JP2021105102A - Rotaxane polyurea crosslinked body, rotaxane polyurea-urethane crosslinked body, and method for producing the same - Google Patents

Abstract

To provide a novel rotaxane and a production method therefor.SOLUTION: A rotaxane polyurea crosslinked body has at least one cyclodextrin and a polyurea chain penetrating the cyclodextrin. The cyclodextrin of the rotaxane polyurea is crosslinked with a crosslinker.SELECTED DRAWING: Figure 1

Description

The present invention relates to a novel rotaxane and a method for producing the same.

Various studies and developments have been made on rotaxane crosslinked products.

For example, Patent Document 1 describes a first polyrotaxane in which a first linear molecule is included in an opening of a first cyclic molecule in a skewered manner, and both of the first linear molecule. A first polyrotaxane having a first blocking group at the end and the first blocking group being arranged so that the first cyclic molecule cannot be desorbed, and a second at the opening of the second cyclic molecule. A second polyrotaxane in which a linear molecule is encapsulated in a skewered manner, the second blocking group having a second blocking group at both ends of the second linear molecule, and the second blocking group is the second. The ring of the first and second cyclic molecules is a substantial ring, and at least one of the first cyclic molecules and the said A compound having a crosslinked polyrotaxane in which at least one of the second cyclic molecules is bonded via a chemical bond, and the molecular weights of the first linear molecule and the second linear molecule are 10,000. As described above, a compound in which the compound is a viscoelastic material is disclosed.

Patent Document 2 describes a material having a first polyrotaxane and a second polyrotaxane, wherein the opening of the first cyclic molecule is skewered by a first linear molecule. A first blocking group is arranged at both ends of the first pseudo-polyrotaxane that is in contact with each other so that the first cyclic molecule is not detached, and the second polyrotaxane is an opening of the second cyclic molecule. A second blocking group is arranged at both ends of the second pseudopolyrotaxane, which is skewered by the second linear molecule, so that the second cyclic molecule is not detached. The first and second polyrotaxans are crosslinked via the first and second cyclic molecules, the material is solvent-free, and the material has an X) compressive permanent strain of 10% or less; Y) tensile stress. Materials with at least one property selected from the group consisting of relaxation of 15% or less; and Z) hysteresis loss of 25% or less are disclosed.

Japanese Patent No. 3475252 Japanese Unexamined Patent Publication No. 2011-241401

An object of the present invention is to provide a novel rotaxane and a method for producing the same.

The cross-linked product of rotaxane polyurea of the present invention is a cross-linked product of rotaxane polyurea having at least one cyclodextrin and a polyurea chain penetrating the cyclodextrin, and the cyclodextrin of the rotaxane polyurea is cross-linked by a cross-linking agent. It is characterized by being done. The present invention is characterized in that the shaft molecule penetrating cyclodextrin is a polyurea chain, and cyclodextrin is crosslinked.

In the method for producing a crosslinked rotaxane polyurea of the present invention, at least one rotaxane diamine having a cyclodextrin and a diamine penetrating the cyclodextrin is reacted with a diisocyanate capable of penetrating the cyclodextrin. It is characterized by having a step of producing a rotaxane polyurea having the cyclodextrin of the above and a polyurea chain penetrating the cyclodextrin, and a step of cross-linking the cyclodextrin of the rotaxane polyurea with a cross-linking agent.

The present invention provides a novel rotaxane crosslinked product and a method for producing the same.

It is a schematic diagram schematically explaining one aspect of the molecular structure of the rotaxane polyurea crosslinked product of the present invention. It is a schematic diagram schematically explaining one aspect of the molecular structure of the rotaxane polyurea crosslinked product of the present invention. It is a schematic diagram schematically explaining one aspect of the molecular structure of the rotaxane polyurea crosslinked product of the present invention. It is a schematic diagram schematically explaining one aspect of the molecular structure of rotaxane diamine used in the present invention. It is a schematic diagram schematically explaining an example of the reaction scheme for producing rotaxane polyurea used in this invention. It is explanatory drawing which shows an example of the reaction scheme for producing rotaxane polyurea used in this invention. It is explanatory drawing which shows an example of the reaction scheme for producing the rotaxane polyurea cross-linked product of this invention. ^{It is 1} H-NMR spectrum of an example of rotaxane polyurea used in this invention. ¹ H-NMR spectrum of an example of a crosslinked rotaxane polyurea of the present invention.

The cross-linked product of rotaxane polyurea of the present invention is a cross-linked product of rotaxane polyurea having at least one cyclodextrin and a polyurea chain penetrating the cyclodextrin, and the cyclodextrin of the rotaxane polyurea is cross-linked by a cross-linking agent. It is characterized by being done. The crosslinked body of rotaxane polyurea of the present invention has a rotaxane structure in which a polyurea chain, which is an axial molecule, penetrates a cavity of cyclodextrin, and the gist is that cyclodextrin is crosslinked.

In the present invention, the "rotaxane" means a molecule having a structure having at least one cyclic molecule (cyclodextrin) and an axial molecule penetrating the cavity of the cyclic molecule (cyclodextrin). It does not matter whether or not the shaft molecule has a structure that blocks the cyclic molecule (cyclodextrin) from desorbing from the shaft molecule. A "rotaxane" having two or more cyclic molecules (cyclodextrin) through which an axial molecule penetrates may be referred to as a "polyrotaxane". The "polyrotaxane" having two or more cyclic molecules (cyclodextrin) penetrating the shaft molecule is contained in the "rotaxane" having at least one cyclic molecule (cyclodextrin) penetrating the shaft molecule. .. When referred to as "rotaxane polyurea" and "rotaxane diamine", "polyurea" and "diamine" mean axial molecules penetrating a cyclic molecule (cyclodextrin), respectively.

The number of cyclodextrins contained in one molecule of rotaxane polyurea used in the present invention is not particularly limited as long as it is at least one. The number of cyclic molecules contained in one molecule of rotaxane polyurea is preferably 3 or more, more preferably 4 or more, further preferably 5 or more, and preferably 100 or less. ..

FIG. 1 is a schematic diagram schematically showing an example of the molecular structure of the crosslinked body 1 of the rotaxane polyurea of the present invention. The rotaxane polyurea 2 has a cyclodextrin 3 and a polyurea chain 5 penetrating the cyclodextrin 3. The cyclodextrin 3 contained in rotaxane polyurea 2 is crosslinked by the cross-linking agent 6. The rotaxane polyurea 2 of the embodiment shown in FIG. 1 does not have a blocking structure in the polyurea chain 5 that blocks the cyclodextrin 3 from desorbing from the polyurea chain 5, but the cyclodextrin 3 is constrained by the cross-linking structure. Therefore, the detachment from the polyurea chain 5 is suppressed. Although FIG. 1 shows an intermolecular crosslinked structure of two rotaxane polyurea molecules, the rotaxane polyurea crosslinked product of the present invention also includes an intramolecular crosslinked structure.

The rotaxane polyurea used in the present invention has at least one cyclodextrin and a polyurea chain penetrating the cyclodextrin, and the polyurea chain blocks the cyclodextrin from detaching from the polyurea chain. It is preferable to have a sealing structure in the main chain or at the end of the main chain. In the embodiment provided at the end of the main chain, it is preferable that the sealing structure is provided only at both ends of the main chain. By having a closed structure, elimination of cyclodextrin from the polyurea chain is suppressed.

FIG. 2 is a schematic diagram schematically showing an example of the molecular structure of the rotaxane polyurea crosslinked product 1 of the present invention. The rotaxane polyurea 2 has a cyclodextrin 3 and a polyurea chain 5 penetrating the cyclodextrin 3. A blocking structure 7 is provided in the main chain of the polyurea chain 5 to block the cyclodextrin 3 from desorbing from the polyurea chain 5. Cyclodextrin 3 can move along the axis molecule between adjacent blockade structures 7. The cyclodextrin 3 contained in rotaxane polyurea 2 is crosslinked by the cross-linking agent 6.

FIG. 3 is a schematic diagram schematically showing an example of the molecular structure of the rotaxane polyurea crosslinked product 1 of the present invention. The rotaxane polyurea 2 has a cyclodextrin 3 and a polyurea chain 5 penetrating the cyclodextrin 3. Only at both ends of the main chain of the polyurea chain 5, a blocking structure 7 is provided to block the cyclodextrin 3 from detaching from the polyurea chain 5. Cyclodextrin 3 can move over the entire area of the polyurea chain 5, which is an axial molecule. The cyclodextrin 3 contained in rotaxane polyurea 2 is crosslinked by the cross-linking agent 6.

The rotaxane polyurea used in the present invention is preferably obtained by reacting a rotaxane diamine having at least one cyclodextrin and a diamine penetrating the cyclodextrin with a diisocyanate.

The polyurea chain, which is the axis molecule of rotaxane polyurea used in the present invention, will be described. The polyurea chain is not particularly limited as long as it has a plurality of urea bonds in the molecular chain and can penetrate cyclodextrin. The polyurea chain is preferably one in which a urea bond is formed in the molecular chain by the reaction of a rotaxane diamine having at least one cyclodextrin and a diamine penetrating the cyclodextrin with a diisocyanate. The diamine contained in rotaxane diamine reacts with diisocyanate to form a polyurea chain having a plurality of urea bonds. Since the formed polyurea chain maintains a state of penetrating the cyclodextrin possessed by the rotaxane diamine, a rotaxane having at least one cyclodextrin and a polyurea chain penetrating the cyclodextrin. The structure is formed.

The rotaxane diamine constituting the rotaxane polyurea used in the present invention will be described.

1. 1. Rotaxane diamine The rotaxane diamine has at least one cyclodextrin and a diamine penetrating the cyclodextrin. That is, the rotaxane diamine has a rotaxane structure in which the diamine, which is an axial molecule, penetrates the cavity of cyclodextrin.

FIG. 4 is a schematic view schematically showing the rotaxane diamine. The rotaxane diamine 9 has two cyclodextrins 11 and a diamine 13 penetrating the cyclodextrin.

The number of cyclodextrins contained in one molecule of rotaxane diamine is not particularly limited as long as it is at least one. The number of cyclodextrins contained in one molecule of rotaxane diamine is preferably 2 or more, preferably 8 or less, and more preferably 4 or less.

The rotaxane diamine may or may not have a blocking group that prevents cyclodextrin from desorbing from the shaft molecule diamine. In the present invention, it is preferable to use a rotaxane diamine that does not have a blocking group that prevents cyclodextrin from being eliminated from the diamine. Without a blocking group, the cyclodextrin contained in rotaxane diamine can move to other molecular chain portions constituting the polyurea chain without being bound by the molecular chain derived from the diamine. In the present invention, the rotaxane diamine having no blocking group may be referred to as "pseudo-rotaxane diamine".

The cyclodextrin is an organic compound having a cyclic structure having a hollow portion in the center. The cyclodextrin is a general term for oligosaccharides having a cyclic structure. Cyclodextrin is, for example, 6 to 8 D-glucopyranose residues linked cyclically by α-1,4-glucosidic bonds. Examples of cyclodextrin include α-cyclodextrin (glucose number: 6), β-cyclodextrin (glucose number: 7), γ-cyclodextrin (glucose number: 8), and α-cyclodextrin. preferable. The inner diameters of the cavities of α-cyclodextrin (glucose number: 6), β-cyclodextrin (glucose number: 7), and γ-cyclodextrin (glucose number: 8) are about 0.57 nm and about, respectively. It is 0.78 nm and about 0.95 nm. In the cyclic structure of cyclodextrin, there are a plurality of hydroxyl groups capable of reacting with isocyanate groups and epoxy groups.

The diamine is an organic compound having two amino groups. The diamine preferably has a small steric hindrance so that it can penetrate the cyclodextrin. From such a viewpoint, the diamine is preferably a linear diamine, and more preferably a linear alkane diamine. The amino group is preferably located at both ends of the molecular chain in order to enhance the reactivity with diisocyanate.

The number of carbon atoms of the diamine is not particularly limited, but is preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, from the viewpoint of the balance between the number of penetrating cyclodextrin and the ease of penetrating cyclodextrin. , 12 or more is particularly preferable, 30 or less is preferable, 25 or less is more preferable, and 20 or less is further preferable.

Examples of the diamine include 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1, 12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecandiamine, 1,17-heptadecanediamine, 1,18-octadecandiamine, 1 , 19-Nonadecanediamine, 1,20-Icosandiamine and the like. The diamine used in the present invention is preferably 1,12-dodecanediamine.

2. Diisocyanate The diisocyanate is an organic compound having two isocyanate groups. The diisocyanate constitutes a polyurea chain which is a shaft molecule. Further, in the polyurea chain, diisocyanate having less steric hindrance is preferable because it constitutes a movable region of cyclodextrin.

Examples of the diisocyanate include a diisocyanate monomer and a diisocyanate macromonomer.

Examples of the diisocyanate monomer include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDI), and 4,4'-diphenylmethane diisocyanate (MDI). ), 1,5-naphthylene diisocyanate (NDI), 3,3'-bitrylene-4,4'-diisocyanate (TODI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), paraphenylene diisocyanate ( Aromatic polyisocyanates such as PPDI); 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI), hydrogenated xylylene diisocyanate (H ₆ XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), norbornene diisocyanate ( Examples thereof include alicyclic polyisocyanates such as NBDI) and aliphatic polyisocyanates.

The diisocyanate macromonomer is, for example, a product obtained by reacting a compound having two functional groups that react with an isocyanate group and the diisocyanate monomer under conditions such that the isocyanate group becomes excessive. The product diisocyanate macromonomer is a macromonomer (prepolymer) having a higher molecular weight than the diisocyanate monomer, and has two isocyanate groups at the ends.

Examples of the compound having two functional groups that react with the isocyanate group include diols, diamines, aminoalcohols and the like.

Examples of the diol include low molecular weight diols having a molecular weight of less than 500 and high molecular weight diols having a number average molecular weight of 500 or more. In the present invention, as the diol component constituting the diisocyanate macromonomer, it is preferable to use a diol having a number average molecular weight of 500 to 10,000, and more preferably to use a diol having a number average molecular weight of 1000 to 5000.

Examples of the low molecular weight diol include diols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, and 1,6-hexanediol.

Examples of the high molecular weight diol include polyether diols, polyester diols, polycaprolactone diols, and polycarbonate diols.

Examples of the polyether diol include polyoxyethylene glycol (PEG), polyoxypropylene glycol (PPG), polyoxyethylene / polyoxypropylene glycol, polyoxytetramethylene glycol (PTMG) and the like. Examples of the polyester polyol include polyethylene adipate (PEA), polybutylene adipate (PBA), polyhexamethylene adipate (PHMA) and the like. Examples of the polycaprolactone polyol include poly-ε-caprolactone (PCL). Examples of the polycarbonate polyol include polyhexamethylene carbonate and the like.

The number average molecular weight of the diisocyanate macromonomer is preferably 500 or more, more preferably 800 or more, further preferably 1000 or more, preferably 10000 or less, further preferably 8000 or less, still more preferably 5000 or less.

In a preferred embodiment of the present invention, the diisocyanate macromonomer is, for example, a prepolymer having an isocyanate group terminal obtained by reacting a diisocyanate monomer with a polyether diol at NCO / OH = 2/1 to 3/2 (molar ratio). Is preferable.

In a more preferable aspect of the present invention, the diisocyanate macromonomer is preferably a compound represented by the following formula (1) formed by reacting 2,4-toluene diisocyanate with polyoxypropylene glycol (PPG).

（１）
［式（１）中、ｎは、繰り返し単位の数を表し、７〜１８０の数である。］

(1)
[In the formula (1), n represents the number of repeating units, which is a number from 7 to 180. ]

3. 3. Other Components Constituting Polyurea Chains The rotaxane polyurea used in the present invention contains diamines and / or diols as components constituting the polyurea chain, which is an axial molecule, in addition to the above-mentioned rotaxane diamine and diisocyanate. You may have.

As the diamine, those listed as diamines, which are the axial components of rotaxane diamine, can be used. Further, as the diol, those listed as diol components constituting the diisocyanate macromonomer can be used.

When the rotaxane polyurea of the present invention contains a diol component as a component constituting the polyurea chain, a urethane bond is formed in the polyurea chain, which is a shaft molecule penetrating cyclodextrin, in addition to the urea bond. Therefore, the polyurea chain becomes a rotaxane polyurea urethane chain. Therefore, the rotaxane polyurea of the present invention contains rotaxane polyurea urethane.

4. Closing Compound The rotaxane polyurea used in the present invention has at least one cyclodextrin and a polyurea chain penetrating the cyclodextrin, and the polyurea chain prevents the cyclodextrin from being detached from the polyurea chain. It is preferable to have a sealing structure to be sealed in the main chain or at the end of the main chain.

The size of the molecule forming the closed structure may be appropriately selected according to the inner diameter of the cyclodextrin. For example, the diameter of the circumscribed circle of the benzene ring is about 0.278 nm, and the length of the CH bond of the benzene ring is 0.110 nm. For example, the CH bond length in the methane molecule is 0.110 nm. The CC bond length in the ethane molecule is about 0.153 nm and the CH bond length is 0.110 nm.

The blocking structure in the polyurea main chain is a compound having two functional groups that react with the rotaxane diamine or diisocyanate, and is a blocking compound that blocks the cyclodextrin by steric hindrance (hereinafter, "bifunctional group blocking compound"). It is preferable that it is formed by.).

The bifunctional group-blocking compound is not particularly limited as long as it has two functional groups capable of reacting with an amino group or an isocyanate group and blocks the cyclodextrin by steric hindrance. Examples of the bifunctional group blocking compound include diamines, diisocyanates and diols.

Specific examples of the bifunctional group-blocking compound include bis (4-isocyanate-3,5-diethylphenyl) methane, bis (4-amino-3,5-diethylphenyl) methane, and bis (4-hydroxy-). 3,5-diethylphenyl) methane and the like.

When the blocking structure is contained in the main chain, the proportion of the bifunctional group blocking compound constituting the polyurea chain is preferably 1.0 mol% or more, more preferably 1.5 mol% or more, and 2.0 mol% or more. More preferably, 10.0 mol% or less is preferable, 8.0 mol% or less is more preferable, and 6.0 mol% or less is further preferable. When the proportion of the bifunctional group-blocking compound is 1.0 mol% or more, the sealing structure can suppress the elimination of cyclodextrin from the polyurea chain. Further, when the ratio of the bifunctional group-blocking compound is 10.0 mol% or less, the movable region of cyclodextrin in the polyurea chain becomes wide. As a result, the physical properties of the obtained rotaxane polyurea are improved. The ratio of the bifunctional group-blocking compound is calculated by the following formula.
Ratio of bifunctional group-blocking compound = 100 × [number of moles of bifunctional group-blocking compound / (number of moles of bifunctional group-blocking compound + number of moles of diisocyanate + number of moles of rotaxanediamine)

The blocking structure at the terminal of the main chain of polyurea is a compound having one functional group that reacts with the rotaxane diamine or diisocyanate, and is a blocking compound that blocks the cyclodextrin by steric hindrance (hereinafter, "monofunctional group blocking compound"). It is preferable that it is formed by.).

The monofunctional group-blocking compound is not particularly limited as long as it has one functional group capable of reacting with an amino group or an isocyanate group and blocks the cyclodextrin by steric hindrance. Examples of the monofunctional group-blocking compound include monoamines, monoisocyanates, and monoalcohols.

Specific examples of the monofunctional group-blocking compound include 3,5-dimethylphenylisocyanate, 3,5-dimethylbenzylamine, and 3,5-dimethylbenzyl alcohol.

The rotaxane polyurea of the present invention may be either a block type or a random type. By appropriately selecting the manufacturing method, it can be made into a block type or a random type.

The number average molecular weight (Mn) of the entire molecule of rotaxane polyurea used in the present invention is preferably 15,000 or more, more preferably 20,000 or more, and even more preferably 25,000 or more. The upper limit is not particularly limited, but is preferably 500,000.

The number average molecular weight (Mn) of the polyurea chain, which is the axial molecule of rotaxane polyurea used in the present invention, is preferably 15,000 or more, more preferably 20,000 or more, still more preferably 25,000 or more. The upper limit is not particularly limited, but is preferably 500,000, more preferably 450,000, and even more preferably 400,000.

The molecular weight distribution (PDI) (Mw / Mn) of the entire molecule of rotaxane polyurea used in the present invention is preferably 1.5 or more, more preferably 1.7 or more, preferably 4.0 or less, and 3.5 or less. More preferably, 3.0 or less is further preferable.

The number average molecular weight and the molecular weight distribution are measured by a method described later.

5. Cross-linking agent The cross-linking agent is not particularly limited as long as it is a compound having two or more functional groups that react with the hydroxy group of cyclodextrin, which is a cyclic molecule of the rotaxane polyurea. Examples of the functional group include an epoxy group and an isocyanate group. Of these, isocyanate groups are preferred.

As the cross-linking agent, polyisocyanate is preferable, and the rotaxane polyurea is cross-linked by reacting with the hydroxy group of cyclodextrin. Examples of the polyisocyanate that can be used as the cross-linking agent include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDI), 4. , 4'-Diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 3,3'-bitrylene-4,4'-diisocyanate (TODI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), aromatic diisocyanates such as paraphenylenediocyanate (PPDI); 4,4'-dicyclohexylmethane diisocyanate (H12MDI), hydrogenated xylylene diisocyanate (H6XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), Alicyclic diisocyanates such as norbornene diisocyanates (NBDI) or aliphatic diisocyanates; and triisocyanates such as alohanates, bullets, isocyanurates, and adducts of these diisocyanates; can be mentioned. The polyisocyanate may be used alone or in combination of two or more.

From the viewpoint of adjusting the distance between the cross-linking points, it is also a preferable embodiment to use a diisocyanate macromonomer capable of forming a polyurea chain of rotaxane polyurea as the cross-linking agent.

As the epoxy-based cross-linking agent, a polyvalent glycidyl compound is preferable. Examples of the epoxy-based cross-linking agent include bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, polyalkylene ether diglycidyl ether, phthalic acid glycidyl ester, tetraglycidyl diaminodiphenylmethane, triglycidyl isocyanurate and the like. Can be mentioned.

The molar ratio of the cross-linking agent to the cyclodextrin contained in the rotaxane polyurea (cross-linking agent / cyclodextrin × 100) is preferably 15 mol% or less, more preferably 10 mol% or less, still more preferably 8 mol% or less. When the amount of the cross-linking agent used is higher than 15 mol%, the degree of cross-linking of the obtained rotaxane polyurea cross-linked product becomes high, and the cross-linked product may become brittle in nature. The lower limit of the molar ratio of the cross-linking agent to the cyclodextrin (cross-linking agent / cyclodextrin × 100) of the rotaxane polyurea is not particularly limited, but is preferably 1.0 mol%, more preferably 2.0 mol%, and 3 .0 mol% is more preferred.

The Young's modulus of the crosslinked rotaxane polyurea of the present invention is preferably 7 MPa or more, more preferably 8 MPa or more, still more preferably 9 MPa or more.

The elongation at break of the crosslinked rotaxane polyurea of the present invention is preferably 5% or more, more preferably 8% or more, further preferably 10% or more, and most preferably 20% or more.

The breaking stress of the crosslinked rotaxane polyurea of the present invention is preferably 0.5 MPa or more, more preferably 1.0 MPa or more, still more preferably 1.5 MPa or more.

The Young's modulus, breaking strain, and breaking stress are measured by a method described later.

In the rotaxane polyurea used in the present invention, the ratio (coverage θ1) in which the diamine component, which is the axis molecule of the rotaxane diamine constituting the polyurea chain, is included in the cyclic molecule cyclodextrin is preferably 10% or more. 15% or more is more preferable, 80% or less is preferable, and 60% or less is more preferable. This is because if the coverage rate θ1 is within the above range, sufficient elongation and strength can be obtained.

In the rotaxane polyurea used in the present invention, the ratio (coverage θ2) in which the entire polyurea chain is encapsulated with cyclodextrin, which is a cyclic molecule, is preferably 0.5% or more, more preferably 1.0% or more, and 15%. % Or less is preferable, and 10% or less is more preferable. This is because if the coverage rate θ2 is within the above range, sufficient elongation and strength can be obtained.

Next, a method for producing the rotaxane polyurea crosslinked product of the present invention will be described.

In the method for producing a crosslinked rotaxane polyurea of the present invention, at least one rotaxane diamine having a cyclodextrin and a diamine penetrating the cyclodextrin is reacted with a diisocyanate capable of penetrating the cyclodextrin. It is characterized by having a step of producing a rotaxane polyurea having the cyclodextrin of the above and a polyurea chain penetrating the cyclodextrin, and a step of cross-linking the cyclodextrin of the rotaxane polyurea with a cross-linking agent.

In the rotaxane polyurea production step, the diamine contained in the rotaxane diamine reacts with the diisocyanate to form a polyurea chain having a plurality of urea bonds. Since the formed polyurea chain maintains a state of penetrating the cyclodextrin possessed by the rotaxane diamine, a rotaxane having at least one cyclodextrin and a polyurea chain penetrating the cyclodextrin. The structure is formed. Next, in the cross-linking step, the cyclodextrin contained in the obtained rotaxane polyurea is cross-linked with a cross-linking agent.

In a preferred embodiment, the diisocyanate macromonomer described above is used as the diisocyanate component. This is because the use of the diisocyanate macromonomer facilitates the increase in the molecular weight of rotaxane polyurea.

In the rotaxane polyurea production step, in addition to the above-mentioned rotaxane diamine and diisocyanate, diamine and / or diol and the like may be used as constituent components as constituents of the polyurea chain which is a shaft molecule.

In the rotaxan polyurea manufacturing process, a one-shot method in which all raw materials are reacted at once, some raw materials are reacted first to prepare a prepolymer having a medium molecular weight, and this prepolymer is used as a chain length extender component. Examples thereof include a prepolymer method in which the polymer is further increased in molecular weight.

In the process for producing rotaxane polyurea, it is preferable that the polyurea chain of rotaxane polyurea is provided with a sealing structure in the main chain or at the end of the main chain to prevent cyclodextrin from being detached from the polyurea chain.

When a blocking structure is provided at the ends of the main chain of the polyurea chain (preferably only at both ends of the main chain), for example, rotaxandiamine and diisocyanate are reacted to prepare a polyurea chain, and amino present at both ends of the polyurea chain. A sealing structure can be provided at the end of the main chain by reacting a group or an isocyanate group with a sealing compound having one functional group that reacts with an amino group or an isocyanate group.

When a blocking structure is provided in the main chain of a polyurea chain, the blocking structure is provided in the main chain by reacting rotaxanediamine and diisocyanate with a blocking compound having two functional groups that react with the rotaxanediamine or diisocyanate. Can be done.

FIG. 5 is a diagram schematically showing an example of a reaction scheme in the rotaxane polyurea production process. In FIG. 5, a random rotaxane polyurea 19 is obtained by reacting rotaxane diamine 9 with a diisocyanate macromonomer 15 with a blocking compound 17 having two functional groups X that react with rotaxane diamine or diisocyanate macromonomer.

Examples of the sealing compound used in the rotaxane polyurea manufacturing process include the above-mentioned sealing compounds. These blocking compounds may be used alone or in combination of two or more.

When a diisocyanate macromonomer (diisocyanate macromonomer having a urethane bond in the molecule) obtained by reacting the above-mentioned diisocyanate monomer and a polyether diol is used as the diisocyanate in the rotaxan polyurea production process, the product is rotaxan polyurea.・ Corresponds to urethane. Therefore, the method for producing the rotaxane polyurea-urethane crosslinked product of the present invention is included in the method for producing the rotaxane polyurea cross-linked product.

In the process of producing rotaxanpolyurea, in the reaction between diisocyanate and rotaxanediamine, the molarity of the isocyanate group of diisocyanate and the functional group of the compound having a functional group that reacts with the isocyanate group (for example, hydroxy group, amino group, imino group, etc.) The ratio is preferably 0.8 / 1.0 to 1.2 / 1.0. This is because the molecular weight is suitable when the molar ratio is within the above range.

The production method of the present invention includes a step of cross-linking the rotaxane polyurea obtained in the rotaxane polyurea production step with a cross-linking agent (in the present invention, it may be simply referred to as a "cross-linking step"). Cross-linking of rotaxane polyurea is not particularly limited as long as it is a method of contacting rotaxane polyurea with a cross-linking agent. Cross-linking of rotaxane polyurea can be carried out, for example, by mixing and reacting a rotaxane polyurea composition containing rotaxane polyurea with a cross-linking agent.

The rotaxane polyurea used in the cross-linking step is the rotaxane polyurea obtained above. One type of rotaxane polyurea may be used alone, or two or more types may be used in combination.

Examples of the cross-linking agent used in the cross-linking step include the above-mentioned cross-linking agent. These cross-linking agents may be used alone or in combination of two or more.

In the production method of the present invention, it is preferable to use a solvent. Specific examples of the solvent include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), and the like, and DMF having high solubility of the raw material. Is preferable.

Known catalysts in the synthesis of polyurethane can be used in the production method of the present invention. Examples of the catalyst include monoamines such as triethylamine, N, N-dimethylcyclohexylamine; N, N, N', N'-tetramethylethylenediamine, N, N, N', N'', N''-. Polyamines such as pentamethyldiethylenetriamine; cyclic diamines such as 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) and triethylenediamine; tin catalysts such as dibutyltin dilaurylate and dibutyltin diacetate, etc. Can be mentioned. These catalysts may be used alone or in combination of two or more. Among these, tin-based catalysts such as dibutyltin dilaurylate and dibutyltin diacetate are preferable, and dibutyltin dilaurylate is particularly preferably used.

In the production method of the present invention, it is preferable to use the catalyst only in the crosslinking step. The cross-linking step is preferably carried out, for example, at a reaction temperature in the range of −10 ° C. to 100 ° C. for 1 hour to 48 hours. Since the reaction between rotaxane diamine and diisocyanate reacts rapidly, it is not necessary to use a catalyst.

The reaction temperature of diisocyanate and rotaxane diamine is not particularly limited, but is preferably less than 100 ° C, more preferably 50 ° C or lower, and even more preferably 30 ° C or lower. Since the isocyanate group and the amino group react violently, it is preferable to react them at a low temperature.

The reaction time between the diisocyanate and the rotaxane diamine is not particularly limited, but is preferably 6 hours or more, more preferably 12 hours or more, still more preferably 18 hours or more. Further, from the viewpoint of production efficiency, the reaction time is preferably 24 hours or less.

The product obtained by the above-mentioned production method may be purified by a usual purification method. For example, the obtained product (containing a solvent or the like) is poured into water, and the obtained precipitate is purified by vacuum heating and drying.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples, and changes and embodiments within the scope of the present invention are all described in the present invention. Included within range.

[Evaluation method]
(1) ¹ Measurement of 1 H-NMR spectrum
^{1 1} H-NMR spectrum was recorded by Bruker Biospin AVANCE DPX-300 and Bruker AVANCE III HD500 using deuterated solvent. The spectrum was calibrated using a non-deuterated solvent and tetramethylsilane as internal standards.

(2) Number average molecular weight, weight average molecular weight, molecular weight distribution (dispersity)
The number average molecular weight and weight average molecular weight were determined by size exclusion chromatography (SEC) using a JASCO PU-2080 system equipped with polystyrene as a standard material, DMF (LiBr 5 mM) as an eluent, and TOSOH TSKgel G2500H and G4000H column sets as columns. It was measured under the conditions of 30 ° C. and a flow velocity of 0.85 ml / min. The molecular weight distribution was calculated by weight average molecular weight / number average molecular weight.

(3) Tensile test The tensile test was measured at an elongation rate of 167% / min at 25 ° C. using SHIMADZU AG-IS equipped with a 50 N load cell. From the results of this tensile test, the tensile physical properties (Young's modulus, fracture strain, fracture stress, fracture energy) were calculated. Young's modulus was calculated using the strain between 0% and 10% and its stress. A sheet made of a crosslinked rotaxane polyurea was punched into a dumbbell shape (60 mm) using a punching blade to prepare a sample for a tensile test.

(4) PU1 coverage rate θ1 (%)
¹ Calculated as follows from the measurement results of 1 H-NMR. ^{FIG. 8 is 1} H-NMR (400 MHz, 298 K, DMF-d ₇ ) data of PU1 produced as shown below. The integral value of-(CH ₂ ) _{10-of the} dodecane chain is 20, the integral value of the methyl group a in the PPG chain is 3 × 33 × 0.9 = 89.1, and the integral value of the methyl group f in the bulky isocyanate. The values are 3 × 4 × 0.1 = 1.2, and the total value of these is 20 + 89.1 + 1.2 = 110.3. This integrated value is used as a reference value. The integral value of C (1) H of cyclodextrin is 3.4. Here, when the dodecane chain is encapsulated by two cyclodextrins, the coverage is defined as 100%. When the dodecane chain is encapsulated by two cyclodextrins, the integral value of C (1) H of cyclodextrins is 12.
Therefore, the coverage rate θ1 of the dodecane chain portion is calculated as follows.
θ1 = (3.4 / 12) × 100 = 28% (PU1)

(5) PU1 coverage rate θ2 (%)
Cyclodextrin can contain two PPG units. That is, when the coverage rate θ2 = 100%, the 16.5 cyclodextrin unit encapsulates the diisocyanate macromer (“NCO-PPG”). When two cyclodextrin units of the dodecane chain are added to this, 18.5 cyclodextrin units are present. Here, as calculated above, the number of cyclodextrin units in the dodecane chain portion of PU1 is 0.57 (= 3.4 / 12 × 2).
Therefore, the coverage rate θ2 of the polyurea chain is calculated as follows.
θ2 = (0.57 / 18.5) × 100 = 3.0% (PU1)

(6) PU10 coverage rate θ1 (%)
¹ Calculated as follows from the measurement results of 1 H-NMR. FIG. 9 is ¹ H-NMR (400 MHz, 298 K, DMSO-d ₆ ) data of PU 10 produced as shown below. The integral value of − (CH ₂ ) ₁₀ − of the dodecane chain is 20 × 0.95 = 19, the integral value of the methyl group a in the PPG chain is 3 × 33 = 99, and the integral value of the methyl group f in the bulky isocyanate. The values are 3 × 4 × 0.05 = 0.6, and the total value of these is 19 + 99 + 0.6 = 118.6. This integrated value is used as a reference value. The integral value of C (1) H of cyclodextrin is 3.4. Here, when the dodecane chain is encapsulated by two cyclodextrins, the coverage is defined as 100%. When the dodecane chain is encapsulated by two cyclodextrins, the integral value of C (1) H of cyclodextrins is 12 × 0.95 = 11.4.
Therefore, the coverage rate θ1 of the dodecane chain portion is calculated as follows.
θ1 = (3.4 / (12 × 0.95)) × 100 = 30% (PU10)

(7) PU10 coverage rate θ2 (%)
Cyclodextrin can contain two PPG units. That is, when the coverage rate θ2 = 100%, the 16.5 cyclodextrin unit encapsulates the diisocyanate macromer (“NCO-PPG”). When 2 × 0.95 = 1.9 cyclodextrin units of the dodecane chain are added to this, 18.4 cyclodextrin units are present. Here, as calculated above, the number of cyclodextrin units in the dodecane chain portion of PU1 is 0.57 (= 2 × 0.30 × 0.95).
Therefore, the coverage rate θ2 of the polyurea chain is calculated as follows.
θ2 = (0.57 / 18.4) x 100 = 3.1% (PU10)

[Raw material for manufacturing rotaxane polyurea]
(1) Rotaxane diamine Rotaxane diamine was synthesized according to the method for synthesizing pseudo [3] rotaxane P1 described in Eur. J. Org. Chem. 2019, 3605-3613. Specifically, 1,12-diaminododecane (8.8 g, 44 mmol) was added to a solution of α-cyclodextrin (86 g, 89 mmol) in water (600 ml), the mixture was refluxed for 1 hour, and then at room temperature. It was allowed to stand overnight. The precipitate was collected by filtration, and the collected precipitate was washed with water and then vacuum dried to obtain rotaxane diamine (95 g) as white crystals.

According to the confirmation method described in Eur. J. Org. Chem. 2019, 3605-3613, this rotaxane diamine is composed of two cyclodextrins (α-cyclodextrin) and the above, as shown in FIG. It did not have a blocking group consisting of a terminal amino group linear diamine (1,12-diaminododecane) penetrating cyclodextrin. Hereinafter, this rotaxane diamine is abbreviated as pseudo [3] rotaxane diamine.

(2) Diisocyanate As the diisocyanate macromonomer, a compound of the following formula (2) (hereinafter, abbreviated as “NCO-PPG”) (Mr., Mn = 2300) was used. This compound is an isocyanate group-terminated urethane prepolymer (trimeric) formed by reacting 2,4-toluene diisocyanate at both ends of polypropylene glycol having an average degree of polymerization of oxypropylene unit of 33.

（２）

(2)

(3) Blockade compound As the blockade compound, bis (4-amino-3,5-diethylphenyl) methane (commercially available) was used. Its structure is represented by the following formula (3).

（３）

(3)

(4) Cross-linking agent 4,4'-diphenylmethane diisocyanate (MDI) was used as the cross-linking agent.

[Manufacture of rotaxane polyurea PU1 (one-shot method)]
In a solution of NCO-PPG (9.6 g, 4.2 mmol) and bis (4-isocyanate-3,5-diethylphenyl) methane (0.17 g, 0.47 mmol) in DMF (60 ml) at 0 ° C. , Pseudo [3] rotaxane diamine (10 g, 4.7 mmol) was added, and the mixture was stirred at room temperature for 24 hours. The obtained mixed solution was poured into water, and the precipitate was vacuum dried at 80 ° C. to obtain rotaxane polyurea PU1 (10.5 g, yield: 53%) as a white solid. The reaction scheme of PU1 is shown in FIG. The obtained rotaxane polyurea has a random structure. The ¹ H NMR data of PU1 is as follows (see FIG. 8).

The composition of rotaxane polyurea PU1 is shown in Table 1.

^{1 1} H NMR (300 MHz, 298 K, DMF-d ₇ ) δ 8.32-7.90 (m, 1.2H), 7.85-6.49 (m, 5.8H), 5.10-4.81 (m, C (1) H, 3.4H ), 3.84-3.15 (m, 113.5H), 2.58 (s, 0.80H), 2.24-2.05 (m, 5.4H), 1.52-0.86 (m, 110.3H) ppm.

[Manufacture of crosslinked rotaxane polyurea (PU10)]
Pseudo [3] rotaxane diamine (9.7 g, 4.5 mmol) was added to a solution of NCO-PPG (10.8 g, 4.7 mmol) in DMF (60 ml) at 0 ° C., and the mixture was stirred at room temperature for 24 hours. Later, bis (4-amino-3,5-diethylphenyl) methane (73 mg, 0.24 mmol) was added, followed by stirring for 24 hours. MDI (77 mg, 0.31 mmol) and dibutyltin dilaurylate (19 mg, 0.032 mmol) were added as cross-linking agents to the obtained mixed solution (containing rotaxane polyurea product, solvent, etc.), followed by 24 hours. Stirred. The obtained mixed solution was poured into water, and the precipitate was vacuum-dried at 80 ° C. to obtain rotaxane polyurea crosslinked product No. as a white solid. 1 (PU10) (12 g, yield: 59%) was obtained. Rotaxane polyurea crosslinked product No. ^{The 1} H-NMR data of 1 (PU10) is as follows (see FIG. 9).

^{1 1} H NMR (300 MHz, 298 K, DMF-d ₆ ) δ 9.64-6.41 (m, 14.9H), 5.70-5.46 (m, 2.7H), 5.04-4.81 (m, C (1) H, 3.4H ), 4.64-4.57 (m, 1.1H), 3.96-2.84 (m, 123.4H), 2.33-1.92 (m, 6.4H), 1.68-0.68 (m, 118.6H) ppm.

Separately, rotaxane polyurea is produced in the same manner as described above, the obtained mixed solution (containing the rotaxane polyurea product, solvent, etc.) is poured into water, and the precipitate is vacuum-dried at 80 ° C. to form a white solid. A purified rotaxane polyurea was obtained. When the obtained purified rotaxane polyurea was confirmed, its Mn was 31000, Mw was 93000, the molecular weight distribution was 3.0, the coverage of cyclodextrin in the diamine chain was 49%, and the coverage of cyclodextrin in the polyurea chain was 5. It was .3%.

In addition, except that the amounts of MDI and dibutyltin dilaurylate used were changed as shown in Table 1, the rotaxane polyurea crosslinked product No. In the same manner as in No. 1, rotaxane polyurea crosslinked product No. 2 and No. 3 was manufactured.

The reaction scheme in the production of the rotaxane polyurea cross-linking agent is shown in FIG.

The rotaxane polyurea crosslinked product No. 1-No. Table 2 shows the measurement results of MDI and dibutyltin dilaurylate, product yield, cyclodextrin coverage, and tensile physical properties (Young's modulus, breaking strain, breaking stress, breaking energy). ..

The crosslinked rotaxane polyurea of the present invention is useful as a novel material.

1: Rotaxane polyurea cross-linked product, 3: cyclodextrin, 5: polyurea chain, 6: cross-linking agent, 7: sealing structure, 9: rotaxane diamine, 11: cyclodextrin, 13: diamine, 15: diisocyanate macromonomer, 17: sealing Compound, 19: Random Rotaxane Polyurea

Claims (21)

A crosslinked body of rotaxane polyurea having at least one cyclodextrin and a polyurea chain penetrating the cyclodextrin, wherein the cyclodextrin of the rotaxane polyurea is crosslinked by a cross-linking agent. Crosslinked body. The crosslinked product of rotaxane polyurea according to claim 1, wherein the cross-linking agent is a polyisocyanate and reacts with a hydroxy group of cyclodextrin to crosslink the rotaxane polyurea. The polyurea chain is claimed 1 or 2 in which a urea bond is formed in the molecular chain by the reaction of a rotaxane diamine having at least one cyclodextrin and a diamine penetrating the cyclodextrin with a diisocyanate. The crosslinked form of rotaxane polyurea described. The crosslinked product of rotaxane polyurea according to claim 3, wherein the diisocyanate is a diisocyanate monomer or a diisocyanate macromonomer. The crosslinked rotaxane polyurea according to claim 3 or 4, wherein the rotaxane diamine has two cyclodextrins and a diamine penetrating the two cyclodextrins. The crosslinked rotaxane polyurea according to any one of claims 3 to 5, wherein the rotaxane diamine does not have a blocking group that prevents cyclodextrin from being eliminated from the diamine. The crosslinked product of rotaxane polyurea according to any one of claims 3 to 6, wherein the diamine contained in the rotaxane diamine is a linear alkane diamine having 6 to 20 carbon atoms. The crosslinked product of rotaxane polyurea according to claim 7, wherein the diamine contained in the rotaxane diamine is dodecane diamine. The crosslinked body of rotaxane polyurea according to claim 1 to 8, wherein the polyurea chain has a blocking structure in the main chain or at the end of the main chain that blocks the cyclodextrin from desorbing from the polyurea chain. The sealing structure in the main chain is the compound having two functional groups that react with the rotaxane diamine or diisocyanate, and is formed by the sealing compound that blocks the cyclodextrin by steric hindrance. A crosslinked form of rotaxane polyurea. The crosslinked product of rotaxane polyurea according to claim 10, wherein the blocking compound is at least one compound selected from the group consisting of diamine, diisocyanate, and diol. The sealing structure at the end of the main chain is a compound having one functional group that reacts with the rotaxane diamine or diisocyanate, and is formed by a blocking compound that blocks the cyclodextrin by steric hindrance. A crosslinked form of rotaxane polyurea. The crosslinked product of rotaxane polyurea according to claim 12, wherein the blocking compound is at least one compound selected from the group consisting of monoamines, monoisocyanates, and monoalcohols. The crosslinked product of rotaxane polyurea according to any one of claims 1 to 13, wherein the cyclodextrin is at least one selected from the group consisting of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. .. The polyurea chain of rotaxane polyurea according to claims 1 to 14 is a crosslinked product of rotaxane polyurea urethane which is a polyurea urethane chain having a urethane bond in the molecular chain of the polyurea chain. A rotaxane diamine having a cyclodextrin and a diamine penetrating the cyclodextrin is reacted with a diisocyanate capable of penetrating the cyclodextrin to penetrate at least one cyclodextrin and the cyclodextrin. A process for producing a rotaxane polyurea having a polyurea chain,
A method for producing a crosslinked rotaxane polyurea, which comprises a step of cross-linking the cyclodextrin contained in the rotaxane polyurea with a cross-linking agent. A rotaxane diamine having a cyclodextrin and a diamine penetrating the cyclodextrin, a diisocyanate capable of penetrating the cyclodextrin, and a compound having two functional groups reacting with the rotaxane diamine or the diisocyanate. A step of producing a rotaxane polyurea having a polyurea chain penetrating the cyclodextrin by reacting with a blocking compound that blocks the cyclodextrin due to steric hindrance.
A method for producing a crosslinked rotaxane polyurea, which comprises a step of cross-linking the cyclodextrin contained in the rotaxane polyurea with a cross-linking agent. The method for producing a crosslinked rotaxane polyurea according to claim 16 or 17, wherein a diisocyanate macromonomer is used as the diisocyanate. The method for producing a crosslinked rotaxane polyurea according to claim 18, wherein the diisocyanate macromonomer is obtained by reacting a diisocyanate monomer with a polyether diol. The method for producing a crosslinked rotaxane polyurea according to claim 17, wherein at least one compound selected from the group consisting of diamine, diisocyanate, and diol is used as the sealing compound. The method for producing a rotaxane polyurea crosslinked product according to any one of claims 16 to 20, wherein polyisocyanate is used as the cross-linking agent and is reacted with a hydroxy group of cyclodextrin to crosslink the rotaxane polyurea.

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