Polymers and unsaturated compounds

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

[Technical Field]

[0001] This invention relates to polymers and unsaturated compounds having a cyclodextrin skeleton. [Background technology]

[0002] Aliphatic polyesters such as polycaprolactone (PCL) are being considered as environmentally friendly resins because they are biodegradable. Furthermore, they are attracting attention from the perspective of being recyclable and reusable due to their ability to be broken down and recombined by enzymes.

[0003] However, aliphatic polyesters lack sufficient strength, and improvements in their properties are needed for widespread use. Many attempts have been made to achieve this, such as crosslinking by covalent bonding. However, when crosslinking by covalent bonding is performed, the elasticity of the resin is greatly 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 with excellent properties in both strength and elasticity using aliphatic polyesters.

[0004] Polymer materials having cyclic cyclodextrin (CD) molecules in their side chains are known (for example, Patent Document 2). In such polymer materials, the polymer main chain penetrates the CD rings to form crosslinking points, and these crosslinking points due to CD slide when stress is applied, exhibiting high stress dispersion properties. Regarding this type of structure, studies have primarily focused on acrylic resins, and no studies have been conducted on polyester resins.

[0005] Non-patent document 1 describes a polyurethane resin polymer having cyclic cyclodextrins in its side chains. However, it does not describe the modification of aliphatic polyester resins. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2019-203082 [Patent Document 2] International release 2022 / 024908 [Non-patent literature]

[0007] [Non-Patent Document 1] Soft Matter, 2022,18,5027-5036 [Overview of the project] [Problems that the invention aims to solve]

[0008] The present invention aims to provide a polymer having an aliphatic polyester resin backbone that is biodegradable while possessing excellent performance in terms of strength and flexibility. [Means for solving the problem]

[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 in at least a portion of it.

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

[0011] The above cyclodextrin skeleton is [ka] (In the formula, R 1 These are the same or different hydrogen atoms, acyl groups with 2 to 50 carbon atoms, alkyl groups with 1 to 30 carbon atoms, or -CONHR 2 (R 2 R represents an alkyl group with 1 to 20 carbon atoms. 1 More than 20% of the group consists of acyl groups with 2 to 50 carbon atoms, alkyl groups with 1 to 30 carbon atoms, or -CONHR groups. 2 It is one of the following. x is an integer from 5 to 7)) It is preferable that it is so.

[0012] The polymer of the present invention preferably has structural units derived from a compound (A) having a functional group reactive with a 2-isocyanate group present in the cyclodextrin skeleton and a structure other than the cyclodextrin skeleton, an aliphatic polyester (B), and a diisocyanate compound (C).

[0013] Compound (A) is

[0014]

Chemical formula

[0015] (In the formula, R 1 is the same or different and 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 is an alkyl group having 1 to 20 carbon atoms), and 20% or more of R 1 is any one of an acyl group having 2 to 50 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or -CONHR 2 any one of them. x is an integer from 5 to 7)) It is preferably a compound represented by.

[0016] The aliphatic polyester (B) is preferably polycaprolactone having a skeleton derived from a diol compound in part. 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 the above ε-caprolactone is preferably further carried out in the presence of a diol compound.

[0018] [[ID=

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

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

[0021] (i) The following general formula (13) -R 5 -NHCONH-R 6 (13) (R 5 This is an alkylene group having 3 to 20 carbon atoms, which may be linear or branched, and may have substituents. R 6 The above R 4 (Same as above) Or (c) the following general formula (14) -R 5 -OCONH-R 6 (14) (R 5 and R 6 (This is the same as above.) It represents one of the following. R 2 This represents a hydrogen atom, an acyl group with 2 to 50 carbon atoms, or an alkyl group with 1 to 30 carbon atoms. R c This represents the group shown in the following general formula (1).

[0022] [ka] (In the formula, R 1 These are identical or different acyl groups having 2 to 50 carbon atoms, alkyl groups having 1 to 30 carbon atoms, or -CONHR 2 (R 2 R represents an alkyl group with 1 to 20 carbon atoms. 1 More than 20% of the group consists of acyl groups with 2 to 50 carbon atoms, alkyl groups with 1 to 30 carbon atoms, or -CONHR groups. 2 It is one of the following. x is an integer between 5 and 7. [Effects of the Invention]

[0023] The resin composition of the present invention is primarily composed of an aliphatic polyester skeleton, which has a low environmental impact, while possessing both elasticity and toughness. [Brief explanation of the drawing]

[0024] [Figure 1] A diagram showing the shape of a tensile test sample. [Figure 2] 1H NMR of SH-2-DiOH (500 MHz, 25°C) [Figure 3] 1H NMR of PCL 1.5 k-diOH (500 MHz, 25°C). [Figure 4] 13C NMR of PCL 1.5k-diOH (125 MHz, 25°C). [Figure 5] ¹H NMR of PCL 2.4 k-diOH (500 MHz, 25°C). [Figure 6] 13C NMR of PCL 2.4 k-diOH (125 MHz, 25°C). [Figure 7] ¹H NMR of PCL 3.5 k-diOH (500 MHz, 25°C). [Figure 8] 13C NMR of PCL 3.5 k-diOH (125 MHz, 25°C). [Figure 9] 1H NMR of PCL1.5k-γCD(2)-PU (500 MHz, 25°C). [Figure 10] 1H NMR of PCL1.5k-γCD(5)-PU (500 MHz, 25°C). [Figure 11] 1H NMR of PCL2.4k-γCD(2)-PU (500 MHz, 25°C). [Figure 12] 1H NMR (500 MHz, 25°C) of PCL 2.4 k-γCD (5)-PU. [Figure 13] 1H NMR (500 MHz, 25°C) of PCL3.5k-γCD(2)-PU. [Figure 14] 1H NMR of PCL3.5k-γCD(5)-PU (500 MHz, 25°C). [Figure 15] 1H NMR of lPCL 1.5 k-PU (500 MHz, 25°C). [Figure 16] 1H NMR of lPCL2.4 k-PU (500 MHz, 25°C). [Figure 17] 1H NMR of lPCL3, 5 k-PU (500 MHz, 25°C). [Figure 18] 1H NMR (500 MHz, 25°C) of PCL1.5k -THEED (2) -PU. [Figure 19] 1H NMR (500 MHz, 25°C) of PCL1.5k-THEED (5) -PU. [Figure 20] 1H NMR (500 MHz, 25°C) of PCL2.4 k-THEED (2)-PU. [Figure 21] 1H NMR (500 MHz, 25°C) of PCL2.4 k-THEED (5)-PU. [Figure 22] 1H NMR (500 MHz, 25°C) of PCL3.5k-THEED (2)-PU. [Figure 23] 1H NMR (500 MHz, 25°C) of PCL3.5k-THEED (5)-PU. [Figure 24](a) GPC curve for PCL 1.5 k-PUs; (b) GPC curve for PCL 2.4 k-PUs; (c) GPC curve for PCL 3.5 k-PUs. [Figure 25] ATR-FTIR for PCL 2.4 k-PUs [Figure 26] DSC curve of second scan for PCL 2.4 k-PUs [Figure 27] (a) Tg and (b) ΔH results for PCL 2.4 k-PUs from the DSC curve of the second scan. [Figure 28] Stress-strain curve of PCL-PUs. [Figure 29] Stress-strain curve of PCL 3.5 k-PUs. [Figure 30] Toughness and Young's modulus of PCL-PUs. [Figure 31] Toughness and Young's modulus of PCL 3.5 k-PUs. [Figure 32] Hysteresis loss calculated from the cyclic stress-strain curve at a fixed strain (200%). Ten cycles were performed. [Figure 33] (a) PCL1.5k-γCD (2)-PU, (b) PCL1.5k-γCD (5)-PU, (c) PCL2.4k-γCD (2)-PU, (d) PCL2.4k-γCD (5)-PU, strain [Figure 34] (a) Repeated tensile test curves of PCL2.4k-γCD(5)-PU recorded with increasing maximum strain (200%, 400%, 600%, 800%, 1000%, 1200%). (b) Energy dissipation and damping capacity of each circle in the repeated tensile test curve. [Figure 35] (a) Repeated tensile test curves of PCL3.5k-γCD(5)-PU recorded with increasing maximum strain (200%, 400%, 600%, 800%, 1000%, 1200%). (b) Energy dissipation and damping capacity of each circle in the repeated tensile test curve. [Figure 36] Stress relaxation time curve of PCL2.4k-γCD(2)-PU. [Figure 37]Stress relaxation time curve of PCL3.5k-γCD (5)-PU [Figure 38] (a) Toughness and (b) Young's modulus (original film (n=1), film after primary recycling (n=2), secondary recycling (n=3)). [Figure 39] A diagram showing the results of an enzymatic decomposition reaction. [Figure 40] A diagram showing the results of an enzyme polymerization reaction. [Figure 41] A diagram showing the results of an enzyme polymerization reaction. [Figure 42] Stress-strain curve of a polymer using SH-02-siOH. [Figure 43] Toughness and Young's modulus of polymers using SH-02-SiOH. [Figure 44] This is a schematic diagram illustrating the hot pressing method. In the diagram, Teflon is a registered trademark. [Figure 45] A diagram showing the shape of a tensile test sample. [Figure 46] 1HNMR of Ac-γ-CD-AAm and pEAγXD_1 [Figure 47] 1HNMR of pEAγCD1_PCL50 and PCL [Figure 48] Dissolution curve of pEAγCD1_PCL50 [Figure 49] The stress-strain curves and the relationship between Young's modulus and fracture strength (a) and (b) are the results for MC elastomer, while (C) and (D) are the results for pEAγCD1_PCL50. [Figure 50] Stress-strain curve and relationship between Young's modulus and fracture strength for MC elastomer (pEAγCD1_PCLx (x=0.50,60,70)). [Figure 51] (a) Stress-strain curves of pEAγCD1_PCL50 and pEAγCD_1 (b) pEAγCD1_PCL50_M. [Modes for carrying out the invention]

[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 chains. The cyclodextrin ring, through which the polymer backbone passes, exhibits excellent elasticity. Furthermore, the bonds do not break when stress is applied; instead, the cyclic structure moves along the backbone to accommodate deformation caused by stress. As a result, the physical properties do not deteriorate due to bond breakage, and it is possible to achieve both excellent elasticity and strength, properties that are normally difficult to reconcile.

[0026] In the present invention, the polymer side chain has a cyclodextrin ring. Such a cyclodextrin ring is preferably structured as shown by the following general formula (1).

[0027] [ka] (In the formula, R 1 These are the same or different hydrogen atoms, acyl groups with 2 to 50 carbon atoms, alkyl groups with 1 to 30 carbon atoms, or -CONHR 2 (R 2 R represents an alkyl group with 1 to 20 carbon atoms. 1 More than 20% of the group consists of acyl groups with 2 to 50 carbon atoms, alkyl groups with 1 to 30 carbon atoms, or -CONHR groups. 2 It is one of the two. x is an integer between 5 and 7.

[0028] The compound represented by the above general formula (1) is preferably one in which 20% or more of the hydroxyl groups bonded to the cyclodextrin ring are replaced by hydrophobic groups. In other words, since the main backbone is a hydrophobic aliphatic polyester resin, it is preferable that the hydroxyl groups of the cyclodextrin ring are hydrophobic, as this improves compatibility and physical properties.

[0029] In the above general formula (1), R 1More than 60% of the group consists of acyl groups with 2 to 50 carbon atoms, alkyl groups with 1 to 30 carbon atoms, or -CONHR groups. 2 It is more preferable that either of these be the case, and even more preferable that it be 90% or more. Furthermore, there is no particular upper limit, and all hydroxyl groups may be substituted. Cyclodextrin rings are preferable because higher hydrophobicity leads to better affinity with organic functional groups, thus increasing affinity with aliphatic polyesters.

[0030] The above dextrin skeleton exists in three forms: α (x=5), β (x=6), and γ (x=7). Any of these may be used, but β or γ are particularly preferred. The use of β or γ is particularly preferred because it tends to result in a structure where the main chain penetrates the ring. It is also acceptable for two or more of α, β, and γ to be present in a mixture.

[0031] The choice of which of these cyclodextrin structures to select is important because it affects the properties of the resulting polymer.

[0032] Generally, β and γ are said to be more likely to form through-structures, so it is preferable to use these. Furthermore, our studies have shown that when the β form is used, a polymer with the best properties in terms of breaking strength, elongation, and toughness is obtained, and when the γ form is used, a polymer exhibiting a high Young's modulus is obtained.

[0033] Neither is inherently superior to the other; rather, it is preferable to select and use them appropriately based on which properties are most important for the intended purpose. Furthermore, if intermediate performance is desired, a combination of the β and γ forms may be used.

[0034] The cyclodextrin represented by the above general formula (1) has some or all of the hydroxyl groups in the proportions described above as R 1 It may also be a substitute for the base. 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 fewer carbon atoms, and -CONHR (where R is a methyl group or an ethyl group). Such substitutions 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% of the total amount of the polymer. By including it in such a proportion, a desirable effect 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 aliphatic polyester as its main constituent unit. In this invention, the main chain skeleton is composed of structural units based on aliphatic polyester. Aliphatic polyester is known as a biodegradable resin, and by using it as the main structural unit, a polymer with low environmental impact can be produced.

[0037] Furthermore, aliphatic polyesters can be broken down into low-molecular-weight compounds by enzymatic decomposition. Moreover, the enzymatically decomposed products can be regenerated into polymers through further enzymatic reactions. Therefore, discarded polymers can be converted into low-molecular-weight compounds by enzymatic decomposition. Then, by performing an ester bond formation reaction again on the recovered low-molecular-weight compounds, the polymer of the present invention can be regenerated.

[0038] Non-patent document 1 discloses a polymer in which polyether is the main structural unit. By using polyester as the main structural unit, it is preferable in that it has superior weather resistance and chemical resistance compared to cases in which polyol-based systems are the main backbone.

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

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

[0041] If the aliphatic polyester is mainly composed of polycaprolactone, it may also have structural units made up of diol compounds. In other words,

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

[0043] It may also be a material whose constituent unit is a polycaprolactone as represented by . Such polycaprolactones are preferred because they are easy to synthesize and both polyester ends are hydroxyl groups.

[0044] Such polycaprolactones HO-R 3 ―OH It has a structural unit based on a diol compound represented by the general formula. While there are no particular limitations on such diol compounds, those with a molecular weight of 4000 or less are preferred.

[0045] Specifically, 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 polymer of the present invention exhibits significantly different physical properties depending on whether the cyclodextrin skeleton is β-form or γ-form. Furthermore, because it uses an aliphatic polyester as its basic skeleton, its physical properties also differ from those of the polymer described in Non-Patent Document 1, which uses a polyether as its basic skeleton.

[0047] When the cyclodextrin skeleton is in the β form, the elongation can be 500 to 10000%. The lower limit is more preferably 1000%, and even more preferably 1500%. The upper limit is more preferably 5000%, and even more preferably 3000%.

[0048] When the cyclodextrin skeleton is in the β form, the tensile 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 the β-isomer, the Young's modulus can be 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 in the β-form, the toughness is 100-1000 MJm -3 This can be done. The lower limit above is 150 MJm -3 It is more preferable that this be the case. The above upper limit is 700 MJm -3 It is preferable that it be so.

[0051] When the cyclodextrin skeleton is in the γ form, the elongation can be 500 to 10000%. The lower limit is more preferably 1000%, and even more preferably 1500%. The upper limit is more preferably 5000%, and even more preferably 3000%.

[0052] When the cyclodextrin skeleton is in the γ form, the tensile strength can be 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 the γ-isomer, the Young's modulus can be 20 to 200 MPa. The lower limit of the above is more preferably 30 MPa. The upper limit of the above is more preferably 150 MPa.

[0054] When the cyclodextrin skeleton is in the γ form, the toughness is 50-700 MJm -3 This can be done. The lower limit above is 80 MJm -3 It is more preferable that this be the case. The above upper limit is 500 MJm -3 It is preferable that it be so.

[0055] Thus, the polymer of the present invention is preferable in that it can provide resins with excellent physical properties. Furthermore, these values ​​were obtained by the measurement method in the example of Embodiment 1 in the examples of this specification.

[0056] The present invention may be a polymer consisting only of the polycaprolactone structure and components for forming a cyclodextrin skeleton in the side chain as described above, but it may also have other constituent units. That is, in order to obtain excellent strength, other constituent units are used in combination, and more specifically, the following embodiments 1 and 2 can be cited.

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

[0058] These embodiments are polymers in which a resin structure other than aliphatic polyester has been introduced to further improve the physical properties of the polymer. Embodiments 1 and 2 are described in detail below.

[0059] (Regarding aspect 1) The polymer of Embodiment 1 is a polyurethane resin having a biodegradable aliphatic polyester backbone into which a structure derived from compound (A) has been introduced. In such a structure, the resin chains penetrate the cyclodextrin rings to form crosslinking points, and it is presumed that the crosslinking points due to CD slide when stress is applied, resulting in a mobile crosslinking material that exhibits high stress dispersion.

[0060] Furthermore, the presence of urethane groups also leads to the formation of a crosslinked structure through hydrogen bonding. Therefore, the synergistic effect of two crosslinked structures with different mechanisms—crosslinking by CD and crosslinking by hydrogen bonding—is preferable in that it achieves even better physical properties.

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

[0062] [ka]

[0063] The compound of the above general formula is a polycaprolactone in which the aliphatic polyester (B) has a diethylene glycol skeleton in part, the isocyanate compound (C) is tetramethylene diisocyanate, and compound (A) is a specific compound represented by general formula (2). Such compounds are examples of polymers of the present invention, and the present invention is not limited to such specific polymers. The following details each of the components (A) to (C).

[0064] (A compound having a cyclodextrin skeleton and two isocyanate groups present in the structure other than the cyclodextrin skeleton, and a functional group that is reactive with these groups) Compound (A) is a compound having a cyclodextrin ring. In the polymer of the present invention, a crosslinked structure is formed when a main chain derived from other components penetrates the cyclodextrin ring of such compound (A).

[0065] Compound (A) has a cyclodextrin skeleton represented by the general formula (1) described above, and further has functional groups that react with two or more isocyanate groups. Examples of functional groups that react 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 by the reactions of each component (A) to (C) described in detail below. This results in a resin having cyclodextrin structures in the side chains relative to the polymer main chain. The main chain then penetrates through these cyclodextrin structures, forming a crosslinked structure.

[0066] Compound (A) must contain two or more functional groups that are 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 its side chains. If there are two functional groups that are reactive with isocyanate groups, a chain-like resin is obtained. If there are three or more functional groups that are reactive with isocyanate groups, the compound itself becomes a crosslinking site. Using a compound with a total of two functional groups that are reactive with isocyanate groups is particularly preferable because it allows for easy control of physical properties and easy handling.

[0067] Such compounds include, [ka] It is preferable to have a structure represented by the following. Compounds having such a structure are preferable because they are easy to synthesize and can be produced using relatively inexpensive raw materials.

[0068] Such compounds can be obtained, for example, by the reaction of 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] [ka] (In the formula, R 1 These are the same or different hydrogen atoms, acyl groups with 2 to 50 carbon atoms, alkyl groups with 1 to 30 carbon atoms, or -CONHR 2 (R 2 R represents an alkyl group with 1 to 20 carbon atoms. 2More than 20% of the group consists of acyl groups with 2 to 50 carbon atoms, alkyl groups with 1 to 30 carbon atoms, or -CONHR groups. 3 It is one of the following. R 3 This is an alkyl chain having 1 to 20 carbon atoms, which may have amide groups, ester groups, or sulfide groups in its main chain. X 1 ,X 2 Each of them is either the same or different, and OH or NH2x is an integer between 5 and 7.

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

[0072] [ka] Furthermore, such compounds are known compounds described in Non-Patent Document 1 mentioned above.

[0073] Also, the following general formula (11) Compounds with structures like those represented by can also be used.

[0074] [ka] (In the formula, R 1 teeth, (a) The following general formula (12) -R 3 -NH-R 4 (12) (R 3 This is an alkylene group having 3 to 20 carbon atoms, which may be linear or branched, and may have substituents. R 4 The structure is represented by the following formula. [ka] In the formula, R 10 represents a hydrogen or methyl group. (i) The following general formula (13) -R 5 -NHCONH-R 6 (13) (R 5 This is an alkylene group having 3 to 20 carbon atoms, which may be linear or branched, and may have substituents. R 6 The above R 4 (Same as above) Or (c) the following general formula (14) -R 5 -OCONH-R 6 (14) (R 5 and R 6 (This is the same as above.) It represents one of the following. R 2 This represents a hydrogen atom, an acyl group with 2 to 50 carbon atoms, or an alkyl group with 1 to 30 carbon atoms. R c This represents the group shown in the following general formula (1).

[0075] [ka] (In the formula, R 1 These are identical or different acyl groups having 2 to 50 carbon atoms, alkyl groups having 1 to 30 carbon atoms, or -CONHR 2 (R 2 R represents an alkyl group with 1 to 20 carbon atoms. 1 More than 20% of the group consists of acyl groups with 2 to 50 carbon atoms, alkyl groups with 1 to 30 carbon atoms, or -CONHR groups. 2 It is one of the following. x is an integer between 5 and 7. More specifically, such compounds include:

[0076] [ka] (In the formula, R 1 These are the same or different hydrogen atoms, acyl groups with 2 to 50 carbon atoms, alkyl groups with 1 to 30 carbon atoms, or -CONHR 2 (R 2 (represents an alkyl group with 1 to 20 carbon atoms) R 7 represents a hydrogen or methyl group. R 8(This refers to an alkylene chain with 2 to 20 carbon atoms.) One could list these:

[0077] Such compounds are preferable because they are relatively easy to synthesize and can be obtained with high purity. Furthermore, the resulting polymers offer a high degree of flexibility in design, as the distance between the main chain and the cyclodextrins can be appropriately controlled, allowing for easy penetration of the main chain. This is preferable.

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

[0079] Using the compound represented by the above general formula (4) is preferable because the resulting polymer has particularly excellent physical properties.

[0080] Such compounds can be obtained by the reaction of compounds having an unsaturated group, as described in International Publication 2022 / 024908, with α-thioglycerol.

[0081] (Aliphatic polyester (B)) In Embodiment 1, the main chain skeleton has structural units based on aliphatic polyester (B). Aliphatic polyester is known as a biodegradable resin, and by using it as the main structural unit, a polymer with a low environmental impact can be made.

[0082] Examples of aliphatic polyester resins (B) that can be used in Embodiment 1 include those described above.

[0083] The aliphatic polyester (B) used as a constituent unit preferably has a number-average molecular weight of 1000 to 4000. The method for measuring the number-average molecular weight is as described in the examples.

[0084] (Polyisocyanate compound (C)) The above polyisocyanate compound (C) is a well-known compound widely used in the field of resins, and any of these can be used. The polyisocyanate compound (C) is preferably a diisocyanate.

[0085] In Embodiment 1 of the present invention, the effect is obtained by a crosslinking structure other than a covalent bond; therefore, a crosslinking structure with three or more polyfunctional structures is not necessary. However, as long as the effect of the present invention is not impaired, the structural units may have three or more polyisocyanate compounds as their constituent units. Even when a polyisocyanate compound with three or more functions is used in part, it is preferable that the amount used be 15.0% by mass or less of the total amount of polyisocyanate compound.

[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, norbornane diisocyanate, and the like.

[0087] (Blend amount) In the present invention, the amounts of each of the above-mentioned components (A) to (C) are not particularly limited, but are preferably within the range shown below.

[0088] (Content of constituent units based on compound (A) having two or more hydroxyl groups present in the cyclodextrin skeleton and structures other than the cyclodextrin skeleton) The amount of compound (A) is preferably 0.1 to 10% by weight relative to the total amount of compounds (A) to (C). This range is preferable because it allows the number of crosslinks in the polymer to be within an appropriate range, thereby obtaining a polymer with the desired physical properties.

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

[0090] (Content of constituent units based on aliphatic polyester (B)) The above compound (B) is preferably in an amount of 85.0 to 95.0% by weight relative to the total amount of compounds (A) to (C). This range is preferable because it allows the number of crosslinks in the polymer to be within an appropriate range, thereby obtaining a polymer with the required physical properties.

[0091] The lower limit of the amount of compound (B) is more preferably 8.0% by weight. 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 constituent units based on isocyanate compound (C)) The above compound (C) is preferably in an amount of 1 to 10% by weight relative to the total amount of compounds (A) to (C). This range is preferable because it allows the number of crosslinks in the polymer to be within an appropriate range, thereby obtaining a polymer with the desired physical properties.

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

[0094] (Method of producing polymers) The polymer of the present invention is composed of the above-described components (A) to (C) as constituent units. Such a polymer can be obtained by mixing the above-described components (A) to (C) in an organic solvent solution and heating it to 40 to 80°C.

[0095] Such reactions may utilize a catalyst. The catalyst is not particularly limited and examples include N,N-dimethylcyclohexylamine, dibutyltin dilaurate, N-ethylmorpholine, bis(2,dimethylaminoethyl) ether, 2,2'-oxybis(N,N-dimethylethylamine), and triethanolamine.

[0096] (Properties of polymers) The polymer according to Embodiment 1 of the present invention has the chemical structure described above, but it is particularly preferable that it has the following physical properties. By satisfying the following properties, a polymer with even better physical properties can be obtained.

[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 method for measuring molecular weight is as 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 method for measuring the glass transition temperature is as 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 method for measuring the melting point is as described in the examples.

[0100] (Molding method) The polymer of the present invention can be molded into a predetermined shape by applying a polymer solution 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 embodiment 2 is obtained by polymerizing ε-caprolactone in the presence of an acrylic polymer (C) having a cyclodextrin skeleton as a side chain of the polymer (this may be hereinafter referred to as the first polymer) (the polymer obtained by this polymerization reaction may be hereinafter referred to as the second polymer). When a polymerization reaction is newly carried out in the presence of the first polymer, the first polymer and the second polymer form a tightly intertwined structure called an interpenetrating structure, which improves the physical properties.

[0102] In this invention, a polymer having a cyclodextrin skeleton is used as the first polymer. Since such a first polymer has a crosslinked structure in which the main chain penetrates the cyclodextrin ring, a more favorable interpenetrating structure is formed. Furthermore, it is presumed that some of the polycaprolactone structure penetrates the cyclodextrin ring.

[0103] Therefore, the polymer of the present invention has significantly different physical properties from resin mixtures obtained by blending acrylic polymer (C) and polycaprolactone, and possesses unique and superior physical properties that cannot be obtained by simple blending.

[0104] (Acrylic Polymer (C)) Known acrylic polymers having a cyclodextrin ring as a side chain can be used. Such polymers are not particularly limited, and examples include copolymers of monomers having a cyclodextrin ring as a side chain and other unsaturated polymers.

[0105] Monomers having a cyclodextrin ring as a side chain are not particularly limited and include known examples. Specifically, examples include monomers described in International Publication 2012 / 036069 and International Publication 2022 / 024908.

[0106] (Other radical polymerizable monomers) Other radical polymerizable monomers are given by the following general formula (a1)

[0107] [ka] (In formula (a1), Ra is a hydrogen atom or a methyl group, R 3 (wherein this character represents a halogen atom, a hydroxyl group, a thiol group, an amino group or a salt thereof which may have one substituent, a carboxyl group or a salt thereof which may have one substituent, an amide group or a salt thereof which may have one or more substituents, or a phenyl group which may have one or more substituents) Examples of compounds represented by [formula] can be given.

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

[0109] In particular, in equation (a1), R 3However, it is preferable that the hydrogen atoms are substituted with C1-C10 alkyl groups, or that the hydrogen atoms are substituted with C1-C10 alkyl groups, or that the hydrogen atoms are substituted with C1-C10 alkyl groups. In this case, other radical polymerizable monomers are relatively hydrophobic, and copolymerization with host group polymerizable monomers proceeds easily. More preferably, the alkyl group substituted has C2-C8, particularly preferably C2-C6, in which case the toughness and strength of the resulting polymer material are also easily improved. This alkyl group may be linear or branched.

[0110] Specific examples of monomers 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, ethoxy-diethylene glycol acrylate, methoxy-triethylene glycol acrylate, methoxy-polyethylene glycol acrylate, styrene, etc. These can be used individually or in combination of two or more.

[0111] In the acrylic polymer used in embodiment 2 of the present invention, it is preferable that the polymer contains constituent units derived from monomers having the cyclodextrin ring as a side chain in a proportion of 5 to 70% by mass of the entire polymer. This range is preferable because it significantly improves the physical properties. 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 general methods. Specifically, examples include radical polymerization by heat, radical polymerization by light, anionic polymerization, cationic polymerization, etc. Among these, polymerization by radical polymerization is particularly preferred.

[0113] When performing the above-mentioned photo-induced radical polymerization, it is preferable to use a photopolymerization initiator. The above-mentioned photopolymerization initiator is not particularly limited and includes, for example, acetophenone-based initiators such as 1-hydroxycyclohexylphenyl ketone (trade name: IRGACURE184), 2-hydroxy-2-methylpropiophenone (trade name: IRGACURE1173), 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-diphenylethane-1-one; benzophenone, [4-(methylphenylthio)phenyl]phenylmethanone, 4-hydroxybenzophenone, and 4-phenylbenzophenone. Benzophenone-based initiators such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone-based initiators such as 2-chlorothioxanthone and 2,4-diethylthioxanthone; acylphosphine oxide-based initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; oxime ester-based initiators such as 1,2-octanedione, 1-[4-(phenylthio)phenyl], 2-(0-benzoyl oxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazoyl-3-yl]-, and 1-(0-acetyl oxime) can be used. The amount of the above photopolymerization initiator used is preferably 0.1 to 2% by weight relative to 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 high-pressure mercury lamps, LED lamps, and metal halide lamps.

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

[0116] (Polycaprolactone polymerization) The polymer of the present invention is produced by polymerizing ε-caprolactone in the presence of the acrylic polymer (C) described above. Examples of ε-caprolactone polymerization include dissolving ε-caprolactone as a raw material in an organic solvent solution of the acrylic polymer (C), removing the solvent and impregnating the acrylic polymer (C), which has been molded into a predetermined shape, with a raw material such as ε-caprolactone and then performing polymerization, dissolving the acrylic polymer in ε-caprolactone and performing polymerization, and melting the acrylic polymer by heating and then performing polymerization in a state where it is mixed with ε-caprolactone.

[0117] During the polymerization of polycaprolactone, a portion of it is HO-R 3 It may also have a constituent 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 with a molecular weight of 500 or less are preferred.

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

[0119] When using the above-mentioned diol compound, the amount used is preferably in the range of 0 to 1% by mass in terms of (diol compound) / (caprolactone + diol compound) (weight ratio). This range is particularly preferable because it allows for the acquisition of desirable physical properties. 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] During polymerization, a catalyst may be used as needed. Specific examples of catalysts include tin(II) 2-ethylhexanoate, titanium(IV) tetrabutoxide, bis(2-ethylhexanoate) zinc, calcium methoxide, tributyltin methoxide, dibutoxyzinc, and lipase. The amount of catalyst 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 Embodiment 2, the amount of polycaprolactone is preferably 20 to 90% by mass of the total polymer. Within this range, the above-mentioned 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 polymers) The polymer according to embodiment 2 of the present invention has the chemical structure described above, but it is particularly preferable that it has the following physical properties. (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 will be measured according to the method described in the examples. Specifically, it will be calculated by size exclusion chromatography. (Eluent: 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) by 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 by differential scanning calorimetry during the first heating process (heating rate 10°C). o The melting peak is determined from the temperature at which it is observed (C / min).

[0123] The polymer of the present invention is not particularly limited in its uses and can be used in molded products and adhesives for automotive parts, electrical products, agricultural materials, office supplies, daily necessities, etc. [Examples]

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

[0125] In the following examples, each monomer refers to the following: [ka] In the formula, X=7 TAcγCD-diOH [ka] In the formula, X=7 Ac-γ-CDAAm

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

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

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

[0130] Tensile test: Tensile tests of the polymers were performed at 25°C with a deformation rate of 1 mm / s using an Autograph AG-X plus (Shimadzu Corporation). All samples were tested using at least three specimens to calculate the mean and standard deviation of the mechanical properties. Young's modulus was calculated from the initial slope of the stress-strain curve in the range of 1–6% strain 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 shapes of the samples used are shown in Figure 45.

[0131] Cycle tensile test: Cycle tensile testing was performed using an Autograph AG-X plus (Shimadzu Corporation). Specimens were continuously stretched and retrieved without intervals, and the maximum strain was set to 200% for 10 cycles 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: The stress relaxation test was performed using Autograph AG-X plus. (Shimadzu Corporation). The specimen was stretched to 800%. The strain was then maintained, 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. 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 rate of 1.50 mL / min. -1The measurements were performed at 40 °C. For the measurements, Tosoh Corporation's HLC-8420GPC EcoSEC (registered trademark) was used, and two Tosoh TSKgel columns (TSKgel G2500HHR and TSKgel G4000HHR) were used.

[0133] Differential scanning calorimeter (DSC): The glass transition temperature (Tg) and melting point (Tm) of the sample were measured using a differential scanning calorimeter under an N2 gas flow (20 mL / min). The instrument used was the Hitachi High-Technologies Corporation DSC 7020 system. Measurements were performed at a temperature range of -100°C to 100°C at a rate of 10°C / min. All samples were first cooled to -100°C and then heated to 100°C; the curve obtained at this stage is called the first scan. After cooling again to -100°C, all samples were heated again to 100°C; the curve obtained at this stage is called the second scan.

[0134] Thermogravimetric analysis (TGA): The thermal degradation of polymers was measured using a TGA system (PerkinElmer STA 6000). Measurements were taken by raising the temperature from 80°C to 500°C at a heating rate of 10°C / min under an N2 gas flow rate of 20 mL / min.

[0135] ATR-FTIR: Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) is performed using a JASCO FT / IR-6100 spectrometer at 4000-800 cm⁻¹. -1 Measurements were taken within the wavenumber range.

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

[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 an 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 the white precipitate was separated by suction filtration. The resulting solid was dried overnight at 50°C in a forced-air dryer, and then dried in vacuum at 50°C for 1 day. The yield was 16% (0.37 g).

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

[0139] [ka]

[0140] Diethylene glycol and Sn(Oct)2 were added to a dry tube under N2. ε-Caprolactone was added to the reaction mixture and reacted at 120°C for 20 hours. After the predetermined time, the reaction mixture was directly precipitated in cold hexane to obtain the desired aliphatic polyester (PCL). x -diOH was obtained. The ratio of raw material usage is shown in Table 1.

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

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

[0143] [ka]

[0144] Before the reaction, a mixture of TAcγCD-diOH and PCLx-diOH was heated overnight under vacuum at 80°C to remove water. 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 heated under N2 at 60°C for 24 hours. After a predetermined time, the reaction mixture was precipitated in the cold solvent DCM / MeOH (v / v=1 / 4) to obtain PCLx-γCD(a)-PU. The raw material supply ratios for each polymer are shown in Table 2. The GPC measurement results are shown in Table 5 and Figure 24.

[0145] [Table 2] X : 1.5k, 2.4k, 3.5k. a: mol% of TAcγCD-diOH.

[0146] Comparative Example 1: Preparation of 4-2 lPCLx-PU (Comparative example without a cyclodextrin ring)

[0147] [ka]

[0148] Before the reaction, all starting materials were heated overnight under vacuum at 80°C to remove moisture. PCLx-diOH was dissolved in dry DMF. Next, HDI ([NCO] / [OH] = 1.05 / 1) and DBTDA (0.25 wt%) dissolved in dry DMF were added. The reaction mixture was heated under N2 at 60°C for 24 hours. After a predetermined time, the reaction mixture was precipitated in the cold solvent DCM / MeOH (v / v=1 / 4) to obtain lPCLx-PU. The supply ratios are shown in Table 3. The GPC measurement results are shown in Table 5 and Figure 24.

[0149] [Table 3] x: 1.5k, 2.4k, 3.5k.

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

[0151] [Chemical Formula]

[0152] Before the reaction, all the reagents were heated at 80 °C under vacuum overnight to remove moisture. THEED (b mol%) and PCLx-diOH (b mol%) were mixed under sonication 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 heated at 60 °C for 24 hours under N2. After a predetermined time, the reaction mixture was precipitated into a cold solvent of DCM / MeOH (v / v = 1 / 4) to achieve 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] [Table 4] X : 1.5k, 2.4k, 3.5k. b: mol% of THEED.

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

[0155] [Table 5]

[0156] Preparation of Film PCLx-γCD (a)-PU was dissolved in DCM and poured into a Teflon (registered trademark) mold. The film was obtained by allowing it to stand still at room temperature for 24 hours and then standing overnight at 35 °C under vacuum.

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

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

[0159] Regarding the Tg and ΔH obtained from the DSC results, the relationships of (a) crosslinking rate / Tg and (b) crosslinking rate / ΔH are shown respectively. From these results, (a) when crosslinking points are introduced, all crosslinked polymers show a higher Tg than lPCL 2.4k -PU, and the higher the crosslinking amount, the higher the Tg. (b) It was revealed that ΔH increases by the introduction of the covalent crosslinking agent THEED, but ΔH slightly decreases by the introduction of the mobile crosslinking agent CD.

[0160] For each polymer of the examples, the stress-strain curves are shown in Figs. 28 and 29. From these results, it became clear that the polymers of the present invention have excellent physical properties in both elongation and breaking strength compared to the comparative examples.

[0161] For each sample, the relationships between Young's modulus and toughness plotted are shown in Figs. 30 and 31. From this, it is clear that the polymers of the present invention achieve excellent performance in both Young's modulus and toughness.

[0162] The hysteresis loss calculated from the repeated stress-strain curve at a fixed strain (200%) is shown in Fig. 32. The cycles were carried out 10 times. From these results, it became clear that the hysteresis loss of all polymers could be quantified and this value tended to stabilize after 5 cycles.

[0163] Figure 33 shows the cyclic stress-strain curves for each sample with a fixed strain (200%). Ten cycles were performed. These results revealed that the hysteresis originating from molecular chain slip in the supramolecular network was greatest in the first cycle.

[0164] (a) The cyclic tensile test curve of PCL-γCD (5-PU) recorded as the maximum strain increased. (b) The energy dissipation and damping capacity of each circle in the cyclic tensile test curve are shown in Figure 34. (a) The cyclic tensile test curve of PCL-γCD (5-PU) recorded when the maximum strain increased, and (b) The energy dissipation and damping capacity of each circle in the cyclic tensile test curve are shown in Figure 35. From these results, (a) the hysteresis loop became larger and the residual strain became more pronounced as the strain increased. (b) The energy loss increased as the strain increased, and it was confirmed that the hysteresis loss of the polymer remained at a high value (over 90%). Thus, it became clear that it has good energy dissipation performance at each strain.

[0165] PCL 2.4 k -γCD (2) -PU stress relaxation time curve is shown in Figure 36, PCL 3.5k The stress relaxation time curve for -γCD 5-PU is shown in Figure 37. These results confirm that in the stress relaxation test, the instantaneous stress at 800% strain disappeared within one hour, demonstrating the effective energy dissipation effect due to the sliding ring effect of the CD.

[0166] Recyclability test Method: After tensile testing, samples were collected and dissolved in DCM at room temperature (25-30°C). The solution was poured into a Teflon® mold. The film was obtained by standing it at room temperature for 24 hours, followed by standing it overnight under vacuum at 35°C. The toughness measured for the obtained film is shown in Fig. 38. In Fig. 38, the measurement results of the Young's modulus of the original film (n = 1), the film after the first recycle (n = 2), and the second recycle (n = 3) are shown. From the results of Fig. 38, it became clear that the resin performance did not significantly decrease even in the recycled resin.

[0167] (Degradation reaction by enzyme) For the PCL-γCD 9-PU obtained by the method described above, a degradation reaction by enzyme was carried out. In the degradation experiment, 50 mg of PCL-γCD 9-PU was dissolved in toluene containing 5 wt% water, and lipase (manufactured by Novozyme) was added at 40 wt% of the enzyme. This solution was reacted at 60 °C under a nitrogen stream. Samples were taken before the reaction, 12 hours, 24 hours, and 84 hours after the start of the reaction, and the molecular weights of these were measured by GPC. The results are shown in Fig. 39. From these results, it became clear that the polymer of the present invention is decomposed by enzyme, and thus has a small environmental load.

[0168] (Polymerization reaction by enzyme) For the PCL-γCD 9-PU obtained by the method described above, a polymerization reaction by enzyme was carried out. In the degradation experiment, 50 mg of PCL-γCD 9-PU was dissolved in anhydrous toluene, and lipase (manufactured by Novozyme) was added at 40 wt%. This solution was reacted at 60 °C under a nitrogen stream. Samples were taken before the reaction, 12 hours, 24 hours, 36 hours, and 48 hours after the start of the reaction, and the molecular weights of these were measured by GPC. The results are shown in Fig. 40. From these results, it became clear that the polymer of the present invention can further proceed with polymerization by enzyme. Therefore, it is also possible to polymerize and reuse again the polymer that was depolymerized and recovered by the above-described degradation reaction. From this point of view as well, it became clear that the polymer has a small environmental load.

[0169] (Relationship with the reaction time of the polymerization reaction by enzyme) The polymer was dissolved in dry toluene equipped with molecular sieves, and Novozyme 435 (weight %) relative to the polymer was added. The reaction was carried out at 60°C under N2. At each reaction time (1 hour, 2 hours, 4 hours, 8 hours, 12 hours, 24 hours, 36 hours, 48 ​​hours, 72 hours, 96 hours, 120 hours), the reaction solvent was collected for GPC analysis. Such experiments were performed on PCL3.5k-γCD(9)-PU, PCL3.5k-γCD(5)-PU, and PCL3.5k-PU. The results are shown in Figure 41. (a) represents 10% by mass of the enzyme, (b) represents 20% by mass of the enzyme, and (c) represents 50% by mass of the enzyme.

[0170] In Figure 41(a), the Mn content of PCL3.5k-γCD(9)-PU shows little change. In Figure 41(b), the Mn content of PCL3.5k-γCD(9)-PU began to decrease after 1 hour and reached its lowest point after 12 hours. The Mn content of PCL3.5k-PU without movable crosslinking remained almost unchanged. In Figure 41(c), the Mn content of PCL3.5k-γCD(9)-PU continued to increase within 8 hours, and then began to decrease. The Mn content of PCL3.5k-γCD(5)-PU continued to increase within 96 hours. The Mn content of PCL3.5k-PU remained almost unchanged even after 120 hours.

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

[0172] (Example 2 of Embodiment 1) [ka] Before the reaction, a mixture of SH-2-DiOH and PCLx-diOH was heated overnight under vacuum at 80°C to remove water. The 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 heated under N2 at 60°C for 24 hours. After a predetermined time, the reaction mixture was precipitated in the cold solvent DCM / MeOH (v / v=1 / 4) to obtain PCLx-βCD(a)-PU. The raw material supply ratios for each polymer are shown in Table 6. The GPC measurement results are shown in Table 6 and Figure 24.

[0173] Table 6 shows the results of molecular weight measurements performed on the polymers obtained by the above method.

[0174] [Table 6]

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

[0176] The results shown in these figures indicate that PCL-PU exhibited higher elongation and tensile strength compared to PCL-PU without cyclodextrin. In particular, it is clear that cyclodextrin showed high elongation and tensile strength at a relatively low molar ratio, resulting in extremely high toughness. This demonstrates that, in Embodiment 1, the physical properties differ depending on the structure of the resin, and that by appropriately selecting and using these according to the purpose, the polymer of the present invention can be used in a wide range of applications.

[0177] (Example of Embodiment 2) reagent All reagents were purchased and used without purification. (1) Ethyl acrylate (EA) (Tokyo Chemical Industries, Ltd.) (2) Acetylated γ-cyclodextrin-acrylamide (Ac-γ-CDAAm) (Yushiro Chemical Industry Co., Ltd., Kyoeisha Chemical Co., Ltd.) (3) 1-Hydroxycyclohexylphenyl ketone (Irgacure 184) (Tokyo Chemical Industries, Ltd.) (4) ε-Caprolactone (CL) (Tokyo Chemical Industries Co., Ltd.) (5) Ethylene glycol (Fujifilm Wako Pure Chemical Corporation) (6) 2-Tin ethylhexylate II (Sn(Oct)2) (Fujifilm Wako Pure Chemical Corporation) (7) Deuterated chloroform (Fujifilm Wako Pure Chemical Corporation) (8) Chloroform (Fujifilm Wako Pure Chemical Corporation) Measuring device 1 ¹H NMR Nuclear Magnetic Resonance Spectrometer "JNM-ECS400 (400 MHz)" (solvent: CDCl3), manufactured by JEOL Ltd.; SEC Size Exclusion Chromatography System "HLC-8420GPC" (solvent: chloroform, standard sample: polystyrene, column: TSKgel GMHHR-M, guard column: TSKgel guardcolumn HHR-L), manufactured by Tosoh Corporation; Tensile Tester "Small Benchtop Tester EZ Graph," manufactured by Shimadzu Corporation; Test conditions: Load cell 10N, test speed 10mm / min

[0178] (Synthesis Example 3) Synthesis of MC Elastomer [ka]

[0179] MC elastomers having a network formed by movable crosslinking were synthesized according to the method described in NPG Asi Mater., 2022, 14, 1. EA (2.3g, 23 mmol) was placed in a sample tube, and Ac-γ-CDAAm (0.55g, 0.23 mmol) and Irgacure184 (9.6mg, 0.047 mmol) were dissolved in it. The solution was then stirred by ultrasonic vibration for 60 minutes. The solution was transferred to a mold and reacted by irradiating with ultraviolet light for 30 minutes while cooling with ice. The resulting elastomer was transferred to a Teflon® petri dish and dried under reduced pressure at 80°C for 12 hours in a vacuum heat dryer to remove unreacted monomers.

[0180] MC elastomers were prepared with varying amounts of Ac-γ-CDAAm (1.0, 2.0, and 3.0 mol%) as shown in Table 7 below.

[0181] [Table 7]

[0182] A colorless, transparent elastomer was obtained by synthesizing MC elastomer. Deuterated chloroform was used as the solvent. 1 1H NMR measurements revealed that the MC elastomer exhibited characteristic peaks originating from the acetyl group of Ac-γ-CDAAm, and the peaks originating from the vinyl group disappeared, confirming that the synthesis of the MC elastomer had progressed. By comparing the integrated values ​​of the peaks from the acetyl group and the ethyl group at the end of γ-CD, the introduction rate of γ-CD was 0.88% for pEAγCD_1 and 2.0% for pEAγCD_2.

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

[0184] [ka]

[0185] [Table 8]

[0186] The resulting polymer turned white as the amount of polycaprolactone introduced increased. Similar to the MC elastomer, deuterated chloroform was used. 1 ¹H NMR measurements revealed peaks originating from polycaprolactone, confirming that polycaprolactone had been introduced (Figure 47).

[0187] Size exclusion chromatography (SEC) was used to analyze the molecular weight of the introduced polycaprolactone. Chloroform was used as the mobile phase, and polystyrene was used as the standard sample. While the MC elastomer showed a single elution peak, the mobile crosslinked network material showed a new peak on the low molecular weight side. From a comparison of the two, the peak on the low molecular weight side is considered to be the elution peak of the introduced PCL (Figure 48). In the material prepared using pEAγCD_1, the number-average molecular weight of PCL was approximately 10,000. On the other hand, a decrease in the molecular weight of PCL was observed in pEAγCD_3. This is thought to be a result of the number of crosslinking sites increasing as the amount of introduced γ-CD increases, and the network structure of the MC elastomer becoming denser, thereby inhibiting the polymerization of CL (Table 9).

[0188] [Table 9]

[0189] (Comparative Example 2) Preparation of a material by simply mixing two types of resins PCL was synthesized alone using the reaction described above. A material (pEAγCD1_PCL50_M) was prepared by simply mixing this polycaprolactone with MC elastomer using the casting method. PCL (0.50 g) and pEAγCD_1 (0.50 g) were placed in a ground-glass test tube. Chloroform (9.0 g) was added and stirred to completely dissolve PCL and pEAγCD_1. The solution was poured into a Teflon® petri dish and heated in a 50 °C oven for 24 hours to remove the chloroform.

[0190] When comparing pEAγCD1_PCL50 prepared by in situ polymerization with pEAγCD1_PCL50_M prepared by simple mixing, pEAγCD1_PCL50 resulted in a highly transparent and uniform material, while pEAγCD1_PCL50_M resulted in a material with a non-uniform appearance. This is thought to be because pEAγCD1_PCL50 forms a dense network in which polycaprolactone polymer chains penetrate a mobile crosslinking network of MC elastomers, whereas pEAγCD1_PCL50_M does not form such a network as much.

[0191] (molding) The fabricated MC elastomer and other materials were formed into a film approximately 300 μm thick by hot pressing. The hot pressing was performed as shown in Figure 44, with a pressure of 20 MPa and a temperature of 80°C. After hot pressing, the samples were cooled with ice.

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

[0193] Figure 49 shows the results of tensile tests on MC elastomer and a movable crosslinked network material. The MC elastomer showed a tendency for the fracture strain to decrease and the maximum stress to increase as the amount of γ-CD introduced increased (Figure 49a). This is thought to be due to the effect of increased crosslinking density in addition to the molecular rigidity of γ-CD itself. Polycaprolactone was introduced at 50 wt% into the MC elastomer.

[0194] Comparing the mechanical properties of pEAγCD1_PCL50, pEAγCD2_PCL50, and pEAγCD3_PCL50, pEAγCD1_PCL50 showed the largest values ​​for both fracture strain and maximum stress. Evaluating the toughness and initial modulus of the fabricated material with MC elastomer, pEAγCD1_PCL50 showed the greatest improvement in both properties. This is thought to be due to the introduction of PCL, a molecular chain with relatively high rigidity, into the network. In pEAγCD3_PCL50, an improvement in toughness was observed due to an increase in fracture strain (Figure 49b). This is thought to be because the polycaprolactone polymer chains interwoven into the network of pEAγCD_3, which has a high crosslink density, broadened the network and improved the flexibility of the material.

[0195] For pEAγCD_1, which showed the greatest improvement in properties, the mechanical properties were investigated when the amount of PCL introduced was varied. As a result, improvements in toughness and initial modulus were observed at all introduction rates (Figure 49a). However, pEAγCD1_PCL80 became a brittle material, making it difficult to prepare test specimens. pEAγCD1_PCL50, which introduced 50 wt% PCL, showed the greatest improvement in mechanical properties, with the initial modulus increasing by approximately 70 times and toughness by approximately 3.5 times. At higher introduction rates, the improvement remained constant (Figure 49b).

[0196] This is thought to be due to the expansion of the mobile crosslinking network of the MC elastomer when it is immersed in the ε-caprolactone solution during synthesis. It is thought that as the volume of the ε-caprolactone solution increases, the mobile crosslinking network of the MC elastomer expands significantly, potentially leading to collapse. Previous studies have also reported that when materials with mobile crosslinks are immersed in a solution, polymer chains may detach from the γ-CD ring. Due to the above factors, the network expansion was large in pEAγCD1_PCL60 and pEAγCD1_PCL70, resulting in limited improvement in mechanical properties. However, in pEAγCD1_PCL50, the introduction of polycaprolactone occurred while maintaining the network provided by the MC elastomer, leading to an improvement in mechanical properties.

[0197] The mechanical properties of pEAγCD1_PCL50, prepared by in situ polymerization, and pEAγCD1_PCL50_M, obtained by simple mixing, were similarly compared. Although pEAγCD1_PCL50_M showed an improvement in its initial modulus, it exhibited results almost identical to those of the MC elastomer pEAγCD_1, and did not show a significant improvement in properties (Figure 51b). This result revealed that the mechanical properties were improved by introducing polycaprolactone into an MC elastomer with a movable crosslinking network to form semi-IPNs.

[0198] From the results above, the following facts became clear. (1) The mechanical properties of the MC elastomer changed as the amount of γ-CD introduced increased. This is thought to be due to an increase in the density of crosslinking points. (2) Among the MC elastomers, pEAγCD_1 showed the largest fracture strain, and the introduction of polycaprolactone improved its initial modulus and consequently increased toughness. The greatest improvement in properties was observed when the amount of polycaprolactone introduced was 50 wt%, with the initial modulus increasing by approximately 70 times and the toughness by approximately 3.5 times. (3) When comparing pEAγCD_PCL50, which was prepared by polymerizing ε-caprolactone in the presence of MC elastomer, with pEAγCD1_PCL50_M, which was prepared by simple mixing, pEAγCD_PCL50 was a material with a uniform appearance, while pEAγCD_PCL50_M was a material with a non-uniform appearance. Furthermore, the improvement in mechanical properties of pEAγCD_PCL50_M due to the introduction of polycaprolactone was limited.

[0199] These findings reveal that introducing polycaprolactone polymer chains into a mobile crosslinking network using MC elastomers via in situ polymerization to construct semi-IPNs leads to an improvement in the material's mechanical properties. [Industrial applicability]

[0200] The polymers disclosed herein have excellent physical properties while being environmentally friendly due to the use of aliphatic polyester resins, and can therefore be used in many fields where such performance is required.

Claims

1. It is obtained by the reaction of compound (A), aliphatic polyester (B), and diisocyanate compound (C). Compound (A) is, 【Chemistry 2】 (In the formula, R １ These are the same or different hydrogen, a carbon 2-50 acyl group, a carbon 1-30 alkyl group, or -CONHR ２ (R ２ R represents an alkyl group having 1 to 20 carbon atoms. １ More than 20% of the group consists of acyl groups with 2 to 50 carbon atoms, alkyl groups with 1 to 30 carbon atoms, or -CONHR groups. ２ It is one of the following. x is an integer between 5 and 7. Compounds represented by or compounds represented by the following general formula (11) 【Transformation 3】 (In the formula, R １ teeth, 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 The structure is represented by the following formula. 【Chemistry 4】 In the formula, R １０ represents a hydrogen or methyl group. R2 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 This represents the group shown in the following general formula (1). 【Transformation 5】 (In the formula, R １ These are the same or different hydrogen, a carbon 2-50 acyl group, a carbon 1-30 alkyl group, or -CONHR ２ (R ２ R represents an alkyl group having 1 to 20 carbon atoms. １ More than 20% of the group consists of acyl groups with 2 to 50 carbon atoms, alkyl groups with 1 to 30 carbon atoms, or -CONHR groups. ２ It is one of the following. x is an integer between 5 and 7. A polymer characterized by the following:

2. The polymer according to claim 1, wherein the aliphatic polyester resin structure is polycaprolactone.

3. The polymer according to claim 1 or 2, wherein the aliphatic polyester (B) is a polycaprolactone having a skeleton derived in part from a diol compound.

4. This resin composition was obtained by polymerizing ε-caprolactone in the presence of an acrylic copolymer having a cyclodextrin skeleton as a side chain of the polymer, wherein the cyclodextrin skeleton is represented by the following general formula (1) 【Chemistry 1】 (In the formula, R １ These are the same or different hydrogen, a carbon 2-50 acyl group, a carbon 1-30 alkyl group, or -CONHR ２ (R ２ R represents an alkyl group having 1 to 20 carbon atoms. １ More than 20% of the group consists of acyl groups with 2 to 50 carbon atoms, alkyl groups with 1 to 30 carbon atoms, or -CONHR groups. ２ A resin composition characterized by being one of the following: x is an integer between 5 and 7.

5. The resin composition according to claim 4, wherein the polymerization of ε-caprolactone is further carried out in the presence of a diol compound.

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