阅读说明：本技术 在环状分子上具备具有聚环氧烷链或其衍生物的取代基的聚轮烷和其制造方法 (Polyrotaxane having cyclic molecule having substituent having polyalkylene oxide chain or derivative thereof, and process for producing the same ) 是由 井上胜成 工藤成史 于 2018-06-05 设计创作，主要内容包括：本发明提供：耐久性、特别是耐水解性高的聚轮烷和其制造方法。本发明提供一种聚轮烷,其特征在于,其为在环状分子的开口部被直链状分子以穿串状包接而成的准聚轮烷的两端以前述环状分子不会脱离的方式配置封端基而得到的聚轮烷,前述环状分子具有下述式I(式I中,R<Sub>1</Sub>表示-CH<Sub>3</Sub>、-CH<Sub>2</Sub>-CH<Sub>3</Sub>等基团,R<Sub>2</Sub>表示H、-CH<Sub>3</Sub>等基团,n为加成于环状分子上的聚环氧烷链或其衍生物的表观上的聚合度,其值为1.1～10.0)所示的取代基。<Image he="211" wi="700" file="DDA0002298396850000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention provides: polyrotaxane having high durability, particularly high hydrolysis resistance, and a process for producing the same. The present invention provides a polyrotaxane comprising a pseudopolyrotaxane in which linear molecules are entangled at openings of cyclic molecules, wherein the cyclic molecules have the following formula I (in formula I, R is R, and R is a linear molecule, and blocking groups are disposed at both ends of the pseudopolyrotaxane so that the cyclic molecules do not detach from the pseudopolyrotaxane 1 represents-CH 3 、‑CH 2 ‑CH 3 Etc. group, R 2 Represents H, -CH 3 N is apparent poly of polyalkylene oxide chain or derivative thereof added to cyclic moleculeA degree of polymerization of 1.1 to 10.0).)

1. A polyrotaxane comprising a pseudopolyrotaxane in which linear molecules are entangled in a cross-chain manner at openings of cyclic molecules, wherein blocking groups are disposed at both ends of the pseudopolyrotaxane so that the cyclic molecules do not detach therefrom,

the cyclic molecule has a substituent represented by the following formula I,

in the formula I, R₁Is selected from-CH₃、-CH₂-CH₃、-CH₂-O-CH₃、-CH₂-O-CH₂-CH₃and-CH₂-O-CH-(CH₃)₂At least 1 group of the group consisting of-phenyl,

R₂is selected from the group consisting of H, -CH₃、-OCONH-(CH₂)₃-CH₃、-OCONH-C₁₈H₃₇and-COCH₃At least 1 group of the group consisting of,

n is the apparent degree of polymerization of a polyalkylene oxide chain or a derivative thereof added to a cyclic molecule and is 1.1 to 10.0,

2. a process for producing a polyrotaxane B, which comprises the following steps to obtain a polyrotaxane B having a cyclic molecule having a substituent represented by the following formula I:

a step (a) of preparing a polyrotaxane A in which a linear molecule is entangled at an opening of a cyclic molecule to form a pseudopolyrotaxane, and blocking groups are disposed at both ends of the pseudopolyrotaxane so that the cyclic molecule does not detach from the pseudopolyrotaxane; and the combination of (a) and (b),

a step (b) of reacting the compound represented by the following formula II with the polyrotaxane A to provide the cyclic molecule with a substituent represented by the following formula I,

in the formula II, R₁Is selected from-CH₃、-CH₂-CH₃、-CH₂-O-CH₃、-CH₂-O-CH₂-CH₃and-CH₂-O-CH-(CH₃)₂At least 1 group of the group consisting of-phenyl,

in the formula I, R₁Have the same definitions as above-mentioned,

R₂is selected from the group consisting of H, -CH₃、-OCONH-(CH₂)₃-CH₃、-OCONH-C₁₈H₃₇and-COCH₃At least 1 group of the group consisting of,

n is the apparent degree of polymerization of a polyalkylene oxide chain or a derivative thereof added to a cyclic molecule and is 1.1 to 10.0,

3. the method according to claim 2, wherein in the step (b), the reaction is carried out in the presence of i) a superbase or ii) a polymerization initiator.

4. A material comprising the polyrotaxane of claim 1.

5. The material according to claim 4, which further comprises a substance other than the polyrotaxane according to claim 1, and the substance is directly or indirectly bonded to a part of the polyrotaxane according to claim 1.

Technical Field

The present invention relates to: a polyrotaxane having a cyclic molecule with a substituent having a polyalkylene oxide chain or a derivative thereof, a material having the polyrotaxane, and a method for producing the polyrotaxane.

Background

Polyrotaxane has attracted attention because of a special structure in which a cyclic molecule is movable relative to an axial molecule, and its properties are changed by providing various substituents on the cyclic molecule.

For example, patent documents 1 and 2 disclose the following techniques: a cyclic molecule of a polyrotaxane is provided with a graft chain obtained by graft polymerization of a monomer.

Specifically, patent document 1 discloses a polyrotaxane in which a cyclic molecule of the polyrotaxane is modified with a modifying group of-M-A, -M-B and-C. M is a modification group with the average polymerization degree (n) of 1-20 shown in formula IV or formula V, and the modification group is in a polyester or polyamide structure, and specifically is polycaprolactone or polycaprolactam.

Further, patent document 2 discloses a polyrotaxane having a radical polymerization initiation site in a cyclic molecule. Disclosed is a polyrotaxane having a graft chain polymerized from a radically polymerizable monomer via the radical polymerization initiation site. The graft chains formed by polymerization of the monomers are in particular polyacrylate chains.

Further, patent document 3 discloses a crosslinked polyrotaxane in which polyrotaxanes are chemically bonded to each other, and discloses that a part of the hydroxyl groups of cyclodextrin of the polyrotaxane are bonded to each other via a nonionic bonding group. 2-hydroxypropyl is disclosed as the nonionic bonding group.

Further, patent document 4 discloses that a part of the hydroxyl groups of cyclodextrin of polyrotaxane is substituted with a substituent represented by formula (1), for example, a 2-hydroxybutyl substituent.

However, patent documents 1 to 4 have a problem in that they are poor in hydrolysis resistance and have a problem in durability, and/or have a problem in that they are poor in compatibility and affinity with materials other than polyrotaxane. That is, in patent document 1 or patent document 2, even if the cyclic molecule has a graft chain, it has a polyester structure, a polyamide structure (patent document 1), or a polyacrylate structure (patent document 2), and there is a problem in that it lacks hydrolysis resistance and has durability. In addition, in patent documents 3 and 4, since the cyclic molecule does not have a graft chain, compatibility and affinity with a desired material cannot be obtained.

Disclosure of Invention

Problems to be solved by the invention

Accordingly, an object of the present invention is to provide: polyrotaxane which has durability, particularly hydrolysis resistance, and which retains compatibility with a desired material such as a polymer material other than polyrotaxane.

In addition, in addition to the above object, an object of the present invention is to provide: a material having the polyrotaxane.

Further, in addition to or in addition to the above objects, an object of the present invention is to provide: a crosslinked product comprising the polyrotaxane.

In addition to or in addition to the above objects, an object of the present invention is to provide: a molded article comprising the polyrotaxane, the material and/or the crosslinked material.

Further, in addition to or in addition to the above objects, an object of the present invention is to provide: a process for producing the polyrotaxane, the material, the crosslinked product and/or the molded article.

Means for solving the problems

The present inventors have found the following invention.

[ 1] A polyrotaxane characterized by being a polyrotaxane in which a linear molecule is entangled at an opening of a cyclic molecule and blocking groups are disposed at both ends of a pseudopolyrotaxane in such a manner that the cyclic molecule does not detach from the pseudopolyrotaxane,

the cyclic molecule has a substituent represented by the following formula I,

(in the formula I, R₁Is selected from-CH₃、-CH₂-CH₃、-CH₂-O-CH₃、-CH₂-O-CH₂-CH₃and-CH₂-O-CH-(CH₃)₂At least 1 group of the group consisting of-phenyl,

R₂is selected from the group consisting of H, -CH₃、-OCONH-(CH₂)₃-CH₃、-OCONH-C₁₈H₃₇and-COCH₃At least 1 group of the group consisting of,

n is the apparent degree of polymerization of a polyalkylene oxide chain or a derivative thereof added to a cyclic molecule, and is 1.1 to 10.0).

In the above-mentioned < 1 > of < 2 >, the value of n may be 2.0 to 8.0, preferably 3.0 to 6.0.

< 3 > in the above-mentioned < 1 > or < 2 >, R₁Can be selected from the group consisting of-CH₃、-CH₂-CH₃and-CH₂-O-CH₂-CH₃At least 1 group selected from the group consisting of-CH₃and-CH₂-CH₃At least 1 group of the group.

< 4 > any one of the above < 1 > - < 3 >, R₂Can be selected from the group consisting of H, -OCONH- (CH)₂)₃-CH₃、-OCONH-C₁₈H₃₇and-COCH₃At least 1 group selected from the group consisting of H and-OCONH- (CH)₂)₃-CH₃At least 1 group of the group.

< 5 > a process for producing a polyrotaxane B having a cyclic molecule having a substituent represented by the above formula I, which comprises the steps of:

a step (a) of preparing a polyrotaxane A in which a linear molecule is entangled at an opening of a cyclic molecule to form a pseudopolyrotaxane, and blocking groups are disposed at both ends of the pseudopolyrotaxane so that the cyclic molecule does not detach from the pseudopolyrotaxane; and

a step (b) of reacting a compound represented by the following formula II (wherein R is in the formula II)₁Having the same definition as above) with a polyrotaxane A, the compound having the above formula I (in the formula I, R is₁、R₂And n has the same definition as above).

In the step (b) < 6 > or < 5 > above, the reaction may be carried out in the presence of i) a superbase or ii) a polymerization initiator.

< 7 > a material comprising any one of the polyrotaxanes of < 1 > to < 4 > above.

< 8 > a material comprising any one of the polyrotaxanes < 1 > to < 4 > and a substance other than any one of the polyrotaxanes < 1 > to < 4 >, wherein at least a part of the polyrotaxane is directly or indirectly bonded to at least a part of the substance.

< 9 > a molded article comprising any one of the polyrotaxanes of < 1 > to < 4 >.

< 10 > a molded article formed with the material < 7 > or < 8 > described above.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided: polyrotaxane which has durability, particularly hydrolysis resistance, and which retains compatibility with a desired material such as a polymer material other than polyrotaxane.

In addition, according to the present invention, in addition to the above-described effects, there can be provided: a material having the polyrotaxane.

Further, according to the present invention, in addition to or in addition to the above-described effects, there can be provided: a crosslinked product comprising the polyrotaxane.

In addition, according to the present invention, in addition to or in addition to the above-described effects, there can be provided: a molded article comprising the polyrotaxane, the material and/or the crosslinked material.

Further, according to the present invention, in addition to or in addition to the above-described effects, there can be provided: a process for producing the polyrotaxane, the material, the crosslinked product and/or the molded article.

Drawings

FIG. 1 shows a diagram of polyrotaxane A4 obtained in example 4¹H-NMR(DMSO-d⁶) A spectrum of (a).

FIG. 2 shows a diagram of polyrotaxane C1 obtained in comparative example 1¹H-NMR(DMSO-d⁶) A spectrum of (a).

Detailed Description

Hereinafter, the invention described in the present application will be described in detail.

Polyrotaxane of the present invention

The present application provides: the cyclic molecule has a polyrotaxane having a substituent of a polyalkylene oxide chain or a derivative thereof, specifically a substituent represented by the following formula I.

Since the polyrotaxane of the present invention has a substituent represented by the above formula I, which is different from the polyester structure or the polyamide structure, and has hydrolysis resistance, the polyrotaxane of the present invention can have durability.

Further, the following effects can be exhibited by having a polyalkylene oxide chain or a derivative thereof as a substituent represented by the following formula I.

i) The solubility in a solvent is improved, and various solvents can be used when the polyrotaxane of the present invention is used.

ii) the compatibility of the polyrotaxane with the desired material can be maintained. Specifically, the compatibility of the polyrotaxane of the present invention with a polymer other than the polyrotaxane can be maintained. Thus, it is expected that the functional properties of the composition can be improved by compounding with a desired material, for example, a polymer other than polyrotaxane, extending the blend, and compounding the material.

iii) the mechanical properties of the material with the polyrotaxane of the present invention can be controlled. For example, the improvement of flexibility, the improvement of heat resistance, the improvement of characteristics such as dielectric constant, etc. can be expected by the synergistic effect with the flexibility of the polyalkylene oxide chain or the derivative thereof.

In the formula I, n represents an apparent degree of polymerization of a polyalkylene oxide chain or a derivative thereof added to a cyclic molecule.

The added polyalkylene oxide chain or derivative thereof sometimes has dispersion, and therefore, the value of n is represented by a decimal point.

The value of n may be 1.1 to 10.0, preferably 2.0 to 8.0, more preferably 3.0 to 6.0.

The value of n may be determined by the polyrotaxane of the invention¹As a result of H-NMR measurement¹H-NMR spectrum was calculated. However,¹in the H-NMR spectrum, it is difficult to calculate the actual polymerization degree because a large number of peaks overlap. Therefore, n is defined as the apparent degree of polymerization.

The following description will be given as an example of a method for calculating n: the starting polyrotaxane a (hereinafter, sometimes referred to simply as "polyrotaxane a") is reacted with an alkylene oxide monomer or a derivative thereof (hereinafter, sometimes referred to simply as "monomer C") to obtain a polyrotaxane B (hereinafter, sometimes referred to simply as "modified polyrotaxane B") having a substituent of a polyalkylene oxide chain or a derivative thereof in a cyclic molecule according to the present invention. Further, a case where the cyclic molecule of the starting polyrotaxane a is α -cyclodextrin (hereinafter, abbreviated as "α -CD") will be described.

n is the same as the "addition ratio" shown below.

The "addition rate" herein means the number of "monomers C" in the "modified polyrotaxane B" relative to the number of hydroxyl groups of α -CD which is a cyclic molecule in the raw material "polyrotaxane a".

"monomer C" to be reacted is a structure having an oxirane group (epoxy group), and a plurality of monomers may be reacted with 1 hydroxyl group in sequence. Therefore, the addition rate may exceed 100% with respect to the hydroxyl group of the raw material. In the above case, the polyalkylene oxide chain or a derivative thereof is provided to at least a part of the α -CD hydroxyl groups, which are cyclic molecules of the raw material "polyrotaxane a". For example, when the addition rate is 120%, 20% of 18 hydroxyl groups of α -CD are added to a plurality of "monomers C" on average.

Here, in practice, reference is made to the polyrotaxane of the invention obtained¹The "addition rate" is also described in the H-NMR spectrum.

FIG. 1 shows a diagram of a polyrotaxane of the present invention obtained in example 4 described later, that is, a polyrotaxane having a polypropylene oxide chain¹H-NMR spectrum.

In the spectrum, the peak at 1ppm is derived from-CH of the propylene oxide group₃. The integrated value of the peak at 1ppm is set as L.

The peaks at 4.2 to 6.5ppm are derived from a plurality of kinds of H, specifically, H derived from "H of hydroxyl group of α -CD", "H of terminal hydroxyl group of reacted propylene oxide", and "H of C1 at glucose site of α -CD". The integral value of the peak at 4.2 to 6.5ppm is defined as M.

When the addition rate of propylene oxide is Y, the peak at 1ppm (propylene oxide-derived-CH)₃) The integrated value L of (b) is "Y × 3 × 18".

On the other hand, the integrated value M of the peak at 4.2 to 6.5ppm is the sum of "(1-Y). times.18" derived from "H of hydroxyl group of α -CD", "Y.times.18" derived from "H of terminal hydroxyl group of reacted propylene oxide", and "6" derived from "H1C of glucose site of α -CD".

The ratio of the integrated values L and M is represented by the following equation, and the measurement results (L is 307.69 and M is 24.0) are substituted, whereby the addition rate Y can be calculated.

L：M＝(Y×3×18)：{(1-Y)×18+Y×18+6}

54Y：24＝307.69/24.0。

The addition rate Y was 5.69 (569%).

Since the addition rate was the same as n as described above, the apparent polymerization degree n was 5.69.

FIG. 2 shows the preparation of polyrotaxane obtained in comparative example 1 described later¹H-NMR spectrum.

From the integrated value L (26.88) of the peak at 1ppm and the integrated value M (24.0) of the peak at 4.2 to 6.5ppm, the addition rate Y was 0.497 (50%), and the apparent polymerization degree n was 0.5.

The "increase in weight average molecular weight" which is the difference between the weight average molecular weight of the "modified polyrotaxane B" and the weight average molecular weight of the "raw polyrotaxane a" may be used; and "inclusion ratio" of the "raw material polyrotaxane A" (the number of. alpha. -CD in each molecule of the "modified polyrotaxane B") to measure the addition ratio, i.e., the apparent degree of polymerization n. However, it can be said that the calculation of the addition rate from the "increase in weight average molecular weight" is less accurate because of the difference in polarity between the "modified polyrotaxane B" and the "polyrotaxane a as a raw material", the difference in solubility in a solvent for GPC, and the like.

The "packet-to-packet ratio" can be obtained as follows.

"packet ratio" means the following value: the ratio of the number of actually arranged cyclic molecules (. alpha. -CD) to the number of cyclic molecules (. alpha. -CD) in the case where the cyclic molecules (. alpha. -CD) are arranged at the highest density in the "raw material polyrotaxane A" and the "modified polyrotaxane B". Here, the maximum density (maximum amount of inclusion) of α -CD is determined by the length of the linear molecule and the thickness of the cyclic molecule. When the linear molecule is polyethylene glycol (PEG), it can be obtained by the method described in Macromolecules 1993,26, 5698-. Of polyethylene glycol- (O-CH)₂-CH₂)₂The amount of 2 repeating units of-corresponds to the molecular thickness of a-CD. For example, in the case of PEG having a number average molecular weight of 35000, the maximum amount of α -CD included was 35000/88-398, and in the case of 398 α -CD included in PEG having a number average molecular weight of 35000, the inclusion ratio was 100%.

The "α -CD packet-splicing ratio" is determined as follows: based on the H of PEG at the maximum amount of alpha-CD coated with the alpha-CD¹H-NMR was obtained from the ratio of the integral values of H derived from α -CD and H of PEG.

In the formula I, R₁Is selected from-CH₃、-CH₂-CH₃、-CH₂-O-CH₃、-CH₂-O-CH₂-CH₃and-CH₂-O-CH-(CH₃)₂At least 1 group selected from the group consisting of-CH, preferably₃、-CH₂-CH₃and-CH₂-O-CH₂-CH₃At least 1 group selected from the group consisting of-CH₃and-CH₂-CH₃At least 1 group of the group.

In the formula I, R₂Is selected from the group consisting of H, -CH₃、-OCONH-(CH₂)₃-CH₃、-OCONH-C₁₈H₃₇and-COCH₃At least 1 group selected from the group consisting of H, -OCONH- (CH)₂)₃-CH₃、-OCONH-C₁₈H₃₇and-COCH₃At least 1 group selected from the group consisting of H and-OCONH- (CH)₂)₃-CH₃At least 1 group of the group.

The polyrotaxane of the present invention has a cyclic molecule, a linear molecule, and a blocking group in addition to the substituent represented by formula I, and is formed by disposing the blocking group at both ends of a pseudopolyrotaxane in which the linear molecule is entangled in a cross-like manner at an opening of the cyclic molecule so that the cyclic molecule does not detach. The cyclic molecule, the linear molecule, and the blocking group, which are each constituent element contained in the polyrotaxane, will be described below.

Circular molecule

The cyclic molecule is not particularly limited as long as it is cyclic, has an opening, and can be enclosed in a linear molecule in a cross-linked manner.

The cyclic molecule may have a hydroxyl group (-OH group), depending on a desired material described later, a desired crosslinked material described later, a desired molded article described later, and the like.

The hydroxyl group (-OH group) may be directly bonded to the cyclic skeleton of the cyclic molecule or may be bonded to the cyclic skeleton via the 1 st spacer, depending on the desired material, the desired crosslinked material, the desired characteristics of the molded article, and the like.

The cyclic molecule may have, depending on the desired material, the desired crosslinked material, the desired characteristics of the molded article, and the like: other groups such as 1) hydrophobic modification groups such as methoxy, ethoxy, acetyl, butylcarbamoyl; 2) is selected from the group consisting of-NH₂A group of the group consisting of-COOH and-SH; 3) a group selected from the group consisting of an acryloyl group, a methacryloyl group, a styryl group, a vinyl group, a vinylidene group, and a polymerizable group containing a functional group of maleic anhydride; and the like.

As the cyclic molecule, for example, one selected from the group consisting of α -cyclodextrin, β -cyclodextrin and γ -cyclodextrin may be mentioned.

Linear molecule

The linear molecule is not particularly limited as long as it can be bound in a skewered manner at the opening of the cyclic molecule to be used.

Examples of the linear molecules include polyvinyl alcohol, polyvinyl pyrrolidone, poly (meth) acrylic acid, cellulose resins (such as carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl acetal resins, polyvinyl methyl ether, polyamine, polyethyleneimine, casein, gelatin, starch and/or copolymers thereof, polyolefin resins such as polyethylene, polypropylene and copolymer resins with other olefin monomers, polyester resins, polyvinyl chloride resins, polystyrene resins such as polystyrene and acrylonitrile-styrene copolymer resins, acrylic resins such as polymethyl methacrylate, (meth) acrylate copolymers, acrylonitrile-methyl acrylate copolymer resins, polycarbonate resins, and the like, Polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, and the like; and derivatives or modified products thereof, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polyamides, polydienes such as polyimide, polyisoprene and polybutadiene, polysiloxanes such as polydimethylsiloxane, polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides (polysulfides), polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and derivatives thereof. For example, it is preferably selected from the group consisting of polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol and polyvinyl methyl ether. Polyethylene glycol is particularly suitable.

The weight average molecular weight of the linear molecule is 1000 or more, preferably 3000 to 100000, more preferably 6000 to 50000.

In the polyrotaxane, a combination of (cyclic molecule and linear molecule) is preferably (derived from α -cyclodextrin and from polyethylene glycol).

< end capping group >

The blocking group is not particularly limited as long as it is a group that is disposed at both ends of the pseudopolyrotaxane and functions so as not to allow the cyclic molecule to be removed.

For example, as blocking group, a group consisting of: dinitrobenzenes, cyclodextrins, adamantyls, trityls, fluoresins, silsesquioxanes, pyrenes, substituted benzenes (the substituents include, but are not limited to, alkyl, alkoxy, hydroxyl, halogen, cyano, sulfonyl, carboxyl, amino, phenyl, and the like), optionally substituted polynuclear aromatics (the substituents include, but are not limited to, the same as those described above), and steroids. Preferably, the solvent is selected from the group consisting of: dinitrobenzenes, cyclodextrins, adamantyls, trityls, luciferases, silsesquioxanes, and pyrenes, and adamantyls or cyclodextrins are more preferable.

< Material having polyrotaxane of the present invention >

The present application provides materials having the polyrotaxane of the present invention described above.

The material may have a substance other than the polyrotaxane of the present invention described above.

Examples of the substance include, but are not limited to, substances capable of binding to polyrotaxane, such as poly (meth) acrylate, polyamide, polyester, polyether, polyolefin, polydiene, polysiloxane, polystyrene, polyurethane, polyurea, polycarbonate, polyamic acid, and derivatives thereof.

In the material of the present invention, at least a part of the substance is directly or indirectly bonded to at least a part of the polyrotaxane of the present invention to form a crosslinked body.

Here, "indirectly bindable substance" means: and a substance capable of bonding to polyrotaxane by an inclusion substance such as a crosslinking agent, using an inclusion substance such as a crosslinking agent. On the other hand, "directly bindable substance" means: a substance capable of binding to a polyrotaxane in the presence of heat, a catalyst, an initiator or the like without using the above-mentioned inclusion substance.

For example, when the substance is polyacrylic acid, the substance can be directly bonded to polyrotaxane in the presence of a catalyst. In the case where the substance is propylene glycol, the polypropylene glycol and the hydroxyl group of the polyrotaxane of the present invention can be indirectly bonded to each other through a polyfunctional isocyanate compound such as hexamethylene diisocyanate as a crosslinking agent. The crosslinking agent is not particularly limited as long as it is a compound having a functional group which reacts a polyrotaxane with a substance other than a polyrotaxane. Examples of the crosslinking agent include, but are not limited to, polyfunctional isocyanate compounds, polyfunctional carboxylic acids, polyfunctional carboxylic anhydrides, polyfunctional epoxy compounds, polyfunctional carbodiimides, polyols, and polyamines.

< molded article comprising polyrotaxane of the present invention >

The present application provides: a molded article comprising the polyrotaxane of the present invention.

In addition, the present application provides: a molded article comprising the above-mentioned material.

Further, the present application provides: a molded article comprising the above material, particularly a crosslinked material.

These molded articles may have various components that impart desired characteristics to the molded articles. Examples of the components include, but are not limited to, plasticizers, surfactants, UV absorbers, pigments, antioxidants, antibacterial agents, viscosity modifiers, reinforcing fibers, fine particles, and flame retardants.

The polyrotaxane, the material, the crosslinked product and/or the molded article of the present invention can be used in various applications depending on their characteristics. Examples of the applications include adhesives, crack-resistant films, vibration-proof, vibration-damping, vibration-isolating materials, paints, coating agents, sealing materials, ink additives, adhesives, electrical insulating materials, electrical/electronic component materials, optical materials, friction control agents, cosmetic materials, rubber additives, resin modifiers, toughening agents, rheology control agents, thickeners, fibers, medical biomaterials, mechanical/automotive materials, building materials, clothing/sporting goods, and the like, but are not limited thereto.

< method for producing polyrotaxane of the present invention >

The polyrotaxane of the present invention can be produced by the following method.

That is, the polyrotaxane B which is the polyrotaxane of the present invention can be obtained by including the following steps:

a step (a) for preparing a polyrotaxane A in which a linear molecule is entangled at an opening of a cyclic molecule to form a pseudopolyrotaxane, and blocking groups are disposed at both ends of the pseudopolyrotaxane so that the cyclic molecule does not detach from the pseudopolyrotaxane;

a step (b) of reacting a compound represented by the following formula II (wherein R is in the formula II)₁Having the same definition as above) with the polyrotaxane A, and a compound having the following formula I (wherein R is R in the formula I) provided on a cyclic molecule₁、R₂And n has the same definition as above).

< Process (a) >)

The step (a) is a step of preparing a polyrotaxane a.

This step can be carried out by a conventionally known method, and for example, polyrotaxane A can be prepared by the method described in WO2005/052026 or WO 2013/147301. Step (a) can be performed by purchasing polyrotaxane a on the market.

< Process (b) >)

The step (b) is a step of reacting the compound represented by the formula II with a polyrotaxane A to provide a substituent represented by the formula I on a cyclic molecule. In addition, R is₂In the case where the compound other than H is used, after the compound represented by the above formula II is reacted with polyrotaxane a, the corresponding R group may be provided to all or a part of the terminal hydroxyl group (terminal hydroxyl group of R ═ H).

The reaction conditions of the step (b) may be determined depending on the polyrotaxane a used and the compound used, but the reaction may be carried out in the presence of i) a superbase or in the presence of ii) a polymerization initiator.

Examples of the superbase i) include, but are not limited to, phosphazene bases, guanidine bases, phosphorus-containing bicyclic organic nonionic superbases (proazaphosphorathran), and metal bases. Particular preference is given to using phosphazene bases. When a superbase is used, the conditions include, but are not limited to, 20 to 100 ℃ and atmospheric or pressurized conditions.

Examples of the ii) polymerization initiator include, but are not limited to, tetra-n-butylammonium fluoride. When a polymerization initiator is used, it may be used in combination with a strong base. Examples of the strong base include, but are not limited to, Diazabicycloundecene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), trimethylamine, N-dimethyl-4-aminopyridine, sodium hydroxide, and potassium hydroxide. When a polymerization initiator is used, the conditions include, but are not limited to, 20 ℃ to 100 ℃ under normal pressure or under pressure.

In the step (b), a further solvent may or may not be used. When a further solvent is used, examples of the solvent include, but are not limited to, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, toluene, xylene, methyl ethyl ketone, and the like.

The reaction in the step (b) may be carried out under normal pressure to elevated pressure, and the reaction may be accelerated when the pressure is elevated. The reaction temperature depends on the polyrotaxane A to be used, the compound to be used, the solvent to be used, and the like, but may be carried out at room temperature to 130 ℃.

< method for producing Material of the present invention >

The polyrotaxane of the present invention obtained as described above can be used for producing a material.

The method for producing the material depends on substances other than the polyrotaxane of the present invention. For example, the polyrotaxane of the present invention may be used in addition to the polyrotaxane, and when the polyrotaxane is used, at least a part of the polyrotaxane of the present invention and at least a part of the polyrotaxane may be directly or indirectly bonded to each other as described above, and a crosslinked body may be formed.

When a case of using propylene glycol as the substance is described as an example, (c) -1. reacting the polyrotaxane of the present invention with a substance other than the polyrotaxane, specifically, with a polyfunctional isocyanate compound such as propylene glycol and hexamethylene diisocyanate in the presence of a polyfunctional isocyanate compound such as hexamethylene diisocyanate as a crosslinking agent, at least a part of the polyrotaxane of the present invention and at least a part of the propylene glycol can be indirectly bonded through the polyfunctional isocyanate compound such as hexamethylene diisocyanate to form a crosslinked body. The crosslinking agent may be the one described above.

In addition, (c) -2. reacting the polyrotaxane of the present invention with a substance other than the polyrotaxane in the presence of a catalyst and an initiator, at least a part of the polyrotaxane of the present invention and at least a part of the substance can be directly bonded to each other, and a crosslinked body can also be formed.