WO2013099842A1 - Modified polyrotaxane and method for producing same, and material formed using modified polyrotaxane - Google Patents

Abstract

The present invention provides a modified polyrotaxane having improved solubility and high industrial applicability. The present invention provides a modified polyrotaxane produced by modifying a polyrotaxane, wherein the polyrotaxane is produced by arranging capping groups at both ends of a pseudo polyrotaxane that comprises cyclodextrin (CD) and a linear molecule included in a cavity of the CD in a skewer-like form so that the CD cannot be detached. In the modified polyrotaxane, each of at least some of hydroxy groups contained in the CD is substituted by a first substituent represented by formula (I) (wherein -R represents a group selected from the group consisting of -CH₂-CH₃, -CH₂-O-CH₃, -CH₂-O-CH₂-CH₃, -CH₂-O-CH₂-CH₂-CH₃ and -CH₂-O-CH-(CH₃)₂).

Description

Modified polyrotaxane, method for producing the same, and material formed with modified polyrotaxane

The present invention relates to a modified polyrotaxane in which the cyclic molecule is a cyclodextrin and the hydroxyl group of the cyclodextrin is modified with a specific group.
The present invention also relates to a material formed with the modified polyrotaxane and a method for producing the modified polyrotaxane.

Research and development on polyrotaxane, a representative supramolecule, is actively underway, but there is still little development that specifically focuses on product applications.
In particular, polyrotaxane consisting of polyethylene glycol as a linear molecule, cyclodextrin as a cyclic molecule, and adamantane group as a capping group is soluble only in dimethyl sulfoxide, strong alkaline water, dimethylacetamide / LiCl solution, and ionic liquid. It has become a big issue.

For example, Patent Document 1 discloses that a part of the hydroxyl group of cyclodextrin, which is a cyclic molecule of polyrotaxane, is modified with various modifying groups to increase the water solubility of the modified polyrotaxane, thereby obtaining a hydrogel material.
Non-Patent Document 1 examines the solubility of polyrotaxane in organic solvents with various modifying groups.
Patent Document 2 discloses that the solubility of polyrotaxane in an organic solvent is further enhanced by a combination of an acyl group and a specific modifying group.
In Patent Document 3, a caprolactone group is modified on a cyclodextrin via a hydroxypropyl group. Since the solubility of the polyrotaxane modified with a hydroxypropyl group is improved, it is disclosed that the polyrotaxane is used as an intermediate for modifying the caprolactone group.

WO2005 / 080469. WO2008 / 108411. Japanese Patent No. 4521875.

However, by modifying the hydroxyl group of cyclodextrin with a modifying group, a part of the hydroxyl group disappears and the remaining hydroxyl group decreases. Generally, the higher the degree of modification (the ratio of modification to the entire hydroxyl group), the higher the solubility in the solvent. The active hydroxyl group remaining in the modified polyrotaxane is important for the crosslinking reaction and further modification of the chemical structure, and needs to be sufficiently secured. In the above patent documents and non-patent documents, polyrotaxanes modified with hydroxypropyl groups are disclosed. The hydroxypropyl group has a hydroxyl group, so a sufficient hydroxyl group can be secured in the modified polyrotaxane, but the number of hydrocarbons to increase the affinity with a specific solvent is small, and the solubility is improved at a low modification degree. There is a problem that is insufficient.

In addition, for industrial use, the following problems can be considered to modify the hydroxypropyl group in cyclodextrin using propylene oxide (1,2-epoxypropane) described in Patent Document 3. For example, since 1,2-epoxypropane has a low boiling point (34 ° C.), it evaporates due to reaction heat during the reaction, making it difficult to control the physical properties of the reaction product. In addition, 1,2-epoxypropane is highly volatile and highly toxic, making it difficult to handle in mass production and requiring special storage for storage.

An object of the present invention is to solve the above problems.
Specifically, an object of the present invention is to provide a modified polyrotaxane having improved solubility and high industrial utility.
Moreover, the objective of this invention is providing the material which has the said modified polyrotaxane other than the said objective or in addition to the said objective.
Furthermore, the objective of this invention is providing the manufacturing method of the said modified polyrotaxane other than the said objective or in addition to the said objective.

The inventors have found the following invention.
<1> A modified polyrotaxane obtained by modifying a polyrotaxane in which a blocking group is arranged so that cyclodextrin is not detached at both ends of a pseudopolyrotaxane in which an opening of a cyclodextrin is included in a skewered manner by linear molecules Because
At least a part of the hydroxyl groups of cyclodextrin is represented by the following formula (I) (wherein —R is —CH ₂ —CH ₃ , —CH ₂ —O—CH ₃ , —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —O—CH ₂ —CH ₂ —CH ₃ and —CH ₂ —O—CH— (CH ₃ ) ₂ is at least one first group selected from the group consisting of The modified polyrotaxane is substituted with a first substituent.

<2> In the above <1>, at least a part of the hydroxyl group is further modified by the first substituent, and the following formula (II) (wherein X is a straight chain having 2 to 8 carbon atoms or From a branched alkylene group, a linear or branched alkylene group having 3 to 8 carbon atoms having an acetyl group branch, and a linear or branched alkylene group having 3 to 8 carbon atoms having an ether bond And at least one second group selected from the group consisting of n and 1 to 200).

<3> In the above item <1>, the substitution rate of the first substituent is 0.10 to 0.60, preferably 0, when 1.0 is a state in which all of the hydroxyl groups of the cyclodextrin are substituted. 20 to 0.50, more preferably 0.25 to 0.45.
<4> In the above <1> or <3>, the hydroxyl value of the modified polyrotaxane according to JIS K0070 is 440 to 300 mgKOH / g, preferably 420 to 320 mgKOH / g, more preferably 400 to 330 mgKOH / g. Good.
<5> In the above item <2>, —X— represents — (CH ₂ ) ₃ —, — (CH ₂ ) ₅ —, —CH (CH ₃ ) —CH ₂ —CH ₂ — and — (CH ₂ ) ₂ At least one alkylene group selected from the group consisting of —O— (CH ₂ ) ₂ —, preferably — (CH ₂ ) ₃ —, — (CH ₂ ) ₅ —, —CH (CH ₃ ) —CH ₂ — At least one alkylene group selected from the group consisting of CH ₂ —, more preferably — (CH ₂ ) ₅ — is preferred.

<6> In the above item <2> or <5>, the molecular weight distribution of the modified polyrotaxane is 2.0 or less, preferably 1.8 or less, more preferably 1.6 or less.
<7> A cross-linking material in which the modified polyrotaxane described in <2>, <5> or <6> is included in the cross-linking.
<8> A material formed with the modified polyrotaxane described in <2>, <5> or <6> above.

<9> A method for producing a modified polyrotaxane,
a) a step of preparing a polyrotaxane in which blocking groups are arranged so that cyclodextrin is not detached at both ends of a pseudopolyrotaxane in which an opening of a cyclodextrin is clasped with a linear molecule; and b) At least a part of the hydroxyl groups of cyclodextrin is represented by the following formula (I) (wherein —R is —CH ₂ —CH ₃ , —CH ₂ —O—CH ₃ , —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —O—CH ₂ —CH ₂ —CH ₃ and —CH ₂ —O—CH— (CH ₃ ) _2. Substituting with a group;
The above method.

<10> In the above <9>, the substitution in step b) is selected from the group consisting of at least a part of a hydroxyl group and 1,2-butylene oxide, glycidyl methyl ether, glycidyl ethyl ether, glycidyl propyl ether, and glycidyl isopropyl ether. The reaction is preferably performed by reacting with at least one first compound.
<11> In the above <9> or <10>, the substitution rate of the first substituent is 0.10 to 0.60 when 1.0 is a state in which all the hydroxyl groups of the cyclodextrin are substituted. , Preferably 0.20 to 0.50, more preferably 0.25 to 0.45.
<12> In any one of the above items <9> to <11>, the hydroxyl value of the modified polyrotaxane according to JIS K0070 is 440 to 300 mgKOH / g, preferably 420 to 320 mgKOH / g, more preferably 400 to 330 mgKOH / g. There should be.

<13> In any one of the above items <9> to <12>, c) ring-opening polymerization of the lactone monomer starting from the first substituent, and at least a part of the hydroxyl group is represented by the following formula (II) (formula Wherein X is a linear or branched alkylene group having 2 to 8 carbon atoms, a linear or branched alkylene group having 3 to 8 carbon atoms having an acetyl group branch, and a carbon having an ether bond A second substituent represented by the following formula: at least one second group selected from the group consisting of a linear or branched alkylene group having a number of 3 to 8 and n is 1 to 200) It is preferable to further include a step of substituting.

<14> In step c) of <13> above, the lactone monomer is at least one compound selected from the group consisting of ε-caprolactone, γ-valerolactone, α-methyl-γ-butyrolactone and γ-butyrolactone. Thus, ring-opening polymerization is preferably performed.

According to the present invention, it is possible to provide a modified polyrotaxane having improved solubility and high industrial utility.
Moreover, according to the present invention, a material having the modified polyrotaxane can be provided in addition to or in addition to the above effects.
Furthermore, according to the present invention, a method for producing the modified polyrotaxane can be provided in addition to or in addition to the above effects.

Hereinafter, the invention described in the present application will be described in detail.
<Modified polyrotaxane in which at least a part of the hydroxyl group of cyclodextrin is substituted with the first substituent represented by the above formula (I)>
The present application is a modified polyrotaxane obtained by modifying a polyrotaxane in which a blocking group is arranged so that cyclodextrin is not detached at both ends of a pseudopolyrotaxane in which an opening of a cyclodextrin is clasped with a linear molecule. Wherein the modified polyrotaxane is substituted with at least a part of the hydroxyl groups of the cyclodextrin with the first substituent represented by the above formula (I). “Modified polyrotaxane at least partially substituted with the first substituent represented by the above formula (I)” may be simply abbreviated as “first modified polyrotaxane”.

In the formula (I), —R represents —CH ₂ —CH ₃ , —CH ₂ —O—CH ₃ , —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —O—CH ₂ —CH ₂ —. A group consisting of CH ₃ and —CH ₂ —O—CH— (CH ₃ ) ₂ , preferably —CH ₂ —CH ₃ , —CH ₂ —O—CH ₂ —CH ₃ and —CH ₂ —O—CH— ( CH ₃ ) is at least one first group selected from the group consisting of ₂ .

The substitution rate of the first substituent is 0.10 to 0.60, preferably 0.20 to 0.50, and more preferably, when 1.0 is a state in which all the hydroxyl groups of cyclodextrin are substituted. Is preferably 0.25 to 0.45.
If it is the said range, it exists in the tendency for the solubility with respect to the solvent of a 1st modification polyrotaxane, and compatibility with another material to improve, and it exists in the tendency for the yield in manufacture of a 1st modification polyrotaxane to become high. . In particular, the lower limit tends to be related to the solubility of the first modified polyrotaxane in the solvent and compatibility with other materials, and the upper limit tends to be related to the yield in the production of the first modified polyrotaxane. is there.

The substitution rate of the first substituent can be obtained by measuring ¹ H-NMR of the ^first modified polyrotaxane (and polyrotaxane before modification if necessary).
Specifically, “C1 proton (—O—CH ^* —O—) and hydroxyl group (glucose of the first substituent and hydroxyl group derived from cyclodextrin) derived from glucose of the cyclodextrin in the first modified polyrotaxane” Measured integrated amount of ¹ H peak derived from “proton derived” (A: abbreviated as “actual measured integrated amount of proton derived from hydroxyl group, etc.”) and measured integrated amount of ¹ H peak derived from “proton unique to the first substituent” (B: “actual proton integration amount peculiar to the first substituent”).

The case where the cyclodextrin is α-cyclodextrin (hereinafter sometimes abbreviated as “α-CD”) and the first substituent R is an ethyl group (—CH ₂ CH ^* ₃ ) will be described as an example. .
“Proton peculiar to the first substituent” focuses on “the H ^{* in which} R of the first substituent is an ethyl group (—CH ₂ CH ^* ₃ )”. This “H ^* ” peak appears around 0.87 ppm. When all 18 hydroxyl groups of “α-CD” are substituted with the first substituent, the number of “H ^* ” is (18 × 3). When replaced with a certain replacement rate instead of all, the number of “H ^* ” is (18 × 3 × replacement rate).

On the other hand, “C1 proton derived from glucose (—O—CH ^* —O—) and hydroxyl group (hydroxyl group of the first substituent and hydroxyl group derived from cyclodextrin) in the first modified polyrotaxane” "Appears around 4 to 6 ppm. The number of protons is 24 regardless of the substitution rate of the first substituent.

From this, the ratio of A: “actually accumulated amount of protons derived from hydroxyl group etc.” and B: “actually accumulated amount of protons unique to the first substituent” is {24 / (18 × 3 × substitution rate)}.
In short, A / B = {24 / (18 × 3 × replacement rate)}, from which the replacement rate can be obtained.
In the above description, the case where cyclodextrin is α-CD and R of the first substituent is an ethyl group (—CH ₂ CH ₃ ) has been described, but in other cases as well, The substitution rate of one substituent can be determined.

The first modified polyrotaxane may have a hydroxyl value according to JIS K0070 of 440 to 300 mgKOH / g, preferably 420 to 320 mgKOH / g, more preferably 400 to 330 mgKOH / g.
When the hydroxyl value according to JIS K0070 is in the above range, the first modified polyrotaxane can be reacted with other materials, so that it becomes soluble in various solvents and at the same time, sufficient hydroxyl groups as reactive groups are secured. It tends to be advantageous in that it allows a wide range of material designs. Examples of reactions with other materials include, but are not limited to, curing reactions (crosslinking reactions) with other materials, new modifications by reaction with other functional functional groups, and the like. .

The cyclodextrin in the first modified polyrotaxane may have a substituent other than the first substituent.
Substituents other than the first substituent include -O-acyl groups such as -O-acetyl group and -O-propionyl group; alkyloxy groups such as methoxy group, ethoxy group and propyloxy group; butylcarbamoyl group and cyclohexyl Alkyl or arylcarbamoyl groups such as carbamoyl group, phenylethylcarbamoyl group, acryloyloxyethylcarbamoyl group, methacryloyloxyethylcarbamoyl group; polyalkyloxy groups such as polyoxyethylene group, polyoxypropylene group; carboxylic acid group, amino group, etc. Although the substituent which has this reactive group can be mentioned, it is not limited to these.

<Modified polyrotaxane in which at least a part of the hydroxyl group of cyclodextrin is substituted with the second substituent represented by the above formula (II)>
Further, the present application relates to a modified polyrotaxane in which at least a part of hydroxyl groups of cyclodextrin is substituted with the second substituent represented by the above formula (II) (in the present application, “at least the hydroxyl groups of cyclodextrin have” “Modified polyrotaxane partially substituted with the second substituent represented by the above formula (II)” may be simply abbreviated as “second modified polyrotaxane”.

In the formula (II), X represents a linear or branched alkylene group having 2 to 8 carbon atoms, a linear or branched alkylene group having 3 to 8 carbon atoms having an acetyl group branch, and ether It is at least one second group selected from the group consisting of a linear or branched alkylene group having 3 to 8 carbon atoms having a bond.

Examples of the linear or branched alkylene group having 2 to 8 carbon atoms include, for example, — (CH ₂ ) ₃ —, — (CH ₂ ) ₅ —, —CH (CH ₃ ) —CH ₂ —CH ₂ —. , — (CH ₂ ) ₃ —CH (CH ₃ ) —, but is not limited thereto.
Examples of the linear or branched alkylene group having 3 to 8 carbon atoms having an acetyl group branch include —CH (CH ₃ CO) — (CH ₂ ) ₂ —, but are not limited thereto. Not.
Examples of the linear or branched alkylene group having 3 to 8 carbon atoms having an ether bond include — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, but are not limited thereto. Not.

—X— represents — (CH ₂ ) ₃ —, — (CH ₂ ) ₅ —, —CH (CH ₃ ) —CH ₂ —CH ₂ — and — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ — At least one alkylene group selected from the group consisting of: preferably selected from the group consisting of — (CH ₂ ) ₃ —, — (CH ₂ ) ₅ —, —CH (CH ₃ ) —CH ₂ —CH ₂ —. It may be at least one alkylene group, more preferably — (CH ₂ ) ₅ —.

R has the same definition as above.
n is 1 to 200, preferably 2 to 100, more preferably 3 to 50. Note that n is an integer in terms of structure, but in practice, it is often produced by ring-opening polymerization described later. In this case, the ring-opening polymerization has dispersibility, and thus is not limited to an integer. n will be described in detail in the second method for producing a modified polyrotaxane.

Since the second substituent represented by the formula (II) is a group obtained by further modifying the first substituent, the second modified polyrotaxane can also be obtained from the first modified polyrotaxane. Alternatively, the second modified polyrotaxane can be obtained, for example, by directly replacing the second substituent with the hydroxyl group of cyclodextrin without passing through the first modified polyrotaxane.

The second modified polyrotaxane has only to have the second substituent, whether it has only the second substituent, the first and second substituents, You may have substituents other than a 2nd substituent.
Examples of the substituent other than the first and second substituents include, but are not limited to, those described above as the substituent other than the first substituent.

The second modified polyrotaxane has a molecular weight distribution Mw / Mn of 2.0 or less, preferably 1.8 or less, more preferably 1.6 or less.
In the present application, the molecular weight distribution Mw / Mn can be measured by gel permeation chromatography (GPC).

In addition to the same reason as the first modified polyrotaxane, the second modified polyrotaxane has a hydroxyl value according to JIS K0070 of 50 to 120 mgKOH / g, from the viewpoint of securing excellent viscoelastic properties after material processing. 60 to 100 mgKOH / g is preferable, and 65 to 90 mgKOH / g is more preferable.

<Components of Modified Polyrotaxane>
Hereinafter, components common to the first and second modified polyrotaxanes will be described.
<< cyclodextrin >>
In the present application, the cyclodextrin depends on the selection of the linear molecule, the properties required for the modified polyrotaxane, and the like, and examples thereof include α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.
Cyclodextrin has a hydroxyl group, but may have other groups. Examples of the “other group” include, but are not limited to, the groups listed as “substituents other than the first substituent”.

<< Linear molecule >>
The polyrotaxane linear molecule of the present invention is not particularly limited as long as it can be included in a skewered manner in the opening of the cyclodextrin used.
For example, as linear molecules, polyvinyl alcohol, polyvinyl pyrrolidone, poly (meth) acrylic acid, cellulosic resins (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl Polyolefin resins such as acetal resins, polyvinyl methyl ether, polyamines, polyethyleneimine, casein, gelatin, starch, and / or copolymers thereof, polyethylene, polypropylene, and copolymers of other olefin monomers; Polyester resins, polyvinyl chloride resins, polystyrene resins such as polystyrene and acrylonitrile-styrene copolymer resins, polymethyl Acrylic resin such as tacrylate, (meth) acrylic acid ester copolymer, acrylonitrile-methyl acrylate copolymer resin, polycarbonate resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, etc .; and derivatives or Modified products, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polyimides, polydienes such as polyisoprene and polybutadiene, polysiloxanes such as polydimethylsiloxane , Polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and It may be selected from the group consisting of these derivatives. For example, it may be selected from the group consisting of polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol and polyvinyl methyl ether. Particularly preferred is polyethylene glycol.

The linear molecule may have a weight average molecular weight of 3,000 or more, preferably 5,000 to 100,000, more preferably 10,000 to 50,000.
In the modified polyrotaxane of the present application, the combination of (cyclodextrin, linear molecule) is preferably (derived from α-cyclodextrin, derived from polyethylene glycol).

<< Blocking group >>
The blocking group of the modified polyrotaxane of the present application is not particularly limited as long as it is a group that is arranged at both ends of the pseudopolyrotaxane and acts so that the cyclodextrin used does not leave.
For example, as a blocking group, dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, pyrenes, substituted benzenes (substituents are alkyl, alkyloxy, hydroxy, Examples include, but are not limited to, halogen, cyano, sulfonyl, carboxyl, amino, phenyl, etc. One or more substituents may be present), optionally substituted polynuclear aromatics (substituted) Examples of the group include, but are not limited to, the same as described above, and one or more substituents may be present.) And a group consisting of steroids. It is preferably selected from the group consisting of dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, and pyrenes, more preferably adamantane groups or cyclodextrins. It should be similar.

The present application discloses a material formed with a second modified polyrotaxane, and a cross-linking material in which the second modified polyrotaxane is included in the cross-linking.
The material formed with the second modified polyrotaxane means that the material contains the second modified polyrotaxane. The second modified polyrotaxane may or may not have bonds and / or crosslinks with other substances contained in the material. In addition, the 2nd modification polyrotaxane can exhibit the characteristic of this 2nd modification polyrotaxane by couple | bonding with another substance in a material. Since the second modified polyrotaxane bonded (crosslinked) can move along the cyclodextrin molecule, the stress can be uniformly distributed. Since the crosslinking point is movable, the stretchability of the material can be maintained even when the crosslinking density is increased. Utilizing such characteristics, for example, it can be used for paint (coating) materials, actuator materials, organic dispersion type electroluminescent materials, binders for heat conducting materials, and the like. In addition, because of its excellent flexibility and strength, it can be expected to be applied particularly to low driving pressure actuator materials and other piezoelectric elements. In addition, electrical insulation materials, electrical / electronic component materials, optical materials, friction control materials, medical biomaterials, machinery / automotive materials, building materials, anti-vibration / vibration isolation materials, damping materials, adhesives / adhesives, Chip-shaped anti-vibration members, electric device vibration-damping pads, shoe soles, sports equipment, clothing and sports wear cushioning materials, architectural cushioning materials, soundproofing materials, automobiles, electrical appliances, furniture and other paints and coating materials, Electronic materials such as interior materials, printing plate materials, dental hygiene materials, friction materials such as machinery and automatic companies, sealing materials, waterproofing materials, insulating materials, sealing materials, heat transfer materials, conductive material binders, cosmetics Applications to materials, rheology control agents, fiber materials, medical biomaterials, rubber modifiers, etc. are also conceivable.

The cross-linking material in which the second modified polyrotaxane is included in the cross-linking includes not only the second modified polyrotaxane in the material but also the second modified polyrotaxane is cross-linked and / or It means a material in which a substance other than the second modified polyrotaxane and the second modified polyrotaxane are crosslinked.
The cross-linking method depends on the second modified polyrotaxane to be used and, if present, a substance other than the second modified polyrotaxane to be used. However, the cross-linking method is the same as the general thermosetting resin cross-linking method. can do. For example, a method of adding a cross-linking agent to a material, applying it on a substrate and heating and cross-linking, a method of injecting it into a mold and heating and cross-linking, a method of applying pressure and heating and cross-linking can be mentioned. It is not limited to.

Moreover, although the bridge | crosslinking formation material in which a 2nd modification polyrotaxane is contained in bridge | crosslinking can be manufactured with the following method, it is not limited to this.
That is, E- (1) providing a second modified polyrotaxane;
E- (2) preparing a crosslinking agent; and E- (3) reacting the second modified polyrotaxane with the crosslinking agent;
By having this, a cross-linking material can be obtained.

In step E- (1), a polymer other than the second modified polyrotaxane may be mixed with the second modified polyrotaxane. In addition, the second modified polyrotaxane or a polymer other than the second modified polyrotaxane and the second modified polyrotaxane may be dissolved in a solvent.

As polymers other than the second modified polyrotaxane, polyethers such as polyethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polypropylene glycol, polypropylene glycol monobutyl ether, polytetramethylene glycol; polycaprolactone, hydroxylated polycaprolactone at one end Polyesters such as polylactide; polysiloxanes such as polydimethylsiloxane and hydroxylated polydimethylsiloxane at one end; polycarbonates such as polycarbonate and hydroxylated polycarbonate at one end; polyacrylic acid, polymethylacrylate, polymethylmethacrylate, etc. Polyenes such as polybutadiene and polyisoprene; polystyrene; Polyamide; polyimides; polyphenylene oxide; although their copolymers include, but are not limited to.

As a solvent used in step E- (1), acetates such as toluene, xylene, ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and cyclohexanone; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; methyl cellosolve, Examples include, but are not limited to, cellosolves such as ethyl cellosolve and cellosolve acetate; dimethylacetamide, dimethylformamide, dimethylsulfoxide, and mixed solvents thereof.

As a crosslinking agent in step E- (2)
(I) using an existing cross-linking agent (such as a polyfunctional isocyanate compound),
(Ii) using a prepolymer, or (iii) using the above (i) and (ii) in combination,
be able to.

As an example of the above (i) crosslinking agent, polyfunctional isocyanate is preferable. Examples include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane isocyanate, tetramethylxylene diisocyanate. And a multimer of these isocyanates: adduct, burette, isocyanurate, uretidinedione, and the like, but are not limited thereto.

The prepolymer (ii) can generally be produced by the following method. A cross-linking agent (prepolymer) having as a main component a polymer having an isocyanate group can be produced by reacting a hydroxyl group of the polyol with an equivalent or more polyfunctional isocyanate compound. This prepolymer may be blended with the second modified polyrotaxane and / or a polymer other than the second modified polyrotaxane as it is.
Further, the isocyanate group may be protected (blocked) by reacting with a compound having active hydrogen in the isocyanate group of the prepolymer, and a block prepolymer may be obtained. By making it into a block prepolymer, it is deprotected when heated to a specific temperature, and an isocyanate group can be regenerated. By using a block prepolymer, a one-component thermosetting polyrotaxane-containing composition having excellent storage stability can be provided. The reaction temperature (crosslinking temperature) can also be controlled by the type of compound having active hydrogen. A catalyst is preferably used for the deprotection reaction.

Examples of compounds having active hydrogen include ε-caprolactam, 1,2-pyrazole, butanone oxime, 1,2,4-triazole, diisopropylamine, 3,5-dimethylpyrazole, diethyl malonate, dimethyl malonate, acetoacetic acid It may be selected from the group consisting of methyl, ethyl acetoacetate, and N, N′-diphenylformamidine. Preferred is ε-caprolactam, 3,5-dimethylpyrazole or butanone oxime, and more preferred is ε-caprolactam or 3,5-dimethylpyrazole.

Dibutyltin dilaurate, dioctyltin dilaurate, tri (acetate) butyltin, di (acetate) dibutyltin, acetate tributyltin, methoxytributyltin, tri (2-ethylhexanoate) Butyltin, bis (2-ethylhexanoate) dibutyltin, tri (laurate) butyltin, di (octanoate) dibutyltin, tri (octanoate) butyltin, dibutyltin oxide, monobutyltin hydroxide oxide, 2-ethylhexane Tin-based catalysts such as tin oxide; triethylenediamine, triethylamine, N, N, N ', N'-tetramethylpropylenediamine, N, N, N', N'-tetrakis (2-hydroxypropyl) ethylenediamine, N-methyl Morpholine, 1,2-dimethylimidazole, 1,5-diazabicyclo (4,3,0) Nonene-5, 1,8-diazabicyclo (5,4,0) -undecene-7 (hereinafter abbreviated as DBU), borane salts of these amine catalysts, DBU phenol salts, DBU octylates, DBU carbonates, etc. Various amine salt catalysts; carboxylates such as magnesium naphthenate, lead naphthenate and potassium acetate; trialkylphosphines such as triethylphosphine and tribenzylphosphine; alkoxides of alkali metals such as sodium methoxide; zinc-based organic metals Although a catalyst etc. can be mentioned, it is not limited to this.

Examples of the polyol include polyethers, polyesters, polysiloxanes, polycarbonates, poly (meth) acrylates or polyenes, copolymers thereof, or mixtures thereof. More specifically, polyethylene glycol diol, polyethylene glycol dicarboxylic acid terminal, polyethylene glycol dithiolic acid terminal, polypropylene diol, polytetrahydrofuran, poly (tetrahydrofuran) bis (3-aminopropyl) terminal, polypropylene glycol bis (2-aminopropyl ether) ), Glycerol propoxylate, glycerol tris [poly (propylene glycol) amino terminus], polyethers such as pentaerythritol ethoxylate, pentaerythritol propoxylate; poly (ethylene adipate), poly (1,3-propylene adipate) diol terminus Polyesters such as poly (1,4-butylene adipate) diol ends, polylactones; modified polybutadiene, modified polymers Polyenes such as isoprene; polydimethylsiloxane disilanol end, polydimethylsiloxane hydrogenated end, polydimethylsiloxane bis (aminopropyl) end, polydimethylsiloxane diglycidyl ether end, polydimethylsiloxane dicarbinol end, polydimethylsiloxane di Examples thereof include, but are not limited to, siloxanes having vinyl ends, polydimethylsiloxane dicarboxylic acid ends, and the like; polyalkylene carbonate diols having 1,5-pentanediol, 1,6-hexanediol, and the like as components. In particular, the polymer sites may be polyethers or polycarbonates.

As said (ii) polyfunctional isocyanate compound, the same thing as the polyfunctional isocyanate of said (i) can be used.
Before the step E- (3), an antioxidant, an antibacterial / bacterial agent, a UV absorber, a viscosity modifier, a plasticizer, a surfactant, fine particles, and the like may be added.
Examples of antioxidants include phenolic antioxidants, polyphenolic antioxidants, sulfur antioxidants, phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, and phosphorus antioxidants. Although it can, it is not limited to these.
Antibacterial / bacterial agents include, but are not limited to, silver, zinc, copper compounds or complexes and their ions; organosilicon compounds; organophosphorus compounds.

As UV absorbers, 2-dimethylhexyl paradimethylaminobenzoate, 2-ethylhexyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octylbenzophenone, 2- (2′-hydroxy-5′-t- Butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, 2-ethylhexyl paramethoxycinnamate, isopropyl paramethoxycinnamate, ethylhexyl methoxycinnamate, methoxycinnamate Although octyl acid etc. can be mentioned, it is not limited to these.
Examples of the viscosity modifier include, but are not limited to, carboxyvinyl polymer, propylene glycol alginate, ethyl cellulose, sodium carboxymethyl cellulose, sodium polyacrylate, and the like.

Nonionic surfactants such as polyoxyethylene (8) octylphenyl ether, sorbitan polyoxyethylene trioleate, sorbitan polyoxyethylene monostearate as surfactants: sodium dodecyl sulfate, sodium dodecyl sulfonate, dodecyl sulfate Examples include, but are not limited to, ionic surfactants such as triethanolamine, dodecyltrimethylammonium salt, and dodecylpyridinium chloride.
Examples of the fine particles include silica; alumina, magnesium oxide, zinc oxide, diamond, silicon nitride, titanium dioxide, barium titanate, strontium titanate, zeolite, talc, calcium carbonate, clay, polymer fine particles, and the like. It is not limited.

In the step E- (3), reaction conditions differ depending on the presence or absence of a solvent, the type of solvent, the type of crosslinking agent, and the like. For example, when polyfunctional isocyanate or prepolymer is used, the reaction temperature can be from room temperature to 150 ° C. and normal pressure. When a block prepolymer is used, it can be deblocked and performed at a temperature equal to or higher than the temperature at which the isocyanate group is regenerated, for example, 80 ° C. to 200 ° C., at normal pressure or under pressure.

<Method for producing first modified polyrotaxane>
Said 1st modified polyrotaxane can be manufactured as follows.
That is,
a) a step of preparing a polyrotaxane in which blocking groups are arranged so that cyclodextrin is not detached at both ends of a pseudopolyrotaxane in which an opening of a cyclodextrin is clasped with a linear molecule; and b) A step of substituting at least a part of the hydroxyl group of cyclodextrin with the first substituent represented by the above formula (I);
By having this, the first modified polyrotaxane can be produced.
The terms such as cyclodextrin, linear molecule, blocking group, and first substituent have the same definitions as above.

In the above method, the step b) is preferably provided after the step a).
The step a) is a step for preparing a polyrotaxane. This step can be obtained from WO2005 / 052026.

The step b) preferably has the following steps.
b) -1) a step of dissolving polyrotaxane in a suitable solvent;
b) -2) a step of adding a compound having an epoxy group to react and replacing with a first substituent; and b) -3) a step of purifying and separating the reaction product.

Although depending on the polyrotaxane used as the solvent in step b) -1), dimethyl sulfoxide, dimethylacetamide, a solvent composed of dimethylformamide and a LiCl salt, a sodium hydroxide aqueous solution, and the like can be mentioned, but not limited thereto.

Examples of the compound having an epoxy group in step b) -2) include, but are not limited to, 1,2-butylene oxide, glycidyl methyl ether, glycidyl ethyl ether, glycidyl propyl ether, and glycidyl isopropyl ether.
As a catalyst for the step b) -2), a base such as triethylamine, diethylamine, pyridine, diisopropylethylamine, dimethylaminopyridine or the like can be used.
The conditions of the step b) -2) depend on the polyrotaxane used, the solvent used, the compound having an epoxy group used, and the like, and examples include conditions of room temperature to 150 ° C. for 1 hour to 24 hours. However, it is not limited to these.

Step b) -3) is a step for purifying and separating the reaction product. Methods such as a reprecipitation method in which the reaction solution is poured into a poor solvent for precipitation and a method of removing impurities using a dialysis membrane can be used. Centrifugation, shelf drying, spray drying (eg, pressure nozzle, two-fluid nozzle, four-fluid nozzle, ultrasonic nozzle method, rotating disk method, etc.), thin-film drying of the purified first modified polyrotaxane It can be dried by a method such as freeze-drying (eg, a method using a drum dryer or a centrifugal thin film dryer).

In the first modified polyrotaxane obtained, the substitution rate of the first substituent and the hydroxyl value in accordance with JIS K0070 are preferably in the above-mentioned ranges.

<Method for producing second modified polyrotaxane>
The second modified polyrotaxane can be obtained by further modifying the first modified polyrotaxane obtained by the above production method.
That is, after the a) step and b) step,
c) ring-opening polymerization of the lactone monomer from the first substituent as a starting point, and further comprising the step of substituting at least part of the hydroxyl group with the second substituent represented by the above formula (II), A second modified polyrotaxane can be obtained.

The second substituent has the same definition as above.
Note that n has the definition as described above. n is an integer in structure, but is not limited to an integer because it is produced by ring-opening polymerization of a lactone monomer and the ring-opening polymerization has dispersibility. Next, the calculation method of n will be described by taking as an example the case where ε-caprolactone monomer is used as the lactone monomer and hydroxybutyl group is used as the first substituent.

Using ε-caprolactone monomer, ring-opening polymerization is performed on the hydroxyl group of the first substituent. The consumption of the monomer used for the reaction is confirmed by gas chromatography (GC) (for example, GC-2014, Shimadzu Corporation, column CBP1-W12-100 used). Monomer consumption is almost identical to the supply (almost all reacts). Therefore, the value of [monomer] / [OH] in the polyrotaxane grafted with polycaprolactone, which is the second modified polyrotaxane, can be calculated, and the value is taken as an average n. Here, [OH] is a calculated value of [OH] of the hydroxybutylated polyrotaxane, and the inclusion rate of polyrotaxane (0.25) calculated by ¹ H-NMR measurement and the substitution rate of hydroxybutyl group (0 .26) (see Example 1 below). In the above example, if 1 g of hydroxybutyl group-modified polyrotaxane is used and 4.5 g of ε-caprolactone is used and all is consumed, n = (4.5 / 114.1 * 1000) / 10 .8 = 3.7.

The step c) preferably includes the following steps.
c) -1) a step of dissolving the first modified polyrotaxane in the lactone monomer; and c) -2) a step of initiating and growing the polymerization reaction.

In step c) -1), a solvent other than the lactone monomer may or may not be used.
When a solvent is used, examples of the solvent include acetates such as toluene, xylene, ethyl acetate, and butyl acetate; ketones such as methyl ethyl ketone and cyclohexanone; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; dimethylacetamide, dimethylformamide , Dimethyl sulfoxide, a mixed solvent thereof and the like, but are not limited thereto.

Lactone monomers include 4-membered ring lactones such as β-propiolactone and β-methylpropiolactone; γ-butyrolactone, γ-hexanolactone, γ-heptanolactone, γ-octanolactone, α-heptyl-γ 5-membered ring lactones such as -butyrolactone, α-methylene-γ-butyrolactone, α, α-dimethyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, α-methylene-γ-butyrolactone; δ- Examples thereof include 6-membered ring lactones such as valerolactone, δ-hexanolactone, and δ-octanolactone; 7-membered ring lactones such as ε-caprolactone; lactide and 1,5-dioxepan-2-one. It is not limited to.
The lactone monomer is preferably at least one compound selected from the group consisting of ε-caprolactone, γ-valerolactone, α-methyl-γ-butyrolactone, and γ-butyrolactone.

C) In step 1), dissolution may be performed by heating. Since moisture in the material may lower the purity in this step, there may be provided a step of removing residual moisture in the first modified polyrotaxane as necessary before or after step c) -1). Good. For example, a method of previously drying the first modified polyrotaxane to remove residual moisture, a method of drying the composition after dissolving in the monomer under a stream of dry air or nitrogen, and removing residual moisture, etc. It is not limited to these.

The step c) -2) depends on the first modified polyrotaxane used, the solvent used, and the monomer used, but can be carried out at 80 ° C. to 160 ° C.
The pressure in the reaction is not particularly limited, but it is usually good to carry out at atmospheric pressure.

Monomer polymerization is preferably carried out in the presence of a catalyst. Examples of the catalyst include dibutyltin dilaurate, dioctyltin dilaurate, tri (acetate) butyltin, di (acetate) dibutyltin, acetate tributyltin, methoxytributyltin, tri (2-ethylhexanoate) butyltin, bis ( Tin such as 2-ethylhexanoate) dibutyltin, tri (laurate) butyltin, di (octanoate) dibutyltin, tri (octanoate) butyltin, dibutyltin oxide, monobutyltin hydroxide oxide, tin 2-ethylhexanoate Examples thereof include, but are not limited to, system catalysts, titanium catalysts such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, and titanium tribromide, molybdenum acetate, zirconium acetate, and tungsten acetate.

The reaction product may be recovered without solvent. It may be dissolved in another resin and recovered as a mixture. You may melt | dissolve in a suitable solvent and collect | recover as a solution.
EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to a present Example.

<Preparation of polyrotaxane>
Linear molecule: polyethylene glycol (weight average molecular weight: 35,000), cyclic molecule: α-cyclodextrin (hereinafter sometimes simply referred to as “α-CD”), blocking group: polyrotaxane comprising an adamantaneamine group ( Hereinafter, it may be simply abbreviated as “APR”), and was produced by the method described in WO2005 / 052026. The inclusion ratio of APR calculated by ¹ H-NMR measurement (400 MHz JEOL JNM-AL400 (manufactured by JEOL Ltd.). Hereinafter, ¹ H-NMR measurement is by this apparatus) is 0.25. The inclusion rate was obtained by assuming that the amount of α-CD included to the maximum when α-CD was included in a skewered manner with polyethylene glycol (Macromolecules 1993, 26, 5698-5703). (Note that the entire contents of this document are incorporated herein). The calculated hydroxyl amount of APR is 13.3 mmol / g.

<Preparation of First Modified Polyrotaxane BAPR1>
100 ml of 1.5N NaOH aqueous solution was put into the reaction vessel, and 10 g of APR was dissolved. While maintaining the reaction solution at room temperature (about 20 ° C.), 20 g (0.28 mol) of butylene oxide was added dropwise over 20 minutes, followed by stirring for 20 hours. The reaction solution was neutralized with 6N hydrochloric acid. This solution was dialyzed with a dialysis tube (fraction molecular weight: 12,000) for 48 hours under running tap water. Further, it was performed twice in purified water for 3 hours. The yield of hydroxybutylated APR1 (hereinafter, “hydroxybutylated APR” may be simply abbreviated as “BAPR”) obtained by lyophilization was 12 g.
By GPC, the weight average molecular weight Mw was 150,000, and the molecular weight distribution Mw / Mn was 1.2.

The substitution rate of the hydroxybutyl group was measured and determined by the above-described method, specifically using ¹ H-NMR. The C1 proton of α-CD glucose appearing at 4 to 6 ppm and the proton integrated amount of hydroxyl group (derived from 2-hydroxybutyl and α-CD) of the modified polyrotaxane were 24.0 and appeared at 0.87 ppm 2 Since the actual integrated amount of the peak derived from —CH _{3 of the} —hydroxybutyl group is 14.0, (3 × 18 × substitution rate) /24=14.0/24.0. From this, the substitution rate was 0.26. The calculated [OH] is 10.8 mmol / g.

In the present application, GPC was measured under the following conditions. Using TOSOH HLC-8220 GPC apparatus, column: TSK guard column Super AW-H and TSKgel Super AWM-H (two-linked), eluent: dimethyl sulfoxide / 0.01 M LiBr, column oven: 50 ° C., flow rate: 0 0.5 ml / min, sample concentration: about 0.2 wt / vol%, injection amount: 20 μl, pretreatment: filtration through a 0.2 μm filter, standard molecular weight: PEO (polyethylene oxide).
¹ H-NMR, (DMSO-d ⁶ , 400 MHz), δ (ppm) 0.87 (t, 14.0H), 1.27 (broad, 4.7H), 1.44 (broad, 4.7H), 3.0-4.0 (m, 115H) , 4.0-6.0 (m, 24.0H).

<Preparation of First Modified Polyrotaxane BAPR2>
In Example 1, 12.1 g of BAPR2 was synthesized in the same manner as in Example 1 except that the amount of butylene oxide was changed to 30 g (0.42 mol).
By GPC, the weight average molecular weight Mw was 154,000, and the molecular weight distribution Mw / Mn was 1.2. The substitution rate of the hydroxybutyl group was measured by ¹ H-NMR by the above-described method, specifically in substantially the same manner as in Example 1, and found to be 0.33. The calculated [OH] is 10.3 mmol / g. In addition, the hydroxyl value according to JIS K0070 was 400 mgKOH / g.
¹ H-NMR, (DMSO-d ⁶ , 400 MHz), δ (ppm) 0.87 (t, 17.8H), 1.27 (broad, 5.9H), 1.44 (broad, 5.9H), 3.0-4.0 (m, 120H) , 4.0-6.0 (m, 24.0H).

<Preparation of First Modified Polyrotaxane BAPR3>
In Example 1, 11.8 g of BAPR3 was synthesized in the same manner as in Example 1 except that the amount of butylene oxide was changed to 30 g (0.42 mol) and the amount of 1.5N NaOH aqueous solution was changed to 50 ml.
By GPC, the weight average molecular weight Mw was 180,000, and the molecular weight distribution Mw / Mn was 1.2. The substitution rate of hydroxybutyl group was measured by ¹ H-NMR by the method described above and found to be 0.35. The calculated [OH] is 10.1 mmol / g.
¹ H-NMR, (DMSO-d ⁶ , 400 MHz), δ (ppm) 0.87 (t, 18.9H), 1.27 (broad, 6.3H), 1.44 (broad, 6.3H), 3.0-4.0 (m, 122H) , 4.0-6.0 (m, 24.0H).

<Preparation of First Modified Polyrotaxane BAPR4>
In Example 2, 12.0 g of BAPR4 was synthesized in the same manner as in Example 2 except that the reaction temperature was changed to 50 ° C. and the reaction time was changed to 5 hours.
By GPC, the weight average molecular weight Mw was 185,000, and the molecular weight distribution Mw / Mn was 1.2. In GPC measurement, since the change disappeared after 3 hours or more, 3.5 hours was set as the reaction end point. The substitution rate of hydroxybutyl group was measured by ¹ H-NMR and found to be 0.40. The calculated [OH] is 9.8 mmol / g.
¹ H-NMR, (DMSO-d ⁶ , 400 MHz), δ (ppm) 0.87 (t, 21.6 H), 1.27 (broad, 7.2 H), 1.44 (broad, 7.2 H), 3.0-4.0 (m, 125 H) , 4.0-6.0 (m, 24.0H).

<Preparation of First Modified Polyrotaxane EGAPR1>
50 ml of 1.5N NaOH aqueous solution was put into the reaction vessel, and 10 g of APR was dissolved. While maintaining the reaction solution at room temperature (20 ° C.), 20 g (0.20 mol) of glycidyl ethyl ether was added dropwise over 20 minutes, followed by stirring for 20 hours. The reaction solution was neutralized with 6N hydrochloric acid. This solution was dialyzed with a dialysis tube (fraction molecular weight: 12,000) for 48 hours under running tap water. Further, it was performed twice in purified water for 3 hours. Lyophilization was performed to obtain hydroxypropyl ethyl etherified APR1 (hereinafter, “hydroxypropyl ethyl etherified APR” may be simply abbreviated as “EGAPR”). The yield of EGAPR1 was 12 g.
By GPC, the weight average molecular weight Mw was 158,000, and the molecular weight distribution Mw / Mn was 1.3. The substitution rate of the hydroxypropyl ethyl ether group was measured by ¹ H-NMR and found to be 0.35. The calculated [OH] is 9.1 mmol / g.
¹ H-NMR, (DMSO-d ⁶ , 400 MHz), δ (ppm) 1.10 (t, 18.8H), 3.0-4.0 (m, 157H), 4.0-6.0 (m, 24.0H).

<Preparation of First Modified Polyrotaxane EGAPR2>
In Example 5, 11.0 g of EGAPR2 was synthesized in the same manner as in Example 5 except that the amount of glycidyl ethyl ether was changed to 30 g (0.30 mol).
By GPC, the weight average molecular weight Mw was 203,000 and the molecular weight distribution Mw / Mn was 1.3. The substitution rate of the hydroxypropylethyl ether group was measured by ¹ H-NMR and found to be 0.44. The calculated [OH] is 8.3 mmol / g. In addition, the hydroxyl value according to JIS K0070 is 325 mgKOH / g.
¹ H-NMR, (DMSO-d ⁶ , 400 MHz), δ (ppm) 1.10 (t, 23.7 H), 3.0-4.0 (m, 173 H), 4.0-6.0 (m, 24.0 H).

<Preparation of first modified polyrotaxane IGAPR1>
50 ml of 1.5N NaOH aqueous solution was put into the reaction vessel, and 10 g of APR was dissolved. While maintaining the reaction solution at room temperature (20 ° C.), 20 g (0.17 mol) of glycidyl isopropyl ether was added dropwise over 20 minutes, followed by stirring for 20 hours. The reaction solution was neutralized with 6N hydrochloric acid. This solution was dialyzed with a dialysis tube (fraction molecular weight: 12,000) for 48 hours under running tap water. Further, it was performed twice in purified water for 3 hours. Lyophilization was performed to obtain hydroxypropyl isopropyl ether APR1 (hereinafter, “hydroxypropyl isopropyl ether APR” may be simply abbreviated as “IGAPR”). The yield of IGAPR1 was 11.7 g.
By GPC, the weight average molecular weight Mw was 154,000, and the molecular weight distribution Mw / Mn was 1.3. The substitution rate of the hydroxypropyl isopropyl ether group was measured by ¹ H-NMR and found to be 0.25. The calculated [OH] is 9.7 mmol / g.
¹ H-NMR, (DMSO-d ⁶ , 400 MHz), δ (ppm) 1.07 (d, 27.1H), 3.0-4.0 (m, 133H), 4.0-6.0 (m, 24.0H).

<Preparation of first modified polyrotaxane IGAPR2>
In Example 7, 12.0 g of IGAPR2 was synthesized in the same manner as in Example 7 except that the amount of glycidyl isopropyl ether was changed to 30 g (0.26 mol).
By GPC, the weight average molecular weight Mw was 168,000, and the molecular weight distribution Mw / Mn was 1.3. The substitution rate of the hydroxypropyl isopropyl ether group was measured by ¹ H-NMR and found to be 0.39. The calculated [OH] is 8.4 mmol / g. The hydroxyl value according to JIS K0070 was 330 mgKOH / g.
¹ H-NMR, (DMSO-d ⁶ , 400 MHz), δ (ppm) 1.07 (d, 42.1H), 3.0-4.0 (m, 154H), 4.0-6.0 (m, 24.0H).

(Comparative Example 1)
<Preparation of HAPR1>
250 ml of 1.5N NaOH aqueous solution was put into the reaction vessel, and 50 g of APR was dissolved. While maintaining the reaction solution at 5 ° C., 65 g (1.12 mol) of propylene oxide was added dropwise over 50 minutes, followed by stirring for 20 hours. The reaction solution was neutralized with 6N hydrochloric acid. This solution was dialyzed with a dialysis tube (fraction molecular weight: 12,000) for 48 hours under running tap water. Further, it was performed twice in purified water for 3 hours. Lyophilization was performed to obtain hydroxypropylated APR1 (hereinafter, hydroxypropylated APR may be simply abbreviated as “HAPR”). The yield of HAPR1 was 55 g.
By GPC, the weight average molecular weight Mw was 110,000, and the molecular weight distribution Mw / Mn was 1.3. The substitution rate of the hydroxypropyl group was measured by ¹ H-NMR and found to be 0.33. The calculated [OH] is 10.8 mmol / g.
¹ H-NMR, (DMSO-d ⁶ , 400 MHz) δ (ppm) 1.0 (s, 17.8H), 3.0-4.0 (m, 94H), 4.0-6.0 (m, 24.0H).

(Comparative Example 2)
<Preparation of HAPR2>
HAPR2 was synthesized in the same manner as in Comparative Example 1 except that the amount of propylene oxide was changed to 110 g in Comparative Example 1.
By GPC, the weight average molecular weight Mw was 120,000, and the molecular weight distribution Mw / Mn was 1.3. The substitution rate of hydroxypropyl group was measured by ¹ H-NMR and found to be 0.50. The calculated [OH] is 9.7 mmol / g.
¹ H-NMR, (DMSO-d ⁶ , 400 MHz) δ (ppm) 1.0 (s, 27.1H), 3.0-4.0 (m, 105H), 4.0-6.0 (m, 24.0H).

<Solubility and affinity of the first modified polyrotaxane>
The solubility / affinity of the first modified polyrotaxane of Examples 1 to 8 and the HAPR1 and HAPR2 of Comparative Examples 1 and 2 in each solvent was evaluated.
Evaluation of solubility / affinity was performed as follows. The solid polyrotaxane as each sample was added to various solvents so as to be 0.5 wt%, and vigorously stirred with a stir bar at room temperature to evaluate the solubility. In the evaluation, the following indicators were used.
○: Dissolved.
Δ: There is a little unmelted residue.
X: It does not melt.
These results are shown in Table 1.

From Table 1, the solubility of the first modified polyrotaxane of the present invention (Examples 1 to 8) is improved compared to unmodified polyrotaxane (APR) and hydroxypropyl modified polyrotaxanes having the same substitution rate (HAPR1 and HAPR2). You can see that In particular, it can be seen that the improvement effect on alcohols and lactone monomers having high industrial utility value is remarkable.
Moreover, in the synthesis | combination of the material of this invention, as shown in Example 4, it was confirmed by heating that the reaction time can be shortened and the substitution rate is slightly improved.

(Example 9 to Example 16)
<Preparation of Second Modified Polyrotaxane>
Using the first modified polyrotaxane obtained in Examples 1 to 8 as a raw material, the second modified polyrotaxane (Example 9: BAPR1-g-PCL; Example 10: BAPR2-g-PCL) Example 11: BAPR3-g-PCL; Example 12: BAPR4-g-PCL; Example 13: EGAPR1-g-PCL; Example 14: EGAPR2-g-PCL; Example 15: IGAPR1-g-PCL Example 16: IGAPR2-g-PCL) was prepared.

Specifically, ring-opening polymerization of a monomer such as ε-caprolactone was carried out starting from the first substituent of the first modified polyrotaxane. More specifically, it was performed as follows.
5.0 g of the first modified polyrotaxane (Example Y (Y represents 1 to 8)) was placed in a three-necked flask, and 22.5 g of ε-caprolactone was introduced while slowly flowing nitrogen. After stirring uniformly with a mechanical stirrer at 100 ° C. for 30 minutes, the reaction temperature was raised to 130 ° C., and 0.40 g of 2-ethylhexanoic acid tin (50 wt% solution) previously diluted with toluene was added and reacted for 6 hours. The solvent was removed to obtain a reaction product. As a result of measuring an infrared absorption spectrum (IR, Nicolet 6700 FT-IR (manufactured by Thermo Fisher)), a peak derived from an ester at 1736 cm ⁻¹ was observed. As a result of analysis by gas chromatography (GC-2014, manufactured by Shimadzu Corporation), the amount of unreacted ε-caprolactone was 1.0 wt% or less with respect to the input amount.

Regarding the obtained second modified polyrotaxane, the following physical properties: weight average molecular weight, molecular weight distribution, purity (measured by GPC), hydroxyl value (in Table 2, “mgKOH / g” value), grind gauge test As a result, the viscosity was measured. The results are shown in Table 2. In addition, the grind gauge test result and the viscosity were measured as follows.
The viscosity was measured using a digital viscometer TVB-10 (manufactured by TOYO SANGYO). The values in Table 2 are described as “mPa · s” when a 40 ° C., 35 wt% xylene solution is used.
Grind gauge test (abbreviated as “GG test” in Table 2): A 35 wt% xylene solution of the second modified polyrotaxane was prepared, and this solution was bladed using a grindometer GW-3098M (manufactured by Dazai Equipment Co., Ltd.). And visually confirmed the presence or absence of a foreign substance immediately after that, and evaluated as follows.
○: No foreign matter.
Δ: Slightly foreign matter is present.
×: Obviously foreign matter is present.

(Comparative Example 3 and Comparative Example 4)
Using the HAPR1 of Comparative Example 1 and the HAPR2 of Comparative Example 2, a graft polyrotaxane grafted with polycaprolactone by ring-opening graft polymerization of ε-caprolactone by the same method as in Examples 9 to 16 (Comparative Example 3: HAPR1-g-PCL; and Comparative Example 4: HAPR2-g-PCL). These physical properties are also shown in Table 2.

Table 2 shows the following. That is, the second modified polyrotaxane (Examples 9 to 16) has a relatively high substitution rate of the first substituent of the first modified polyrotaxane as compared with the modified polyrotaxane of Comparative Example 3 and Comparative Example 4. Even if it is low, the viscosity of the obtained second modified polyrotaxane is low and an insoluble matter-free product can be produced. In particular, Comparative Example 3 shows that the effects in Examples 9 to 16 are remarkable compared to Comparative Example 3 because there are many foreign substances and the viscosity measurement is not possible as a result of the grinding gauge test results.

(Example 17)
<Crosslinked product formed with second modified polyrotaxane>
Using the second modified polyrotaxane, a thermosetting elastomer was produced by crosslinking with a polyol prepolymer. A synthesis example of a prepolymer necessary for production is shown below.

<< Synthesis of Prepolymer P1 >>
2.80 kg of 1,3-bis (isocyanatomethyl) cyclohexane (Takenate 600 manufactured by Mitsui Chemicals, Inc.) was placed in the reaction vessel and heated to 80 ° C. with stirring under a nitrogen stream. Polycarbonate diol (polyalkylene carbonate diol, Duranol (registered trademark) T-5650J (manufactured by Asahi Kasei Chemicals Corporation, Mn: 800; 1,5-pentanediol and / or 1,6-hexanediol as repeating units. 4.98 kg (simply abbreviated as “polycarbonate diol Duranol (registered trademark) T5650J”) was warmed to 70 ° C., slowly dropped into the reaction vessel over 4 hours, and further stirred for 3 hours. Prepolymer 1 (P1) (7.78 kg) having a group-modified polycarbonate diol and 1,3-bis (isocyanatomethyl) cyclohexane was obtained.

<< Synthesis of Block Prepolymer BP1 >>
P1 (7.78 kg) obtained above was placed in a reaction vessel and heated to 100 ° C. with stirring under a nitrogen stream. Ε-Caprolactam (2.04 kg) was added thereto and stirred for 6 hours to obtain block prepolymer 1 (BP1) in which the isocyanate groups at both ends of the polycarbonate were protected with ε-caprolactam. As a result of measurement by FT-IR (Nicolet 6700 FT-IR), the peak derived from the isocyanate group in the vicinity of 2250 cm ⁻¹ disappeared, so that it was confirmed that the isocyanate group was protected.

<< Synthesis of crosslinked E-1 >>
Using BAPR2-g-PCL of Example 10, each component was mixed at the composition ratio shown in Table 3, defoamed at 80 ° C., and then placed in a cylindrical mold having a radius of 30 mm and a height of 15 mm at 150 ° C. The reaction was carried out in the oven for 5 hours to obtain a crosslinked product E-1. By infrared spectroscopy, from the decrease of the peak around 3450 cm ⁻¹ derived from the OH group of BAPR2-g-PCL, the isocyanate group of BP1 reacts with the OH group of BAPR2-g-PCL to form a bridge. I confirmed that.

(Example 18)
<< Synthesis of crosslinked product E-2 >>
Using the IGAPR2-g-PCL of Example 16, each component was mixed at the composition ratio shown in Table 3, defoamed at room temperature, then placed in a Teflon (registered trademark) mold and left at 50 ° C. for 1 day. . The product was taken out from the mold and dried under reduced pressure at 80 ° C. to obtain a crosslinked product E-2.

(Comparative Example 5)
<< Synthesis of crosslinked product H-1 >>
Using HAPR2-g-PCL of Comparative Example 4, a reaction was carried out in the same manner as in Example 17 to obtain a crosslinked product H-1.

(Comparative Example 6)
<< Synthesis of crosslinked product H-2 >>
Using HAPR2-g-PCL of Comparative Example 4, a reaction was carried out in the same manner as in Example 18 to obtain a crosslinked product H-2.

For the obtained crosslinked products E-1 and E-2 and crosslinked products H-1 and H-2, the stress at an elongation rate of 50% (hereinafter sometimes abbreviated as “50% modulus”), elongation The stress at a rate of 100% (hereinafter sometimes abbreviated as “100% modulus”), maximum stress, elongation at break, and compression set were measured. The results are also shown in Table 3.
Each measurement item was measured as follows.
The 50% modulus, 100% modulus, maximum stress, and elongation at break were measured by using a dumbbell No. 3 test piece or a dumbbell No. 7 test piece at room temperature according to JIS K6251.
The compression set (100 ° C., 24 hours) was measured by a method according to JIS K6262 using a cross-linked product to be measured as a cylindrical test piece (radius 30 mm, thickness 15 mm).

As can be seen from Table 3, by using the second modified polyrotaxane of the present application, it is possible to provide an elastomer (low modulus, high elongation at break) with excellent flexibility. Further, when the crosslinked product E-1 (Example 17) and the crosslinked product H-1 (Comparative Example 5) are compared, it is crosslinked with the same composition except for whether or not the second modified polyrotaxane of the present application is used. Although the body is made, it can be seen that when the second modified polyrotaxane of the present application is used, a compression set is considerably reduced, and a material with less sag can be provided.

Claims (11)

1. This is a modified polyrotaxane modified with a polyrotaxane in which a blocking group is arranged so that the cyclodextrin is not detached at both ends of a pseudopolyrotaxane in which the opening of the cyclodextrin is clasped with a linear molecule. And
   At least a part of the hydroxyl groups of the cyclodextrin is represented by the following formula (I) (wherein —R represents —CH ₂ —CH ₃ , —CH ₂ —O—CH ₃ , —CH ₂ —O—CH ₂ —). And at least one first group selected from the group consisting of CH ₃ , —CH ₂ —O—CH ₂ —CH ₂ —CH ₃ and —CH ₂ —O—CH— (CH ₃ ) ₂ ) The modified polyrotaxane is substituted with the first substituent.
   

   
2. The following formula (II) wherein at least a part of the hydroxyl group further modifies the first substituent (wherein X is a linear or branched alkylene group having 2 to 8 carbon atoms, acetyl At least selected from the group consisting of a linear or branched alkylene group having 3 to 8 carbon atoms having a group branch and a linear or branched alkylene group having 3 to 8 carbon atoms having an ether bond, The modified polyrotaxane according to claim 1, wherein the modified polyrotaxane is substituted with a second substituent represented by the following formula: one kind of second group, and n is 1 to 200.
   

   
3. The modified polyrotaxane according to claim 1, wherein the substitution rate of the first substituent is 0.10 to 0.60, where 1.0 is a state in which all of the hydroxyl groups of the cyclodextrin are substituted.
4. The —X— is — (CH ₂ ) ₃ —, — (CH ₂ ) ₅ —, —CH (CH ₃ ) —CH ₂ —CH ₂ — and — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ The modified polyrotaxane according to claim 2, which is at least one alkylene group selected from the group consisting of-.
5. The modified polyrotaxane according to claim 2 or 4, wherein the molecular weight distribution of the modified polyrotaxane is 2.0 or less.
6. A cross-linking material in which the modified polyrotaxane according to claim 2, 4 or 5 is included in the cross-linking.
7. A material formed with the modified polyrotaxane according to claim 2, 4 or 5.
8. A method for producing a modified polyrotaxane comprising the steps of:
   a) preparing a polyrotaxane in which blocking groups are arranged so that the cyclodextrin is not detached at both ends of the pseudopolyrotaxane in which the opening of the cyclodextrin is clasped by linear molecules; and b ) At least part of the hydroxyl groups of the cyclodextrin is represented by the following formula (I) (wherein —R represents —CH ₂ —CH ₃ , —CH ₂ —O—CH ₃ , —CH ₂ —O—CH _2). A first group represented by the formula: —CH ₃ , —CH ₂ —O—CH ₂ —CH ₂ —CH ₃ and —CH ₂ —O—CH— (CH ₃ ) ₂ . Substituting with a substituent of
   The above method.
   

   
9. The substitution in the step b) includes at least a part of the hydroxyl group and at least one first selected from the group consisting of 1,2-butylene oxide, glycidyl methyl ether, glycidyl ethyl ether, glycidyl propyl ether, and glycidyl isopropyl ether. The method of Claim 8 performed by making it react with the compound of this.
10. c) ring-opening polymerization of a lactone monomer starting from the first substituent, and at least a part of the hydroxyl group is represented by the following formula (II) (wherein X is a straight chain having 2 to 8 carbon atoms) Linear or branched alkylene group having 3 to 8 carbon atoms having branched or acetyl groups, and straight chain or branched alkylene having 3 to 8 carbon atoms having an ether bond 10. The method according to claim 8, further comprising a step of substitution with a second substituent represented by: at least one second group selected from the group consisting of groups, wherein n is 1 to 200. the method of.
    

    
11. In the step c), the ring-opening polymerization is performed using at least one compound selected from the group consisting of ε-caprolactone, γ-valerolactone, α-methyl-γ-butyrolactone and γ-butyrolactone in the step c). The method according to claim 10 to be performed.