Polymer and unsaturated compound

Abstract

Provided is a polymer that has an aliphatic polyester resin skeleton and has excellent performance in strength while being biodegradable. The polymer has a cyclodextrin skeleton as a side chain of the polymer, and has a fatty acid polyester resin structure in at least one section.

Description

Polymers and Unsaturated Compounds

[0001] The present invention relates to a polymer and an unsaturated compound having a cyclodextrin skeleton.

[0002] Aliphatic polyesters such as polycaprolactone (PCL) are being investigated as environmentally friendly resins due to their biodegradability. They are also attracting attention from the perspective of being reusable through recycling, as they can be decomposed and recombined using enzymes.

[0003] However, since aliphatic polyesters do not have sufficient strength, improvements in their physical properties are required for their widespread use. Many attempts have been made to achieve this, and for example, crosslinking by covalent bonds has been considered. However, when crosslinking by covalent bonds is performed, the elasticity of the resin is significantly reduced, and although the strength can be increased, the resin becomes hard and brittle, and sufficient performance cannot be obtained. For this reason, it has been difficult to obtain a resin having excellent properties in both strength and elasticity using aliphatic polyesters.

[0004] Polymeric materials with cyclic molecules, cyclodextrin (CD), in their side chains are known (see, for example, Patent Document 2). In such polymeric materials, the polymer backbone penetrates the CD rings to form crosslinks, which slide when stress is applied, demonstrating high stress dispersibility. Regarding such structures, studies have been conducted mainly on acrylic resins, but not on polyester resins.

[0005] Non-Patent Document 1 describes the use of a polyurethane resin as a polymer having cyclic cyclodextrin in the side chain, but does not describe the modification of an aliphatic polyester resin.

[0006] JP 2019-203082 A International Publication No. 2022 / 024908

[0007] Soft Matter, 2022, 18, 5027-5036

[0008] An object of the present invention is to provide a polymer having an aliphatic polyester resin skeleton that is biodegradable and has excellent properties in terms of strength and flexibility.

[0009] The present invention is a polymer characterized by having a cyclodextrin skeleton as a side chain of the polymer and having a fatty acid polyester resin structure at least in part.

[0010] The fatty acid polyester resin structure is preferably polycaprolactone.

[0011] The cyclodextrin skeleton is (In the formula, R １ are the same or different and each represents a hydrogen atom, an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR ２ (R ２ represents an alkyl group having 1 to 20 carbon atoms, and R １ At least 20% of the groups are acyl groups having 2 to 50 carbon atoms, alkyl groups having 1 to 30 carbon atoms, or -CONHR ２ It is preferably any one of the following: x is an integer of 5 to 7.

[0012] The polymer of the present invention preferably has structural units derived from a compound (A) having a functional group reactive with two isocyanate groups present in a cyclodextrin skeleton and in a structure other than the cyclodextrin skeleton, an aliphatic polyester (B), and a diisocyanate compound (C).

[0013] Compound (A) is

[0014]

[0015] (In the formula, R １ are the same or different and each represents a hydrogen atom, an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR ２ (R ２ represents an alkyl group having 1 to 20 carbon atoms, and R １ At least 20% of the groups are acyl groups having 2 to 50 carbon atoms, alkyl groups having 1 to 30 carbon atoms, or -CONHR ２ It is preferably a compound represented by the following formula: where x is an integer of 5 to 7.

[0016] The aliphatic polyester (B) is preferably a polycaprolactone having a skeleton derived from a diol compound in part thereof. The polymer of the present invention may be obtained by polymerizing ε-caprolactone in the presence of an acrylic polymer having a cyclodextrin skeleton as a side chain of the polymer.

[0017] The polymerization of ε-caprolactone is preferably carried out further in the presence of a diol compound.

[0018] The present invention also relates to an unsaturated compound having a structure represented by the following general formula (11):

[0019] (In the formula, R １ (A) The following general formula (12) -R ３ -NH-R ４ (12) (R ３ is an alkylene group having 3 to 20 carbon atoms, which may be linear or branched, and may have a substituent. ４ is a structure represented by the following formula:

[0020] In the formula, R １０ represents hydrogen or a methyl group.

[0021] (A) The following general formula (13) -R ５ -NHCONH-R ６ (13) (R ５ is an alkylene group having 3 to 20 carbon atoms, which may be linear or branched, and may have a substituent. ６ is the above R ４ or (c) a compound represented by the following general formula (14): ５ -OCONH-R ６ (14) (R ５ and R ６ is the same as above.) R ２ represents a hydrogen atom, an acyl group having 2 to 50 carbon atoms, or an alkyl group having 1 to 30 carbon atoms. ｃ represents a group represented by the following general formula (1).

[0022] (In the formula, R１ are the same or different and each represents an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR ２ (R ２ represents an alkyl group having 1 to 20 carbon atoms, and R １ At least 20% of the groups are acyl groups having 2 to 50 carbon atoms, alkyl groups having 1 to 30 carbon atoms, or -CONHR ２ x is an integer of 5 to 7.

[0023] The resin composition of the present invention is mainly composed of an aliphatic polyester skeleton which has a small environmental impact, and yet has both elasticity and toughness.

[0024] Figure showing the shape of a tensile test sample. SH-2-DiOH １ H NMR (500 MHz, 25°C) PCL 1.5 k -diOH １ H NMR (500 MHz, 25°C). P.C.L. 1.5k -diOH １３ C NMR (125 MHz, 25°C). P.C.L. 2.4 k -diOH １ H NMR (500 MHz, 25°C). P.C.L. 2.4 k -diOH １３ C NMR (125 MHz, 25°C). P.C.L. 3.5 k -diOH １ H NMR (500 MHz, 25°C). P.C.L. ３．５ k -diOH １３ C NMR (125 MHz, 25°C). P.C.L. １．５ｋ -γCD (2) -PU １ H NMR (500 MHz, 25°C). P.C.L. １．５ｋ -γCD (5) -PU １ H NMR (500 MHz, 25°C). P.C.L. ２．４k -γCD (2) -PU 1 H NMR (500 MHz, 25°C). 2.4 k -γCD (5) -PU 1 H NMR (500 MHz, 25°C). ３．５ｋ -γCD (2) -PU1 H NMR (500 MHz, 25°C). ３．５ｋ -γCD(5)-PU 1 H NMR (500 MHz, 25°C). lPCL 1.5 k -PU 1 H NMR (500 MHz, 25°C). lPCL 2.4 k -PU 1 H NMR (500 MHz, 25°C). lPCL 3, 5 k -PU 1 H NMR (500 MHz, 25°C). 1.5k -THEED (2) -PU's 1 H NMR (500 MHz, 25°C). １．５k 1H NMR (500 MHz, 25°C) of -THEED (5) -PU. P.C.L. 2.4 k -THEED (2) -PU's 1 H NMR (500 MHz, 25°C). 2.4 k -THEED (5) -PU 1 H NMR (500 MHz, 25°C). ３．５k -THEED (2) -PU's 1 H NMR (500 MHz, 25°C). ３．５ｋ -THEED (5) -PU 1 H NMR (500 MHz, 25°C). (a) PCL 1.5 k -GPC curves of PUs; (b) PCL 2.4 k -GPC curves of PUs; (c) PCL 3.5 k -GPC curve of PUs. 2.4 k ATR-FTIRPCL of -PUs 2.4 k -DSC curve of second scan of PUs 2.4 k (a) Tg and (b) ΔH results of PCL-PUs. Stress-strain curves of PCL-PUs. 3.5 k -Stress-strain curves of PUs. Toughness and Young's modulus of PCL-PUs. PCL 3.5 k-Toughness and Young's modulus of PUs. Hysteresis loss calculated from cyclic stress-strain curves at a fixed strain (200%). 10 cycles were performed. (a) PCL １．５ｋ -γCD (2) -PU, (b) PCL １．５ｋ -γCD (5) -PU, (c) PCL ２．４ｋ -γCD (2) -PU, (d) PCL ２．４ｋ -γCD (5) -PU, strain (a) PCL recorded with increasing maximum strain (200%, 400%, 600%, 800%, 1000%, 1200%) ２．４ｋ (b) Energy dissipation and damping capacity of each circle of the cyclic tensile test curve for -γCD (5)-PU. (a) PCL recorded with increasing maximum strain (200%, 400%, 600%, 800%, 1000%, 1200%). ３．５ｋ (b) Energy dissipation and damping capacity (PCL) of each circle in the cyclic tensile test curve of -γCD(5)-PU. 2.4k -γCD (2) -Stress relaxation time curve of PU. PCL ３.５ｋ Stress relaxation time curves of (a) toughness and (b) Young's modulus of -γCD (5) -PU (original film (n=1), film after first recycling (n=2), second recycling (n=3)). Graph showing the results of enzymatic decomposition reaction. Graph showing the results of enzymatic polymerization reaction. Graph showing the results of enzymatic polymerization reaction. Stress-strain curve of polymer using SH-02-siOH. Toughness and Young's modulus of polymer using SH-02-siOH. Schematic diagram showing the hot pressing method. In the figure, Teflon is a registered trademark. Graph showing the shape of tensile test sample. Ac-γ-CD-AAm and pEAγXD_1 １ HNMR of pEAγCD1_PCL50 and PCL １HNMR dissolution curve of pEAγCD1_PCL50. Stress-strain curve and relationship between Young's modulus and breaking strength. (a) and (b) are the results for MC elastomer, and (C) and (D) are the results for pEAγCD1_PCL50. Stress-strain curve and relationship between Young's modulus and breaking strength for MC elastomer (pEAγCD1_PCLx (x = 0.50, 60, 70)). Stress-strain curves of (a) pEAγCD1_PCL50 and pEAγCD_1 (b) pEAγCD1_PCL50_M.

[0025] The present invention will be described in detail below. As described above, the polymer of the present invention has an aliphatic polyester skeleton as its main structural unit, and in order to improve its physical properties, it is a polymer having a cyclodextrin skeleton in its side chain. The cyclodextrin ring has a polymer main chain penetrating through its center, which gives it excellent elastic properties. Furthermore, when stress is applied, the bond is not broken, and the cyclic structure moves along the main chain, responding to deformation due to stress. Therefore, the physical properties are not deteriorated by bond scission, and it is possible to achieve both excellent elasticity and strength, properties that are normally difficult to achieve together.

[0026] In the present invention, the polymer side chain has a cyclodextrin ring, and such a cyclodextrin ring preferably has a structure represented by the following general formula (1).

[0027] (In the formula, R １ are the same or different and each represents a hydrogen atom, an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR ２ (R ２ represents an alkyl group having 1 to 20 carbon atoms, and R １ At least 20% of the groups are acyl groups having 2 to 50 carbon atoms, alkyl groups having 1 to 30 carbon atoms, or -CONHR ２ x is an integer of 5 to 7)

[0028] The compound represented by the general formula (1) is preferably one in which 20% or more of the hydroxyl groups bonded to the cyclodextrin ring are substituted with hydrophobic groups. That is, since the main skeleton of the compound is a hydrophobic aliphatic polyester resin, it is preferable that the hydroxyl groups on the cyclodextrin ring are hydrophobized, in terms of increasing compatibility and improving physical properties.

[0029] In the above general formula (1), R １ 60% or more of which are acyl groups having 2 to 50 carbon atoms, alkyl groups having 1 to 30 carbon atoms, or -CONHR ２ It is more preferable that the hydroxyl group content is either one of the above, and even more preferable that the hydroxyl group content is 90% or more. There is no particular upper limit, and all hydroxyl groups may be substituted. The cyclodextrin rings having a higher hydrophobicity are preferred in that they have a better affinity with organic functional groups and therefore have a higher affinity with aliphatic polyesters.

[0030] There are three types of dextrin skeletons: α (x = 5), β (x = 6), and γ (x = 7). Any of these may be used, but β or γ is particularly preferred. When β or γ is used, it is particularly preferred because the main chain tends to have a structure in which it penetrates the ring. It is also acceptable to mix two or more of α, β, and γ.

[0031] The choice of which of these cyclodextrin structures to use will have an effect on the properties of the resulting polymer, so the choice of which of these structures to use is important.

[0032] Generally, it is said that β and γ are the ones that are most likely to form a penetrating structure, and therefore it is more preferable to use these. Furthermore, the inventors' studies have shown that when the β form is used, a polymer having the best properties in terms of breaking strength, elongation, and toughness is obtained, and when the γ form is used, a polymer having the property of exhibiting a high Young's modulus is obtained.

[0033] It is not the case that one is superior to the other, but it is preferable to select and use an appropriate one depending on the purpose of use and which property is important. Furthermore, when it is desired to obtain intermediate performance between these two, the β-isomer and the γ-isomer may be used in combination.

[0034] The cyclodextrin represented by the general formula (1) has a structure in which some or all of the hydroxyl groups in the proportions described above are R １ In general formula (1), R can be at least one group selected from the group consisting of an acetyl group, an alkyl group having 50 or less carbon atoms, and -CONHR (R is a methyl group or an ethyl group). Such substitution can be carried out by known methods.

[0035] In the polymer of the present invention, the cyclodextrin skeleton is preferably contained in a proportion of 0.1 mol to 10 mol % relative to the total amount of the polymer. By being contained in such a proportion, favorable effects can be obtained. The lower limit is more preferably 0.2 mol %, and even more preferably 0.3 mol %. The upper limit is more preferably 8.0 mol %, and even more preferably 7.0 mol %.

[0036] The polymer of the present invention has an aliphatic polyester as a main structural unit. In the present invention, the polymer has a structural unit based on an aliphatic polyester as a main chain skeleton. Aliphatic polyesters are known as biodegradable resins, and by using them as a main structural unit, a polymer with a low environmental impact can be obtained.

[0037] Aliphatic polyesters can also be decomposed into low molecular weight compounds by enzymatic degradation. Furthermore, the enzymatic degradation products can be regenerated into polymers by enzymatic reactions. Therefore, discarded polymers can be converted into low molecular weight compounds by enzymatic degradation. The polymers of the present invention can then be regenerated by subjecting the recovered low molecular weight compounds to an ester bond formation reaction again.

[0038] Non-Patent Document 1 discloses a polymer having a polyether as a main structural unit. By using a polyester as the main structural unit, the polymer is preferable in that it has better weather resistance and chemical resistance than a polymer having a polyol-based main skeleton.

[0039] Such aliphatic polyesters may be those obtained by polymerization of hydroxycarboxylic acids or ring-opening polymerization of lactams, or may be those obtained by polycondensation of aliphatic dicarboxylic acids and aliphatic diols, or may be copolymers thereof.

[0040] Specific examples of such aliphatic polyesters include polycaprolactone, polylactic acid, poly(1,4-butylene adipate), and poly(ethylene adipate).

[0041] When the aliphatic polyester is mainly composed of polycaprolactone, it may contain a structural unit consisting of a diol compound in part.

[0042] n is 1 to 29, m is 29 to 1, n+m≦30

[0043] Such polycaprolactone is preferred because it is easy to synthesize and both polyester terminals are hydroxyl groups.

[0044] Such polycaprolactones are HO-R ３ The diol compound has a structural unit based on a diol compound represented by the general formula: --OH. There are no particular limitations on such diol compounds, but for example, those having a molecular weight of 4,000 or less are preferred.

[0045] Specific examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, triethanolamine, and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine.

[0046] As described above, the physical properties of the polymer of the present invention differ significantly depending on whether the cyclodextrin skeleton is a β- or γ-form. Furthermore, since the polymer has an aliphatic polyester as its basic skeleton, its physical properties differ from those of the polymer described in Non-Patent Document 1, which has a polyether as its basic skeleton.

[0047] When the cyclodextrin skeleton is a β-form, the elongation can be 500 to 10,000%. The lower limit is more preferably 1,000%, and even more preferably 1,500%. The upper limit is more preferably 5,000%, and even more preferably 3,000%.

[0048] When the cyclodextrin skeleton is a β-form, the breaking strength can be 10 to 200 MPa. The lower limit is more preferably 20 MPa, and even more preferably 30 MPa. The upper limit is more preferably 150 MPa, and even more preferably 100 MPa.

[0049] When the cyclodextrin skeleton is a β-form, the Young's modulus can be set to 10 to 100 MPa. The lower limit is more preferably 20 MPa. The upper limit is more preferably 80 MPa.

[0050] When the cyclodextrin skeleton is a β-form, the toughness is 100 to 1000 MJm －３ The lower limit is 150 MJm －３ The upper limit is more preferably 700 MJm －３ It is more preferable that:

[0051] When the cyclodextrin skeleton is a γ-form, the elongation can be 500 to 10,000%. The lower limit is more preferably 1,000%, and even more preferably 1,500%. The upper limit is more preferably 5,000%, and even more preferably 3,000%.

[0052] When the cyclodextrin skeleton is a γ-form, the breaking strength can be set to 5 to 100 MPa. The lower limit is more preferably 10 MPa. The upper limit is more preferably 70 MPa.

[0053] When the cyclodextrin skeleton is a γ-form, the Young's modulus can be set to 20 to 200 MPa. The lower limit is more preferably 30 MPa. The upper limit is more preferably 150 MPa.

[0054] When the cyclodextrin skeleton is a γ-form, the toughness is 50 to 700 MJm －３ The lower limit is 80 MJm －３ The upper limit is more preferably 500 MJm －３ It is more preferable that:

[0055] Thus, the polymer of the present invention is preferable in that it can be made into a resin having excellent physical properties. Furthermore, these numerical values ​​are values ​​obtained by the measurement method in the example of Aspect 1 in the examples of the present specification.

[0056] The present invention may be a polymer consisting only of the above-mentioned polycaprolactone structure and components for forming a cyclodextrin skeleton in the side chain, but may also contain other structural units. That is, examples of polymers in which other structural units are used in combination to obtain excellent strength include the following embodiments 1 and 2.

[0057] (Aspect 1) A polymer having structural units derived from a compound (A) having a functional group reactive with two isocyanate groups present in a cyclodextrin skeleton and a structure other than the cyclodextrin skeleton, an aliphatic polyester (B), and a polyisocyanate compound (C). (Aspect 2) A polymer obtained by polymerizing ε-caprolactone in the presence of an acrylic polymer having a cyclodextrin skeleton as a side chain of the polymer.

[0058] In these embodiments, a resin structure other than the aliphatic polyester is introduced into the polymer in order to further improve the physical properties of the polymer. Hereinafter, such embodiments 1 and 2 will be described in detail.

[0059] (Regarding Aspect 1) The polymer of Aspect 1 is a polyurethane resin having a biodegradable aliphatic polyester skeleton, to which a structure derived from compound (A) has been introduced. In such a structure, the resin chain penetrates the cyclodextrin ring to form crosslinking points, and it is presumed that the crosslinking points due to CD undergo sliding motion when stress is applied, resulting in a mobile crosslinked material that exhibits high stress dispersibility.

[0060] Furthermore, the presence of urethane groups also results in the formation of a crosslinked structure due to hydrogen bonds, which is advantageous in that it achieves even better physical properties due to the synergistic effect of two types of crosslinking structures with different mechanisms, namely crosslinking due to CD and crosslinking due to hydrogen bonds.

[0061] To introduce a cyclodextrin skeleton into such a polymer, it is necessary to have a skeleton derived from a compound having two or more hydroxyl groups in a structure other than the cyclodextrin skeleton in addition to the cyclodextrin ring. Since such a compound (A) has a functional group that reacts with isocyanate, it can be introduced into the polymer by reacting it with a polyisocyanate compound. An example of the chemical formula of the compound obtained by such a reaction is shown below.

[0062]

[0063] In the compound of the above general formula, the aliphatic polyester (B) is polycaprolactone partially having a diethylene glycol skeleton, the isocyanate compound (C) is tetramethylene diisocyanate, and the specific compound represented by general formula (2) is used as the compound (A). Such a compound is an example of the polymer of the present invention, but the present invention is not limited to such a specific polymer. Each of the components (A) to (C) will be described in detail below.

[0064] (Compound (A) Having Functional Groups Reactive with 2 Isocyanate Groups Present in a Cyclodextrin Skeleton and in a Structure Other Than the Cyclodextrin Skeleton) Compound (A) is a compound having a cyclodextrin ring. In the polymer of the present invention, a crosslinked structure is formed by the main chain derived from another component passing through the cyclodextrin ring of such compound (A).

[0065] Compound (A) has, in addition to the cyclodextrin skeleton represented by the general formula (1) described above, two or more functional groups reactive with isocyanate groups. Examples of functional groups reactive with isocyanate groups include hydroxyl groups, amino groups, and carboxyl groups. These functional groups readily react with polyisocyanate compounds. Therefore, they are incorporated into the resin through the reactions of the components (A) to (C), which will be described in detail below. This results in a resin having a cyclodextrin structure in a side chain relative to the polymer main chain. The main chain then penetrates through this cyclodextrin structure, forming a crosslinked structure.

[0066] Compound (A) must have two or more functional groups reactive with isocyanate groups. This allows compound (A) to be incorporated into the polymer main chain, resulting in a polymer having a cyclodextrin structure in the polymer side chain. When there are two functional groups reactive with isocyanate groups, a linear resin is obtained. When there are three or more functional groups reactive with isocyanate groups, such a compound itself becomes a crosslinking point. It is particularly preferred to use a compound having a total of two functional groups reactive with isocyanate groups, as this makes it easy to control the physical properties and handle the compound.

[0067] Such compounds include compounds having the following structures in the molecule: It is preferable that the compound has a structure represented by the following formula: Compounds having such a structure are preferable in that they can be easily synthesized and can be produced from relatively inexpensive raw materials.

[0068] Such compounds can be obtained, for example, by reacting a compound having an unsaturated bond and a cyclodextrin structure with α-thioglycerol. That is, they can be obtained by adding α-thioglycerol to the unsaturated bond. Therefore, any compound having an unsaturated bond and a cyclodextrin structure can be converted into such a compound.

[0069] More specifically, such compounds include

[0070] (In the formula, R １ are the same or different and each represents a hydrogen atom, an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR ２ (R ２ represents an alkyl group having 1 to 20 carbon atoms, and R ２ At least 20% of the groups are acyl groups having 2 to 50 carbon atoms, alkyl groups having 1 to 30 carbon atoms, or -CONHR ３ Either one. R ３ is an alkyl chain having 1 to 20 carbon atoms which may have an amide group, an ester group, or a sulfide group in the main chain. １ , X ２ are the same or different and are OH or NH ２ x is an integer from 5 to 7

[0071] More specifically, it is preferable to use a compound represented by the following general formula (2).

[0072] Such compounds are known compounds described in Non-Patent Document 1 mentioned above.

[0073] Furthermore, a compound having a structure represented by the following general formula (4) can also be used.

[0074] (In the formula, R １ (A) The following general formula (12) -R ３ -NH-R ４ (12) (R ３ is an alkylene group having 3 to 20 carbon atoms, which may be linear or branched, and may have a substituent. ４is a structure represented by the following formula: In the formula, R １０ represents hydrogen or a methyl group. ５ -NHCONH-R ６ (13) (R ５ is an alkylene group having 3 to 20 carbon atoms, which may be linear or branched, and may have a substituent. ６ is the above R ４ or (c) a compound represented by the following general formula (14): ５ -OCONH-R ６ (14) (R ５ and R ６ is the same as above.) R ２ represents a hydrogen atom, an acyl group having 2 to 50 carbon atoms, or an alkyl group having 1 to 30 carbon atoms. ｃ represents a group represented by the following general formula (1).

[0075] (In the formula, R １ are the same or different and each represents an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR ２ (R ２ represents an alkyl group having 1 to 20 carbon atoms, and R １ At least 20% of the groups are acyl groups having 2 to 50 carbon atoms, alkyl groups having 1 to 30 carbon atoms, or -CONHR ２ and x is an integer of 5 to 7. Specific examples of such compounds include:

[0076] (In the formula, R １ are the same or different and each represents a hydrogen atom, an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR ２ (R ２ represents an alkyl group having 1 to 20 carbon atoms), ７ represents hydrogen or a methyl group. ８ is an alkylene chain having 2 to 20 carbon atoms).

[0077] Such compounds are preferred because they are relatively easy to synthesize and can be obtained with high purity.Furthermore, the resulting polymer is preferred because it allows for appropriate control of the distance between the main chain and the cyclodextrin, allowing for a high degree of freedom in designing the main chain to easily penetrate.

[0078] Such compounds can be particularly suitably used for the purposes of the present invention.

[0079] The use of the compound represented by the above general formula (4) is preferred in that the resulting polymer has particularly excellent physical properties.

[0080] Such compounds can be obtained by reacting the compounds having unsaturated groups described in WO 2022 / 024908 with α-thioglycerol.

[0081] (Aliphatic Polyester (B)) In Aspect 1, the main chain skeleton has a structural unit based on the aliphatic polyester (B). Aliphatic polyesters are known as resins having biodegradability, and by using them as the main structural unit, a polymer with a low environmental impact can be obtained.

[0082] Examples of the aliphatic polyester resin (B) that can be used in the first embodiment include those mentioned above.

[0083] The aliphatic polyester (B) as a constituent unit preferably has a number average molecular weight of 1000 to 4000. The number average molecular weight is measured by the method described in the Examples.

[0084] (Polyisocyanate Compound (C)) The polyisocyanate compound (C) is a well-known compound widely known in the field of resins, and any of these can be used. As the polyisocyanate compound (C), diisocyanates are preferred.

[0085] In Aspect 1 of the present invention, the effect is obtained by a crosslinked structure based on a structure other than a covalent bond, and therefore a crosslinked structure based on a polyfunctional structure of three or more functional groups is not necessary. Note that, as long as the effect of the present invention is not impaired, a crosslinked structure based on a polyisocyanate compound of three or more functional groups may be included. Even when a polyisocyanate compound of three or more functional groups is used in part, the amount used is preferably 15.0 mass% or less based on the total amount of polyisocyanate compounds.

[0086] Examples of diisocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, (o-, m-, or p-)xylene diisocyanate, methylenebis(cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene isocyanate, 1,5-naphthalene diisocyanate, and norbornane diisocyanate.

[0087] (Amounts of Blends) In the present invention, the amounts of the above-mentioned components (A) to (C) to be blended are not particularly limited, but are preferably within the ranges shown below.

[0088] (Content of structural units based on compound (A) having two or more hydroxyl groups present in the cyclodextrin skeleton and in a structure other than the cyclodextrin skeleton) The content of compound (A) is preferably 0.1 to 10% by weight based on the total amount of compounds (A) to (C). By setting the content within this range, the number of crosslinks in the polymer can be kept within an appropriate range, which is preferable in that a polymer having the required physical properties can be obtained.

[0089] The lower limit of the amount of the compound (A) is more preferably 0.7% by weight, and the upper limit of the amount of the compound (A) is more preferably 1.3% by weight, and even more preferably 1.0% by weight.

[0090] (Content of Structural Units Based on Aliphatic Polyester (B)) The content of the compound (B) is preferably 85.0 to 95.0% by weight based on the total amount of the compounds (A) to (C). By setting the content within this range, the number of crosslinks in the polymer can be kept within an appropriate range, which is preferable in that a polymer having the required physical properties can be obtained.

[0091] The lower limit of the amount of compound (B) is more preferably 8.0% by weight, and the upper limit of the amount of compound (B) is more preferably 93.0% by weight, and even more preferably 90.0% by weight.

[0092] (Content of structural units based on isocyanate compound (C)) The content of the compound (C) is preferably 1 to 10% by weight based on the total amount of the compounds (A) to (C). By setting the content within this range, the number of crosslinks in the polymer can be set within an appropriate range, which is preferable in that a polymer having required physical properties can be obtained.

[0093] The lower limit of the amount of compound (C) is more preferably 1.5 wt %, and the upper limit of the amount of compound (C) is more preferably 3.0 wt %, and even more preferably 4.8 wt %.

[0094] (Method for Producing Polymer) The polymer of the present invention has the above-described components (A) to (C) as structural units. Such a polymer can be obtained by mixing the above-described components (A) to (C) in an organic solvent solution state and heating the mixture to 40 to 80°C.

[0095] In such a reaction, a catalyst may be used, and the catalyst is not particularly limited, but examples thereof include N,N-dimethylcyclohexylamine, dibutyltin dilaurate, N-ethylmorpholine, bis(2,dimethylaminoethyl)ether, 2,2′-oxybis(N,N-dimethylethylamine), and triethanolamine.

[0096] (Properties of Polymer) The polymer of Aspect 1 of the present invention has the chemical structure described above, but it is particularly preferable that it has the physical properties shown below. By satisfying the properties below, it is possible to obtain a polymer with more suitably excellent physical properties.

[0097] (Molecular Weight) The polymer of the present invention preferably has a number average molecular weight of 10.0 to 65.0 kDa. The polymer of the present invention preferably has a weight average molecular weight of 15.0 to 100 kDa. The molecular weight is measured according to the method described in the Examples.

[0098] (Glass Transition Temperature) The polymer of the present invention preferably has a glass transition temperature of −50.0° C. to −60.0° C. The glass transition temperature is measured according to the method described in the Examples.

[0099] (Melting Point) The polymer of the present invention preferably has a melting point of 40.0° C. to 45.0° C. The melting point is measured according to the method described in the Examples.

[0100] (Molding method) The polymer of the present invention can be molded into a predetermined shape by applying a solution of the polymer to a substrate and drying it, although the molding method is not particularly limited. The polymer of the present invention can also be molded by hot press molding.

[0101] (Aspect 2) The polymer of Aspect 2 is obtained by polymerizing ε-caprolactone (the polymer obtained by this polymerization reaction may be referred to as the second polymer) in the presence of an acrylic polymer (C) having a cyclodextrin skeleton as a side chain of the polymer (hereinafter, this may be referred to as the first polymer). When a new polymerization reaction is performed in the presence of the first polymer, the first polymer and the second polymer form a closely entangled structure known as an interpenetrating structure, which improves physical properties.

[0102] In the present invention, a first polymer having a cyclodextrin skeleton is used. Such a first polymer has a crosslinked structure in which the main chain penetrates the cyclodextrin ring, and therefore an interpenetrating structure is more preferably formed. It is also presumed that a portion of the polycaprolactone structure penetrates the cyclodextrin ring.

[0103] Therefore, the polymer of the present invention has physical properties that are significantly different from those of a resin mixture obtained by blending the acrylic polymer (C) with polycaprolactone, and has unique and excellent physical properties that cannot be obtained by simple blending.

[0104] (Acrylic Polymer (C)) As the acrylic polymer having a cyclodextrin ring in the side chain, a known polymer can be used. Such a polymer is not particularly limited, and examples thereof include a copolymer of a monomer having a cyclodextrin ring in the side chain and another unsaturated polymer.

[0105] The monomer having a cyclodextrin ring in the side chain is not particularly limited, and examples thereof include known monomers, such as those described in International Publication Nos. 2012 / 036069 and 2022 / 024908.

[0106] (Other radical polymerizable monomers) The other radical polymerizable monomers are those represented by the following general formula (a1):

[0107] (In formula (a1), Ra is a hydrogen atom or a methyl group, R ３ represents a halogen atom, a hydroxyl group, a thiol group, an amino group which may have one substituent or a salt thereof, a carboxyl group which may have one substituent or a salt thereof, an amide group which may have one or more substituents or a salt thereof, or a phenyl group which may have one or more substituents).

[0108] In formula (a1), R ３is a carboxyl group having one substituent, examples thereof include a carboxyl group (i.e., an ester) in which the hydrogen atom of the carboxyl group is substituted with a hydrocarbon group, methoxypolyethylene glycol (the number of ethylene glycol units is 1 to 20, preferably 1 to 10, particularly preferably 2 to 5), ethoxypolyethylene glycol (the number of ethylene glycol units is 1 to 20, preferably 1 to 10, particularly preferably 2 to 5), etc. ３ is an amide group having one or more substituents, i.e., a secondary amide or a tertiary amide, examples thereof include amide groups in which one hydrogen atom or two hydrogen atoms of the primary amide are substituted independently with a hydrocarbon group or a hydroxyalkyl group (for example, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group).

[0109] Among them, in formula (a1), R ３ However, it is preferably a carboxyl group in which a hydrogen atom is substituted with an alkyl group having 1 to 10 carbon atoms, or an amide group in which one or more hydrogen atoms are substituted with an alkyl group having 1 to 10 carbon atoms. In this case, the other radical polymerizable monomer is relatively highly hydrophobic, and copolymerization with the host group polymerizable monomer proceeds easily. More preferably, the alkyl group as a substituent has 2 to 8 carbon atoms, and particularly preferably 2 to 6 carbon atoms, and in this case, the toughness and strength of the resulting polymer material are also likely to be improved. This alkyl group may be either linear or branched.

[0110] Specific examples of the monomer represented by formula (a1) include (meth)acrylic acid, allylamine, maleic anhydride, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, N,N-dimethyl(meth)acrylamide, N,N-diethylacrylamide, N-isopropyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylamide, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol acrylate, styrene, etc. These can be used alone or in combination of two or more.

[0111] The acrylic polymer used in Aspect 2 of the present invention preferably contains the structural units derived from the monomer having a cyclodextrin ring in a side chain thereof in a proportion of 5 to 70% by mass of the entire polymer. Amounts within this range are preferred in that significant improvements in physical properties can be achieved. The lower limit is more preferably 10% by mass, and even more preferably 15% by mass. The upper limit is more preferably 65% ​​by mass, and even more preferably 60% by mass.

[0112] The polymerization method for the polymer constituting the copolymer or resin composition of the present invention is not particularly limited, and can be carried out by a general method. Specific examples include thermal radical polymerization, photoradical polymerization, anionic polymerization, and cationic polymerization. Among these, radical polymerization is particularly preferred.

[0113] When the radical polymerization is carried out by light, it is preferable to use a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and examples thereof include acetophenone-based initiators such as 1-hydroxycyclohexyl phenyl ketone (trade name: IRGACURE 184), 2-hydroxy-2-methylpropiophenone (trade name: IRGACURE 1173), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one; benzoin-based initiators such as benzoin and 2,2-dimethoxy-1,2-diphenylethan-1-one; benzophenone, [4-(methylphenylthio)phenyl]phenylmethanone, 4-hydroxybenzophenone, and 4-phenylbenzophenone. Examples of initiators that can be used include benzophenone initiators such as 2-chlorothioxanthone and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone initiators such as 2-chlorothioxanthone and 2,4-diethylthioxanthone; acylphosphine oxide initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; and oxime ester initiators such as 1,2-octanedione, 1-[4-(phenylthio)phenyl], 2-(0-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazoyl-3-yl], and 1-(0-acetyloxime). The amount of the photopolymerization initiator used is preferably 0.1 to 2 wt % based on the total amount of monomers constituting the copolymer or resin composition of the present invention.

[0114] The conditions for photopolymerization are not particularly limited, and examples of light sources include a high-pressure mercury lamp, an LED lamp, and a metal halide lamp.

[0115] When the radical polymerization reaction is carried out by thermal reaction, it is preferable to use a radical polymerization initiator. The radical polymerization initiator is not particularly limited, and examples that can be used include azobisisobutyronitrile (AIBN), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-methylpropionate)dimethyl, 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, and cumene hydroperoxide. The amount of the thermal polymerization initiator used is preferably 0.1 to 2% by weight based on the total amount of monomers constituting the copolymer or resin composition of the present invention.

[0116] (Polymerization of Polycaprolactone) The polymer of the present invention is obtained by polymerizing ε-caprolactone in the presence of the above-mentioned acrylic polymer (C). Examples of the polymerization of ε-caprolactone include a method in which the raw material ε-caprolactone is dissolved in an organic solvent solution of the acrylic polymer (C), a method in which the solvent is removed and the acrylic polymer (C) is molded into a predetermined shape and then impregnated with a raw material such as ε-caprolactone to polymerize, a method in which the acrylic polymer is dissolved in ε-caprolactone to polymerize, and a method in which the acrylic polymer is melted by heating and then mixed with ε-caprolactone to polymerize the melted acrylic polymer.

[0117] During the polymerization of polycaprolactone, HO-R ３ The diol compound may have a structural unit based on a diol compound represented by the general formula -OH. Although there are no particular limitations on such diol compounds, for example, those having a molecular weight of 500 or less are preferred.

[0118] Specific examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, and 1,4-benzenedimethanol.

[0119] When the diol compound is used, the amount used is preferably within a range of 0 to 1% by mass in terms of the weight ratio (diol compound) / (caprolactone + diol compound). Amounts within this range are particularly preferred in that favorable physical properties can be obtained. The lower limit is more preferably 0.001% by mass, and even more preferably 0.01% by mass. The upper limit is more preferably 0.5% by mass, and even more preferably 0.1% by mass.

[0120] A catalyst may be used in combination with the polymerization, if necessary. Specific examples of the catalyst include tin(II) 2-ethylhexanoate, titanium(IV) tetrabutoxide, zinc bis(2-ethylhexanoate), calcium methoxide, tributyltin methoxide, zinc dibutoxide, and lipase. The amount of catalyst blended is preferably 0.001 to 20% by mass. The lower limit is more preferably 0.005% by mass, and even more preferably 0.01% by mass. The upper limit is more preferably 0.5% by mass, and even more preferably 0.1% by mass.

[0121] In the polymer of Aspect 2, the polycaprolactone preferably accounts for 20 to 90% by mass of the entire polymer. Within this range, the above-described effects can be optimally exhibited. The lower limit is more preferably 30% by mass, and even more preferably 40% by mass. The upper limit is more preferably 80% by mass, and even more preferably 70% by mass.

[0122] (Properties of Polymer) The polymer of Aspect 2 of the present invention has the chemical structure described above, but it is particularly preferable that it has the physical properties shown below. (Molecular Weight) The polymer of the present invention preferably has a weight average molecular weight of 5,000 to 2,000,000. The molecular weight is measured in accordance with the method described in the Examples. Specifically, (molecular weight) is calculated by measuring the molecular weight by size exclusion chromatography. (Eluant: chloroform, standard sample: polystyrene) (Glass Transition Temperature) The polymer of the present invention preferably has a glass transition temperature of -150 to 150°C. The glass transition temperature is determined from the temperature at which a baseline shift is observed during the first heating process (heating rate 10°C / min) in differential scanning calorimetry. (Melting Point) The polymer of the present invention preferably has a melting point of 50 to 250°C. The melting point is determined during the first heating process (heating rate 10°C / min) in differential scanning calorimetry. ｏ The melting peak temperature is determined from the temperature at which the melting peak is observed (C / min).

[0123] The polymer of the present invention is not particularly limited in its application, and can be used in molded articles such as automobile parts, electrical appliances, agricultural materials, office supplies, and daily necessities, as well as adhesives.

[0124] The present invention will be specifically described below based on examples, but the present invention is not limited to the following examples.

[0125] The monomers used in the following examples have the following meanings. In the formula, X=7 TAcγCD-diOH In the formula, X=7 Ac-γ-CDAAm

[0126] In the formula, X=6 SH-2-DiOH

[0127] (Example 1 of Aspect 1) (Materials) TAcγCD-diOH (a compound represented by general formula (2)) was prepared according to the method described in Non-Patent Document 1. α-Thioglycerol, hexamethylene diisocyanate (HDI), dibutyltin diacetate (DBTDA), and N,N,N'-tetrakis(2-hydroxyethyl)ethylenediamine (THEED) were purchased from Wako Pure Chemical Industries, Ltd. ε-caprolactone (ε-CL), tin(II) bis(2-ethylhexanoate) (Sn(Oct)2), and diethylene glycol were purchased from Wako Pure Chemical Industries, Ltd. Dry N,N-dimethylformamide (DMF), methanol (MeOH), dichloromethane (DCM), and chloroform-d were purchased from Tokyo Chemical Industry Co., Ltd. Reagents and solvents were used without further purification.

[0128] (Measurement) Nuclear magnetic resonance (NMR) spectroscopy: 1D at 500 MHz using an ECA-500 NMR spectrometer (manufactured by JEOL Ltd.) at 25°C. １ H and １３ C NMR spectra were recorded. In all NMR measurements, chemical shifts were referenced to an internal standard (δ=0 ppm for tetramethylsilane (TMS)).

[0129] Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF MS): MALDI measurements were performed using a Bruker autoflex max LRF with 2,5-dihydroxybenzoic acid as the matrix material. The measurements were performed in reflector mode. TOF-MS measurements were performed using a Bruker autoflex max LRF with 2,5-dihydroxybenzoic acid as the matrix material. The measurements were performed in reflector mode.

[0130] Tensile Test: Tensile tests of the polymers were performed at 25°C using an Autograph AG-X plus (Shimadzu Corporation) at a deformation rate of 1 mm / s. All samples were tested using at least three specimens to calculate the average values ​​of mechanical properties and their standard deviations. Young's modulus was calculated from the initial slope of the stress-strain curve in the range of 1 to 6% strain up to the yield point, and the curve showed a linear increase. Toughness values ​​were calculated as the integral of the stress-strain curve from 0% strain to the fracture strain point. The sample geometry used is shown in Figure 45.

[0131] Cyclic tensile test: Cyclic tensile test was performed using an Autograph AG-X plus (Shimadzu Corporation). The specimen was continuously stretched and recovered without intervals, and the maximum strain was set to 200% 10 times at a deformation rate of 1 mm / s. Repeated tensile tests at different maximum strains were set to 200%, 400%, 600%, 800%, 1000%, and 1200% at a deformation rate of 1 mm / s. Stress relaxation test: Stress relaxation test was performed using an Autograph AG-X plus (Shimadzu Corporation). The specimen was stretched to 800%. After that, the strain was held and the stress was recorded for 3600 seconds.

[0132] Gel permeation chromatography (GPC): The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (PDI, Mw / Mn) were measured by GPC using tetrahydrofuran (THF) as the eluent at 40°C, and the molecular weight of the sample was calculated based on a calibration curve using polystyrene standards. The GPC measurement was performed using THF solvent at a flow rate of 1.50 mL / min. －１ The measurement was carried out at 40 °C. A Tosoh HLC-8420GPC EcoSEC (registered trademark, Tosoh Corporation) was used for the measurement, and two Tosoh TSKgel columns (TSKgel G2500HHR and TSKgel G4000HHR) were used.

[0133] Differential scanning calorimetry (DSC): N ２The glass transition temperature (Tg) and melting point (Tm) of the samples were measured under a gas flow (20 mL / min). The equipment used was a Hitachi High-Technologies Corporation DSC 7020 system. Measurements were performed at a rate of 10°C / min in the temperature range from -100°C to 100°C. All samples were first cooled to -100°C and then heated to 100°C. The curves for this step are called the first scan. After cooling to -100°C again, all samples were heated to 100°C again. The curves for this step are called the second scan.

[0134] Thermogravimetric analysis (TGA): The thermal degradation of the polymer was measured using a TGA system (PerkinElmer STA 6000). ２ Measurements were performed by increasing the temperature from 80°C to 500°C at a rate of 10°C / min under a gas flow rate of 20 mL / min.

[0135] ATR-FTIR: Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was performed using a JASCO FT / IR-6100 spectrometer in the 4000-800 cm －１ The measurements were carried out in the wavenumber range of

[0136] (Synthesis Example 1) Synthesis of SH-2-DiOH

[0137] SH-02 (2.14 g, 1 mmol), α-thioglycerol (1.1 g, 10 mmol), and IRGACURE 184 (20 mg, 0.1 mmol) were dissolved in methanol (10 mL). This mixture was irradiated with UV light from a Hg lamp (HL 100 G, HB 100 A-1, Seritec Co., Ltd., λ = 365 nm) for 2 hours. The solution was then added dropwise to cold water (300 mL) and suction filtered to separate the white precipitate. The resulting solid was dried overnight at 50 °C in a fan dryer and then dried in vacuo at 50 °C for 1 day. The yield was 16% (0.37 g).

[0138] (Synthesis Example 2) Preparation of Aliphatic Polyester Resin

[0139]

[0140] N ２Diethylene glycol and Sn(Oct) in the lower drying tube ２ ε-Caprolactone was added to the reaction mixture, and the mixture was allowed to react at 120°C for 20 hours. After the specified time, the reaction mixture was directly precipitated into cold hexane to obtain the desired aliphatic polyester (PCL). x The ratio of the amounts of raw materials used is shown in Table 1.

[0141] a 1 The Mn of PCLx-diOH was calculated from H NMR.

[0142] Example 1 Preparation of Polymer 4-1 Preparation of PCLx-γCD(a)-PU

[0143]

[0144] Before the reaction, a mixture of TAcγCD-diOH and PCLx-diOH was heated overnight at 80°C under vacuum to remove moisture. The mixture of TAcγCD-diOH (a mol%) and PCLx-diOH ((100-a) mol%) was sonicated at 60°C for 30 minutes and then dissolved in dry DMF. HDI ([NCO] / [OH] =1.05 / 1) and DBTDA (0.25 wt%) dissolved in dry DMF were added to the above mixture. The reaction mixture was then heated under vacuum at 80°C overnight to remove moisture. ２ The mixture was heated at 60°C for 24 hours under reduced pressure. After the specified time, the reaction mixture was precipitated in a cold solvent of DCM / MeOH (v / v = 1 / 4) to obtain PCLx-γCD(a)-PU. The raw material feed ratios for each polymer are shown in Table 2. The GPC measurement results are shown in Table 5 and Figure 24.

[0145] X : 1.5k, 2.4k, 3.5k. a : mol% of TAcγCD-diOH.

[0146] Comparative Example 1 4-2 Preparation of lPCLx-PU (Comparative Example without Cyclodextrin Ring)

[0147]

[0148] Before the reaction, all raw materials were heated at 80°C under vacuum overnight to remove moisture. PCLx-diOH was dissolved in dry DMF. HDI ([NCO] / [OH] = 1.05 / 1) and DBTDA (0.25 wt%) dissolved in dry DMF were then added. The reaction mixture was then heated under vacuum at 80°C overnight to remove moisture. ２ The mixture was heated at 60°C for 24 hours under reduced pressure. After the specified time, the reaction mixture was precipitated in a cold solvent of DCM / MeOH (v / v = 1 / 4) to obtain lPCLx-PU. The feed ratios are shown in Table 3. The GPC measurement results are shown in Table 5 and Figure 24.

[0149] x : 1.5k, 2.4k, 3.5k.

[0150] Comparative Example 2 Preparation of PCLx-THEED(b)-PU

[0151]

[0152] Before the reaction, all reagents were heated at 80 °C under vacuum overnight to remove moisture. THEED (b mol%) and PCLx-diOH (b mol%) were mixed under ultrasonication at 60 °C for 30 min and then dissolved in dry DMF. HDI ([NCO] / [OH] = 1.05 / 1) and DBTDA (0.25 wt%) dissolved in dry DMF were added to the above mixture. The reaction mixture was then heated under vacuum at 80 °C for 30 min to remove moisture. ２ The mixture was heated at 60°C under reduced pressure for 24 hours. After the specified time, the reaction mixture was precipitated in a cold solvent of DCM / MeOH (v / v=1 / 4) to obtain PCLx-THEED(b)-PU. The feed ratios are shown in Table 4. The GPC measurement results are shown in Table 5 and Figure 23.

[0153] X : 1.5k, 2.4k, 3.5k. b : mol% of THEED.

[0154] The results of GPC measurement of the resins of the above-mentioned Examples and Comparative Examples are shown in Table 5.

[0155]

[0156] PCLx-γCD(a)-PU was dissolved in DCM and poured into a Teflon mold. The film was obtained by leaving it at room temperature for 24 hours and then at 35°C under vacuum overnight.

[0157] The FTIR measurement results of the obtained film are shown in Figure 25. From the results of Figure 25, it can be seen that the NHCOO- group and -COO- group are present, and therefore, PCL 2.4k It was revealed that the polymerization of -PU was successful.

[0158] The results of DSC measurement of the obtained polymer are shown in Figure 26. From these results, the thermal properties (particularly the characteristics of the glass transition temperature and melting point) of the polymer of the present invention became clear.

[0159] The Tg and ΔH obtained from the DSC results are shown in the following table. (a) Crosslinking ratio / Tg (b) Crosslinking ratio / ΔH relationship. From these results, (a) when crosslinking points are introduced, all crosslinked polymers are PCL. 2.4k (b) The introduction of the covalent crosslinker THEED increases ΔH, but the introduction of the mobile crosslinker CD slightly decreases ΔH.

[0160] The strain-stress curves for each of the polymers of the Examples are shown in Figures 28 and 29. These results demonstrate that the polymers of the present invention have superior physical properties in both elongation and breaking strength compared to the Comparative Examples.

[0161] The relationship between Young's modulus and toughness for each sample is plotted in Figures 30 and 31. This clearly shows that the polymer of the present invention has excellent performance in both Young's modulus and toughness.

[0162] The hysteresis loss calculated from the cyclic stress-strain curves at a fixed strain (200%) is shown in Figure 32. Ten cycles were performed. The results show that the hysteresis loss of all polymers was quantified and that the value tended to stabilize after five cycles.

[0163] The cyclic stress-strain curves for each sample at a fixed strain (200%) are shown in Figure 33. Ten cycles were performed. The results revealed that the hysteresis due to chain slippage in the supramolecular network was greatest during the first cycle.

[0164] Figure 34 shows (a) the cyclic tensile test curve of PCL-γCD (5-PU) recorded with increasing maximum strain. (b) The energy dissipation and damping capacity of each circle on the cyclic tensile test curve. Figure 35 shows (a) the cyclic tensile test curve of PCL-γCD (5-PU) recorded with increasing maximum strain. (b) The energy dissipation and damping capacity of each circle on the cyclic tensile test curve. From these results, (a) the hysteresis loop became larger with increasing strain, and residual strain became significant. (b) It was confirmed that energy loss increased with increasing strain, and the hysteresis loss of the polymer maintained a high value (over 90%). Thus, it was clear that the polymer had good energy dissipation performance at each strain.

[0165] PCL 2.4 k The stress relaxation time curves of -γCD (2) -PU are shown in Figure 36, and those of PCL 3.5k The stress relaxation time curve of -γCD 5-PU is shown in Figure 37. These results confirmed that the instantaneous stress at 800% strain disappeared within 1 hour in the stress relaxation test, demonstrating the effective energy dissipation effect of the sliding ring effect of CDs.

[0166] Recyclability Test Method: After the tensile test, the samples were collected and dissolved in DCM at room temperature (25-30°C). The solution was poured into a Teflon mold. The film was then left at room temperature for 24 hours, then left overnight at 35°C under vacuum to obtain a film. The toughness of the resulting film was measured and shown in Figure 38. Figure 38 shows the Young's modulus of the original film (n=1), the film after the first recycling (n=2), and the film after the second recycling (n=3). The results in Figure 38 reveal that the resin performance does not deteriorate significantly even after recycling.

[0167] (Enzymatic Degradation Reaction) The PCL-γCD 9-PU obtained by the above-mentioned method was subjected to an enzymatic degradation reaction. For the degradation experiment, 50 mg of PCL-γCD 9-PU was dissolved in toluene containing 5 wt% water, and lipase (Novozyme) was added at 40 wt% enzyme. This solution was reacted at 60°C under a nitrogen stream. Samples were taken before the reaction and 12, 24, and 84 hours after the start of the reaction, and their molecular weights were measured by GPC. The results are shown in Figure 39. These results demonstrate that the polymer of the present invention, which is degraded by enzymes, has a low environmental impact.

[0168] (Enzymatic Polymerization Reaction) The PCL-γCD 9-PU obtained by the above-described method was subjected to an enzymatic polymerization reaction. For the degradation experiment, 50 mg of PCL-γCD 9-PU was dissolved in anhydrous toluene and lipase (Novozyme) was added at 40 wt %. This solution was reacted at 60°C under a nitrogen stream. Samples were collected before the reaction and 12, 24, 36, and 48 hours after the start of the reaction, and their molecular weights were measured by GPC. The results are shown in Figure 40. These results demonstrate that the polymer of the present invention can be further polymerized by the enzyme. Therefore, the polymer recovered after being degraded by the above-described degradation reaction can be repolymerized and reused. From this perspective, it is clear that this polymer has a low environmental impact.

[0169] (Enzyme-Catalyzed Polymerization Reactions as a Function of Reaction Time) The polymer was dissolved in dry toluene equipped with molecular sieves, and Novozym 435 (wt % relative to the polymer) was added. The reaction was carried out at 60 °C under N2. After each reaction time (1 h, 2 h, 4 h, 8 h, 12 h, 24 h, 36 h, 48 h, 72 h, 96 h, and 120 h), the reaction solvent was collected for GPC analysis. This experiment was carried out for PCL3.5k-γCD(9)-PU, PCL3.5k-γCD(5)-PU, and lPCL3.5k-PU. The results are shown in Figure 41. (a) shows the enzyme concentration at 10 wt %, (b) shows the enzyme concentration at 20 wt %, and (c) shows the enzyme concentration at 50 wt %.

[0170] In Figure 41(a), the Mn of PCL3.5k-γCD(9)-PU changed little. In Figure 41(b), the Mn of PCL3.5k-γCD(9)-PU began to decrease after 1 hour and reached a near minimum after 12 hours. The Mn of PCL3.5k-PU without mobile crosslinks remained almost unchanged. In Figure 41(c), the Mn of PCL3.5k-γCD(9)-PU continued to increase within 8 hours and then began to decrease. The Mn of PCL3.5k-γCD(5)-PU continued to increase within 96 hours. The Mn of PCL3.5k-PU remained almost unchanged even after 120 hours.

[0171] These experimental results clearly demonstrate that the decomposition or increase in molecular weight of PCL3.5k-γCD(a)-PU can be controlled by changing the amount of enzyme added.

[0172] Example 2 of Aspect 1 Before the reaction, a mixture of SH-2-DiOH and PCLx-diOH was heated overnight at 80 °C under vacuum to remove moisture. A mixture of SH-2-DiOH (a mol%) and PCLx-diOH ((100-a) mol%) was sonicated at 60 °C for 30 minutes to 1 hour and then dissolved in dry DMF. HDI ([NCO] / [OH] = 1.05 / 1) and DBTDA (0.25 wt%) dissolved in dry DMF were added to the above mixture. The reaction mixture was then heated under vacuum at 80 °C for 30 minutes to 1 hour. ２ The mixture was heated at 60°C for 24 hours under reduced pressure. After the specified time, the reaction mixture was precipitated in a cold solvent of DCM / MeOH (v / v = 1 / 4) to obtain PCLx-βCD(a)-PU. The raw material feed ratios for each polymer are shown in Table 6. The GPC measurement results are shown in Table 6 and Figure 24.

[0173] The polymer obtained by the above method was subjected to molecular weight measurement, and the results are shown in Table 6.

[0174]

[0175] The resin obtained in the above (Example 2 of Aspect 1) was subjected to the same evaluation test as in (Example 1 of Aspect 1). The results are shown in Figures 42 and 43.

[0176] The results in these figures show higher elongation and breaking strength than PCL-PU that does not contain cyclodextrin. In particular, it is clear that high elongation and breaking strength are achieved even at a relatively low molar ratio of cyclodextrin, resulting in very high toughness. This demonstrates that in Aspect 1, physical properties differ depending on the resin structure, and that by using these appropriately depending on the purpose, the polymer of the present invention can be used in a wide range of applications.

[0177] (Example of Aspect 2) Reagents All reagents were purchased and used without further purification. (1) Ethyl acrylate (EA) (Tokyo Chemical Industry Co., Ltd.) (2) Acetylated γ-cyclodextrin-acrylamide (Ac-γ-CDAAm) (Yushiro Chemical Industry Co., Ltd., Kyoeisha Chemical Co., Ltd.) (3) 1-hydroxycyclohexyl phenyl ketone (Irgacure 184) (Tokyo Chemical Industry Co., Ltd.) (4) ε-caprolactone (CL) (Tokyo Chemical Industry Co., Ltd.) (5) Ethylene glycol (Fujifilm Wako Pure Chemical Industries Co., Ltd.) (6) Tin II 2-ethylhexyl ester (Sn(Oct) ２ ) (FUJIFILM Wako Pure Chemical Corporation) (7) Deuterated chloroform (FUJIFILM Wako Pure Chemical Corporation) (8) Chloroform (FUJIFILM Wako Pure Chemical Corporation) Measuring equipment １ H NMR nuclear magnetic resonance spectrometer "JNM-ECS400 (400 MHz)" (solvent: CDCl) ３ ) SEC size exclusion chromatography "HLC-8420GPC" manufactured by JEOL Ltd. (solvent: chloroform, standard sample: polystyrene, column: TSKgel GMHHR-M, guard column: TSKgel guard column HHR-L) manufactured by Tosoh Corporation; tensile testing machine "Small tabletop testing machine EZ Graph" manufactured by Shimadzu Corporation, test conditions: load cell 10N, test speed 10mm / min

[0178] (Synthesis Example 3) Synthesis of MC elastomer

[0179] An MC elastomer with a mobile crosslinked network was synthesized according to the method described in NPG Asi Mater., 2022, 14, 1. EA (2.3 g, 23 mmol) was placed in a sample tube, and Ac-γ-CDAAm (0.55 g, 0.23 mmol) and Irgacure 184 (9.6 mg, 0.047 mmol) were dissolved therein. The solution was then stirred for 60 minutes using ultrasonic vibrations. The solution was transferred to a mold and allowed to react by irradiating with UV light for 30 minutes while cooling on ice. The resulting elastomer was transferred to a Teflon (registered trademark) Petri dish and dried under reduced pressure in a vacuum heat dryer at 80°C for 12 hours to remove unreacted monomers.

[0180] MC elastomers were prepared as shown in Table 7 below, with the amount of Ac-γ-CDAAm introduced being varied to 1.0, 2.0, and 3.0 mol %.

[0181]

[0182] By synthesizing MC elastomer, a colorless and transparent elastomer was obtained. １ H NMR measurements revealed that the MC elastomer exhibited characteristic peaks derived from the acetyl groups of Ac-γ-CDAAm, and that the peaks derived from the vinyl groups had disappeared, confirming that the synthesis of the MC elastomer had progressed. Comparing the integrals of the acetyl group peaks of γ-CD and the peaks derived from the terminal ethyl groups, the introduction rate of γ-CD was found to be 0.88% for pEAγCD_1 and 2.0% for pEAγCD_2.

[0183] Example 2: ε-caprolactone (1.1 g, 1 mL) was placed in a sample tube, and Sn(Oct) ２A catalyst solution was prepared by dissolving caprolactone (0.18 g, 0.44 mmol) in caprolactone (5.4 g, 5 mL) in a sample tube, followed by the addition of ethylene glycol (0.17 g, 2.7 mmol) to prepare an initiator solution. A ground test tube was filled with ε-caprolactone (0.60 g), and 12 μL each of the catalyst solution and initiator solution was added and stirred. MC elastomer (0.60 g) was then added and stirred thoroughly to allow the MC elastomer to swell with the solution. The test tube was sealed with a silicone septum and purged with nitrogen. The test tube was then heated at 110°C for 48 hours to polymerize the CL and incorporate PCL polymer chains into the MC elastomer. Samples were prepared as follows, varying the type of MC elastomer and the amount of PCL incorporated.

[0184]

[0185]

[0186] The resulting polymer turned white as the amount of polycaprolactone introduced increased. １ When H NMR measurement was carried out, a peak derived from polycaprolactone appeared, confirming that polycaprolactone had been introduced (FIG. 47).

[0187] Size-exclusion chromatography (SEC) analysis was performed to examine the molecular weight of the incorporated polycaprolactone. Chloroform was used as the mobile phase, and polystyrene was used as the standard. The MC elastomer exhibited a single elution peak, whereas the mobile crosslinked network material exhibited a new peak at the lower molecular weight side. Comparison of the two suggests that the lower molecular weight peak is the elution peak of the incorporated PCL (Figure 48). The number-average molecular weight of PCL in the material prepared using pEAγCD_1 was approximately 10,000. On the other hand, a decrease in the molecular weight of PCL was observed with pEAγCD_3. This is thought to be due to the increased number of crosslinking points as the amount of γ-CD introduced increased, resulting in a denser network structure of the MC elastomer, which inhibited the polymerization of CL (Table 9).

[0188]

[0189] (Comparative Example 2) Preparation of a Material Composed of Two Resins PCL was synthesized independently using the reaction described above. A material composed of this polycaprolactone and an MC elastomer (pEAγCD1_PCL50_M) was prepared by casting. PCL (0.50 g) and pEAγCD_1 (0.50 g) were placed in a test tube. Chloroform (9.0 g) was added and stirred until the PCL and pEAγCD_1 were completely dissolved. The solution was poured into a Teflon dish and heated in an oven at 50°C for 24 hours to remove the chloroform.

[0190] Comparing pEAγCD1_PCL50 prepared by in situ polymerization with pEAγCD1_PCL50_M prepared by simple mixing, pEAγCD1_PCL50 was a highly transparent, uniform material, whereas pEAγCD1_PCL50_M was a material with a heterogeneous appearance. This is thought to be because pEAγCD1_PCL50 forms a dense network in which polycaprolactone polymer chains penetrate into a mobile crosslinked network of MC elastomer, whereas pEAγCD1_PCL50_M forms less of such a network.

[0191] (Molding) The prepared MC elastomer and materials were molded into a film of approximately 300 μm in thickness by heat pressing. The heat pressing was performed as shown in Figure 44, with a pressure of 20 MPa and a temperature of 80°C. After heat pressing, the sample was cooled on ice.

[0192] (Evaluation of mechanical properties) The mechanical properties of the MC elastomer and the prepared mobile crosslinked network material were evaluated by tensile testing. The film-shaped sample was cut using a cutter to prepare test pieces as shown in Figure 45. A tensile test was performed using a 10 N load cell at a tensile speed of 10 mm per minute.

[0193] Figure 49 shows the results of tensile tests on MC elastomers and mobile crosslinked network materials. As the amount of γ-CD introduced increased, the breaking strain of the MC elastomers decreased and the maximum stress tended to increase (Figure 49a). This is thought to be due to the effect of increased crosslink density in addition to the molecular rigidity of γ-CD itself. 50 wt% polycaprolactone was introduced into the MC elastomer.

[0194] Comparing the mechanical properties of pEAγCD1_PCL50, pEAγCD2_PCL50, and pEAγCD3_PCL50, pEAγCD1_PCL50 exhibited the highest values ​​for both the breaking strain and maximum stress. When the toughness and initial modulus of the MC elastomer and the resulting materials were evaluated, pEAγCD1_PCL50 showed the greatest improvement in both toughness and initial modulus. This is likely due to the introduction of PCL, a relatively rigid molecular chain, into the network. pEAγCD3_PCL50 exhibited improved toughness due to an increase in breaking strain (Figure 49b). This is likely due to the incorporation of polycaprolactone polymer chains into the highly crosslinked pEAγCD_3 network, expanding the network and improving the flexibility of the material.

[0195] For pEAγCD_1, which showed the greatest improvement in properties, we investigated the mechanical properties when varying the amount of PCL incorporated. Improvements in toughness and initial modulus were observed at all incorporation rates (Figure 49a). However, pEAγCD1_PCL80 was a brittle material, making it difficult to prepare test specimens. pEAγCD1_PCL50, with 50 wt% PCL incorporation, showed the greatest improvement in mechanical properties, with an initial modulus approximately 70 times higher and a toughness approximately 3.5 times higher. At incorporation rates higher than this, improvements remained constant (Figure 49b).

[0196] This is thought to be due to the expansion of the mobile crosslink network of the MC elastomer when it is immersed in the ε-caprolactone solution during synthesis. It is thought that an increase in the volume of the ε-caprolactone solution could cause the mobile crosslink network of the MC elastomer to expand significantly, potentially leading to collapse. Previous research has also reported that immersing a material with mobile crosslinks in a solution could result in polymer chains escaping from the γ-CD rings. Due to these factors, the network expansion of pEAγCD1_PCL60 and pEAγCD1_PCL70 was large, limiting the improvement in mechanical properties. However, it is thought that the introduction of polycaprolactone into pEAγCD1_PCL50 allowed the network of the MC elastomer to be maintained, leading to improved mechanical properties.

[0197] The mechanical properties of pEAγCD1_PCL50, prepared by in situ polymerization, and pEAγCD1_PCL50_M, prepared by simple blending, were also compared. Although pEAγCD1_PCL50_M showed an improvement in the initial modulus, it showed results similar to those of the MC elastomer pEAγCD_1, and did not show significant improvement in properties (Figure 51b). These results demonstrate that the mechanical properties were improved by introducing polycaprolactone into the MC elastomer with a mobile crosslinked network to form semi-IPNs.

[0198] These results revealed the following: (1) The mechanical properties of MC elastomers changed with increasing amounts of γ-CD. This is thought to be due to an increase in the density of crosslinking points. (2) pEAγCD_1, which exhibited the largest breaking strain among the MC elastomers, showed an improvement in initial modulus and consequent toughness with the addition of polycaprolactone. The greatest improvement in properties was observed when the amount of polycaprolactone was 50 wt%, with an initial modulus approximately 70 times higher and toughness approximately 3.5 times higher. (3) Comparing pEAγCD_PCL50, prepared by polymerizing ε-caprolactone in the presence of MC elastomer, with pEAγCD1_PCL50_M, prepared by simple mixing, pEAγCD_PCL50 exhibited a uniform appearance, while pEAγCD_PCL50_M exhibited a heterogeneous appearance. Furthermore, the improvement in mechanical properties of pEAγCD_PCL50_M due to the introduction of polycaprolactone was limited.

[0199] These findings demonstrate that introducing polycaprolactone polymer chains into a flexible crosslinked network of MC elastomers by in situ polymerization to construct semi-IPNs leads to improved mechanical properties of the material.

[0200] The polymer of the present disclosure uses an aliphatic polyester resin, which has a low environmental impact, and yet has excellent physical properties, and therefore can be used in many fields where such performance is required.

Claims

1. The polymer has a cyclodextrin skeleton as a side chain thereof and at least a fatty acid polyester resin structure. The cyclodextrin skeleton is 【Chemistry 1】 (In the formula, R 1 s are the same or different and represent hydrogen, an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 (R 2 is an alkyl group having 1 to 20 carbon atoms), and 20% or more of R 1 s are any one of an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 . x is an integer from 5 to 7) A polymer characterized by:

2. 2. The polymer of claim 1, wherein the fatty acid polyester resin structure is polycaprolactone.

3. 3. The polymer according to claim 1 or 2, which has structural units derived from a compound (A) having a functional group reactive with two isocyanate groups present in a cyclodextrin skeleton and in a structure other than the cyclodextrin skeleton, an aliphatic polyester (B), and a diisocyanate compound (C).

4. Compound (A) is 【Chemistry 2】 (In the formula, R １ are the same or different and each represents a hydrogen atom, an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR ２ (R ２ represents an alkyl group having 1 to 20 carbon atoms, and R １ At least 20% of the groups are acyl groups having 2 to 50 carbon atoms, alkyl groups having 1 to 30 carbon atoms, or -CONHR. ２ It is one of them. x is an integer from 5 to 7) or a compound represented by the following general formula (11): 【Chemistry 3】 (In the formula, R 1 is (A) The following general formula (12): -R 3 -NH-R 4 (12) (R 3 is an alkylene group having 3 to 20 carbon atoms, which may be linear or branched, and may have a substituent. R 4 is a structure represented by the following formula. 【Chemistry 4】 In the formula, R 10 represents hydrogen or a methyl group. (a) The following general formula (13): -R 5 -NHCONH-R 6 (13) (R 5 is an alkylene group having 3 to 20 carbon atoms, which may be linear or branched and may have a substituent. R 6 is the same as R 4 above. or (c) a compound represented by the following general formula (14): -R 5 -OCONH-R 6 (14) (R 5 and R 6 are the same as above.) It represents one of the following. R 2 represents a hydrogen atom, an acyl group having 2 to 50 carbon atoms, or an alkyl group having 1 to 30 carbon atoms. R c represents a group represented by the following general formula (1). 【Chemistry 5】 (In the formula, R 1 s are the same or different and represent hydrogen, an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 (R 2 is an alkyl group having 1 to 20 carbon atoms), and 20% or more of R 1 s are any one of an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 . x is an integer from 5 to 7) 3. The polymer according to claim 1 or 2, which is

5. 3. The polymer according to claim 1, wherein the aliphatic polyester (B) is a polycaprolactone having a skeleton derived from a diol compound in part.

6. 3. The polymer according to claim 1, which is obtained by polymerizing ε-caprolactone in the presence of an acrylic polymer having a cyclodextrin skeleton as a side chain of the polymer.

7. 7. The polymer according to claim 6, wherein the polymerization of ε-caprolactone is further carried out in the presence of a diol compound.

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