes of Examples in which the number average molecular weight of the axial molecules was 1500 or more had a very high yield.

  The present invention is useful for producing pseudo-polyrotaxane or polyrotaxane with high yield efficiently. Moreover, the polyrotaxane obtained by this invention can be utilized as a polymer gel which shows the outstanding softness | flexibility by bridge | crosslinking. Moreover, it can utilize as a molecular tube by removing the core substance of a polyrotaxane after bridge | crosslinking the adjacent ring component of a polyrotaxane.

Claims (4)

A modified pseudopolyrotaxane is produced by a reaction of penetrating a shaft molecule into a hole of a cyclic molecule of a modified cyclodextrin to form an inclusion complex, and then the obtained shaft molecule of the modified pseudopolyrotaxane is reacted with a capping agent, In the method for producing a modified polyrotaxane in which a blocking group is added to both ends of an axial molecule,
The modified cyclodextrin is a single type,
The axial molecule is a polyether, polyester or polyorganosiloxane,
The number average molecular weight of the axial molecule is 3000 to 1000000,
The reaction between the modified pseudopolyrotaxane axial molecule and the capping agent is carried out in a solvent ,
A method for producing a modified polyrotaxane, wherein a coverage of the modified cyclodextrin with respect to the axial molecule is 80% or less. The method for producing a modified polyrotaxane according to claim 1 , wherein the modified cyclodextrin is (partially) methylated cyclodextrin. The method for producing a modified polyrotaxane according to claim 2 , wherein the (partial) methylated cyclodextrin is a permethylated cyclodextrin. The method for producing a modified polyrotaxane according to any one of claims 1 to 3 , wherein the axial molecule and the capping agent are reacted with a combination of an isocyanate group and an amino group.

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