Diene-based high-toughness elastomer and method for producing the same

Abstract

To provide a novel diene-based polymer having excellent mechanical properties and a simple production method therefor.SOLUTION: Provided is an elastomer comprising a vicinal amino alcohol unit represented by formula (1) and a but-1-ene-1,4-diyl unit represented by formula (2), the elastomer having a molecular weight of 5000 or more (wherein R1, R2, R3, and R4 are as defined in the present disclosure).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to diene derivative elastomers and methods for making the same. [Background technology]

[0002] In recent years, the use of polymeric materials has increased significantly in various industries and daily necessities due to their excellent mechanical properties and good chemical resistance (Non-Patent Documents 1-3). However, the preparation of polymeric materials with mechanical properties comparable to those of metals and ceramic materials remains a challenge (Non-Patent Document 4). A simple strategy to improve the mechanical properties of polymeric materials is to introduce hydrogen bonds (H-bonds) to achieve high mechanical toughness, self-repairing properties, and self-recovery (Non-Patent Documents 5-8). However, when hydrogen bonds that are too strong are introduced, satisfactory dynamic properties are often not obtained because the hydrogen bonds tend to self-organize or aggregate (Non-Patent Documents 1 and 9).

[0003] In our previous study, we succeeded in introducing entropy-driven hydrogen bonds by embedding vicinal diols into the polybutadiene (PB) skeleton, resulting in excellent mechanical and dynamic properties (Non-Patent Document 10). However, this synthesis method was not versatile and could not be applied as a simple improvement method for existing commercially available materials. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Song, P.; Wang, H. High-performance polymeric materials through hydrogen-bond cross-linking. Advanced Materials 2020, 32 (18), 1901244. [Non-Patent Document 2] Stachowiak, T.; Postawa, P.; Malinska, K.; Drozdz, D.; Pudelko, A. Comparison of Physical and Thermal Properties of Mulching Films Made of Different Polymeric Materials. Materials 2022, 15 (21), 7610.

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Non-Patent Document 9

Non-Patent Document 10

[0005] An object of the present invention is to provide a novel diene-based polymer having excellent mechanical properties and a simple process for producing the same. [Means for solving the problem]

[0006] The present disclosure includes, for example, the subject matter described below. Section 1. A vicinal amino alcohol unit represented by formula (1)

[0007] [ka]

[0008] (In the formula, R 1 and R 2 are independently hydrogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted phenylalkyl, or -OTMS. A but-1-ene-1,4-diyl unit represented by formula (2)

[0009] [ka]

[0010] (In the formula, R 3 and R 4are independently hydrogen or substituted or unsubstituted C1-C5 alkyl. 2. An elastomer comprising:

[0011] Section 2. R 1 and R 2 Item 2. The elastomer according to item 1, wherein one of the groups is hydrogen.

[0012] Section 3. Item 2. The elastomer according to item 1, wherein the proportion of vicinal amino alcohol units represented by formula (1) is 1 to 20 mol % and the proportion of but-1-en-1,4-diyl units represented by formula (2) is 80 to 99 mol % relative to all units constituting the elastomer.

[0013] Section 4. An elastomer represented by formula (I):

[0014] [ka]

[0015] (In the formula, R 1 and R 2 are independently hydrogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted phenylalkyl, or -OTMS; R 3 and R 4 are independently hydrogen or substituted or unsubstituted C1-C5 alkyl; The molar ratio of x:y is 99:1 to 60:40. Section 5. Epoxy units represented by formula (3)

[0016] [ka]

[0017] A but-1-ene-1,4-diyl unit represented by formula (4)

[0018] [ka]

[0019] (In the formula, R 3 and R 4 are independently hydrogen or substituted or unsubstituted C1-C5 alkyl. 1. A method for producing an elastomer, comprising reacting a copolymer comprising:

[0020] Section 6. 6. The method of claim 5, wherein the amine comprises a primary amine.

[0021] Section 7. Item 6. The method according to item 5, further comprising reacting the conjugated diene polymer with m-chloroperoxybenzoic acid to form a copolymer comprising epoxy units represented by formula (3) and but-1-ene-1,4-diyl units represented by formula (4).

[0022] Section 8. Item 8. The method according to item 7, wherein the conjugated diene polymer comprises a butadiene polymer, an isoprene polymer, or an aromatic vinyl-conjugated diene copolymer.

[0023] Section 9. Item 5. A composition comprising the elastomer according to any one of items 1 to 4.

[0024] Section 10. Item 5. A rubber improver comprising the elastomer according to any one of items 1 to 4. [Brief description of the drawings]

[0025] [Figure 1A] FIG. 1A shows the NMR spectra of polymers PB, PB-E20, PB-DE20, and PB-Bu20. [Figure 1B]FIG. 1B shows the NMR data for the elastomers SBS, SBS-Bu12, and SBS-DE12. [Figure 1C] FIG. 1C shows the NMR data for the elastomers PB-AEOTMS12 and PB-AEOH12. [Figure 1D] Figure 1D shows the NMR data for the elastomer PB-AE2OTMS12. [Figure 1E] FIG. 1E shows the NMR data for the elastomer PB-B12. [Figure 1F] Figure 1F shows the NMR data for the elastomer PI-Bu12. [Figure 2A] Figure 2A shows the tensile test results for the elastomers PB, PB-Bu12, and PB-Bu20. Horizontal axis: strain (%), vertical axis: stress (Mpa) [Figure 2B] Figure 2B shows the tensile test results for the elastomers PB-Bu12, PB-Bu20, PB-Bu23, PB-Bu33, and PB-Bu40. Horizontal axis: strain (%), vertical axis: stress (Mpa) [Figure 3A] Figure 3A shows the stress-strain curves of the elastomer PB-Bu12 in a cyclic uniaxial extension experiment. [Figure 3B] Figure 3B shows a graph of the hysteresis recovery force versus cycle number for the elastomer PB-Bu12 stretched with 300% stain. Cycles 2 through 6 correspond to waiting times of 1 min, 30 min, 1 h, 3 h, and 6 h, respectively. [Figure 4] Figure 4 shows the tensile tests of elastomers PB, PB-DE12, and PB-DE20. [Diagram 5] Figure 5 shows the tensile tests of elastomers PB-Et12, PB-DE12, and PB-Et20. [Figure 6] FIG. 6B shows the tensile tests of the elastomers SBS, SBS-Bu12, SBS-Et12, and SBS-DE12. [Figure 7] Figure 7 shows the tensile tests of PB-AEOTMS12 and PB-AEOH12. [Figure 8] Figure 8 shows the tensile test results for PB-AE2OTMS12. [Figure 9] Figure 9 shows the tensile test results for PB-B12. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] In this specification, the term "containing" is a concept that encompasses "consisting essentially only of" and "consisting only of."

[0027] In the numerical ranges described in stages in this specification, the upper or lower limit of a certain numerical range can be arbitrarily combined with the upper or lower limit of another numerical range. In addition, in the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in an example or a value that can be unambiguously derived from an example. Furthermore, in this specification, a numerical value connected with "~" means a numerical range that includes the numerical values ​​before and after "~" as the lower and upper limits.

[0028] The following describes the embodiments included in the present disclosure in further detail. Note that the embodiments described below are representative examples of the present disclosure and do not limit the scope of the invention.

[0029] As used herein, the term vicinal amino alcohol (VAA) refers to a moiety having two adjacent carbon atoms, a nitrogen atom from an amine bonded to one carbon atom, and a hydroxyl bonded to the other carbon atom.

[0030] As used herein, C1-C5 means one to five carbon atoms.

[0031] R in formula (1) or formula (I) 1 When is substituted C1-C5 alkyl, substituted phenyl, or substituted phenylalkyl, the substituents can be halogen (e.g., -F, -Cl, -Br, and -I), alkoxy, or -OTMS. -OTMS refers to -o-trimethylsilyl.

[0032] R in formula (1) or formula (I) 2 When is substituted C1-C5 alkyl, substituted phenyl, or substituted phenylalkyl, the substituents can be halogen (eg, -F, -Cl, -Br and -I), alkoxy, or -OTMS.

[0033] R in formula (2), formula (I) or formula (4) 3 When is a substituted C1-C5 alkyl, the substituents can be halogen (eg, -F, -Cl, -Br and -I) or -OTMS.

[0034] R in formula (2), formula (I) or formula (4) 4 When is a substituted C1-C5 alkyl, the substituents can be halogen (eg, -F, -Cl, -Br and -I) or -OTMS.

[0035] We propose a very simple modification strategy to introduce entropy-driven hydrogen bonding into olefin-derived diene polymers. The resulting polymers exhibit excellent mechanical properties. They may further exhibit excellent dynamic functionalities, including self-healing or self-repairing properties.

[0036] In one embodiment, a vicinal amino alcohol unit represented by formula (1)

[0037] [ka]

[0038] (In the formula, R 1 and R 2 are independently hydrogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted phenylalkyl, or -OTMS. A but-1-ene-1,4-diyl unit represented by formula (2)

[0039] [ka]

[0040] (In the formula, R 3 and R 4 are independently hydrogen or substituted or unsubstituted C1-C5 alkyl. and having a molecular weight of 5000 or greater.

[0041] The molecular weight of the elastomer may be 10,000 or more. The upper limit of the molecular weight of the elastomer is not particularly limited, but is, for example, 1,000,000. In this specification, the molecular weight of the elastomer can be measured by chromatography, and is preferably a number average molecular weight measured by gel permeation chromatography (GPC, also known as size exclusion chromatography (SEC)).

[0042] In some embodiments, R 1 and R 2 One of the atoms is hydrogen.

[0043] In some embodiments, the proportion of vicinal amino alcohol units represented by formula (1) is 1 to 99 mol %, and the proportion of but-1-en-1,4-diyl units represented by formula (2) is 1 to 99 mol %, relative to all units constituting the elastomer.

[0044] In some embodiments, the proportion of vicinal amino alcohol units represented by formula (1) is 1 to 40 mol %, and the proportion of but-1-en-1,4-diyl units represented by formula (2) is 60 to 99 mol %, relative to all units constituting the elastomer.

[0045] In some embodiments, the proportion of vicinal amino alcohol units represented by formula (1) is 1 to 20 mol %, and the proportion of but-1-en-1,4-diyl units represented by formula (2) is 80 to 99 mol %, relative to all units constituting the elastomer.

[0046] In some embodiments, the amount of the epoxy units represented by formula (3)' is 5 mol % or less relative to all units constituting the elastomer.

[0047] [ka]

[0048] (wherein R is hydrogen, or C1-C5 alkyl).

[0049] In some embodiments, any of the above elastomers excludes elastomers having hydroxyl groups at both ends of the polymer chain containing a vicinal amino alcohol unit represented by formula (1) and a but-1-ene-1,4-diyl unit represented by formula (2).

[0050] In one embodiment, there is provided an elastomer according to formula (I):

[0051] [ka]

[0052] (In the formula, R 1 and R 2 are independently hydrogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted phenylalkyl, or -OTMS; R 3 and R 4 are independently hydrogen or substituted or unsubstituted C1-C5 alkyl; The molar ratio of x:y is 99:1 to 60:40.

[0053] In another embodiment, a vicinal amino alcohol unit represented by formula (1)

[0054] [ka]

[0055] (In the formula, R 1 and R 2 are independently hydrogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted phenylalkyl, or -OTMS. A but-1-ene-1,4-diyl unit represented by formula (2),

[0056] [ka]

[0057] (In the formula, R 3 and R 4 are independently hydrogen or substituted or unsubstituted C1-C5 alkyl. A styrene unit represented by formula (15),

[0058] [ka]

[0059] and having a molecular weight of 10,000 or greater.

[0060] The upper limit of the molecular weight of the elastomer is not particularly limited, but is, for example, 1,000,000.

[0061] R in Equation (1) 1 and R 2 , and R in formula (2) 3 and R 4 is as explained above.

[0062] In some embodiments, the proportion of vicinal amino alcohol units represented by formula (1) is 1 to 98 mol %, the proportion of but-1-en-1,4-diyl units represented by formula (2) is 1 to 98 mol %, and the proportion of styrene units represented by formula (15) is 2 to 98 mol %, relative to all units constituting the elastomer.

[0063] In some embodiments, the proportion of the vicinal amino alcohol units represented by formula (1) is 1 to 40 mol %, and the proportion of the but-1-ene-1,4-diyl units represented by formula (2) is 60 to 99 mol %, where the sum of the proportion of the vicinal amino alcohol units represented by formula (1) and the proportion of the but-1-ene-1,4-diyl units represented by formula (2) is 100 mol %.

[0064] In another embodiment, there is provided an elastomer according to formula (II):

[0065] [ka]

[0066] (In the formula, R 1 and R 2 are independently hydrogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted phenylalkyl, or -OTMS; R 3 and R 4 are independently hydrogen or substituted or unsubstituted C1-C5 alkyl; The molar ratio of x:y is 99:1 to 60:40; The molar ratio of m:n is 50:50 to 1:99. The ratio of x:(m+n):y may preferably be from 1:98:1 to 59:2:39 on a molar basis.

[0067] R in formula (II) 1 and R 2 , and R in formula (2) 3 and R 4 Regarding R in Eq. (1), 1 and R 2 , and R in formula (2) 3 and R 4 As explained above.

[0068] In another embodiment, a vicinal amino alcohol unit represented by formula (1)

[0069] [ka]

[0070] (In the formula, R 1 and R 2 are independently hydrogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted phenylalkyl, or -OTMS. A but-1-ene-1,4-diyl unit represented by formula (2),

[0071] [ka]

[0072] (In the formula, R 3 and R 4 are independently hydrogen or substituted or unsubstituted C1-C5 alkyl. A 1,2-butadiene unit represented by formula (16),

[0073] [ka]

[0074] and having a molecular weight of 5000 or greater.

[0075] The molecular weight of the elastomer may be 10,000 or more.

[0076] The upper limit of the molecular weight of the elastomer is not particularly limited, but is, for example, 1,000,000.

[0077] R in Equation (1) 1 and R 2 , and R in formula (2) 3 and R 4 is as explained above.

[0078] In some embodiments, the proportion of vicinal amino alcohol units represented by formula (1) is 1 to 98 mol %, the proportion of but-1-ene-1,4-diyl units represented by formula (2) is 1 to 98 mol %, and the proportion of 1,2-butadiene units represented by formula (16) is 2 to 98 mol %, relative to all units constituting the elastomer.

[0079] In some embodiments, the proportion of the vicinal amino alcohol units represented by formula (1) is 1 to 40 mol %, and the proportion of the but-1-ene-1,4-diyl units represented by formula (2) is 60 to 99 mol %, where the sum of the proportion of the vicinal amino alcohol units represented by formula (1) and the proportion of the but-1-ene-1,4-diyl units represented by formula (2) is 100 mol %.

[0080] In another embodiment, there is provided an elastomer according to formula (IV):

[0081] [ka]

[0082] (In the formula, R 1 and R 2 are independently hydrogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted phenylalkyl, or -OTMS; R 3 and R 4 are independently hydrogen or substituted or unsubstituted C1-C5 alkyl; The molar ratio of (x+y):z is 99:1 to 60:40.

[0083] In another embodiment, a vicinal amino alcohol unit represented by formula (1)

[0084] [ka]

[0085] (In the formula, R 1 and R 2 are independently hydrogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted phenylalkyl, or -OTMS. A but-1-ene-1,4-diyl unit represented by formula (2),

[0086] [ka]

[0087] (In the formula, R 3 and R 4 are independently hydrogen or substituted or unsubstituted C1-C5 alkyl. A styrene unit represented by formula (15),

[0088] [ka]

[0089] A 1,2-butadiene unit represented by formula (16),

[0090] [ka]

[0091] and having a molecular weight of 10,000 or greater.

[0092] The upper limit of the molecular weight of the elastomer is not particularly limited, but is, for example, 1,000,000.

[0093] R in Equation (1) 1 and R 2 , and R in formula (2) 3 and R 4 is as explained above.

[0094] In some embodiments, the proportion of vicinal amino alcohol units represented by formula (1) is 1 to 40 mol %, the proportion of but-1-ene-1,4-diyl units represented by formula (2) is 99 to 60 mol %, the proportion of styrene units represented by formula (15) is 1 to 99 mol %, and the proportion of 1,2-butadiene units represented by formula (16) is 0 to 50 mol %, relative to all units constituting the elastomer.

[0095] In another embodiment, there is provided an elastomer according to formula (V):

[0096] [ka]

[0097] (In the formula, R 1 and R 2 are independently hydrogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted phenylalkyl, or -OTMS; R 3 and R 4 are independently hydrogen or substituted or unsubstituted C1-C5 alkyl; The molar ratio of (x+y):z is 100:0 to 50:50; The molar ratio of (m+n):(x+y+z) is 0:100 to 99:1.

[0098] In another embodiment, an epoxy unit represented by formula (3)

[0099] [ka]

[0100] A but-1-ene-1,4-diyl unit represented by formula (4)

[0101] [ka]

[0102] (In the formula, R 3 and R 4 are independently hydrogen or substituted or unsubstituted C1-C5 alkyl. With an amine in the presence of a Lewis acid catalyst in a solvent is provided a method for making an elastomer, the method comprising reacting a copolymer comprising:

[0103] The above-mentioned production method provides an elastomer containing vicinal amino alcohol units represented by formula (1) and but-1-ene-1,4-diyl units represented by formula (2), the elastomer having a molecular weight of 10,000 or more. In a specific embodiment, an elastomer represented by the above-mentioned formula (I) is also provided.

[0104] In another embodiment, there is provided a method for producing an elastomer, comprising reacting a copolymer comprising epoxy units represented by formula (3), but-1-ene-1,4-diyl units represented by formula (4), and styrene units represented by formula (15) with an amine in a solvent in the presence of a Lewis acid catalyst.

[0105] The above-mentioned production method provides an elastomer containing vicinal amino alcohol units represented by formula (1), but-1-ene-1,4-diyl units represented by formula (2), and styrene units represented by formula (15), the elastomer having a molecular weight of 10,000 or more. In a specific embodiment, an elastomer represented by the above-mentioned formula (II) is also provided.

[0106] In another embodiment, there is provided a method for producing an elastomer, comprising reacting a copolymer comprising epoxy units represented by formula (3), but-1-ene-1,4-diyl units represented by formula (4), and 1,2-butadiene units represented by formula (16) with an amine in a solvent in the presence of a Lewis acid catalyst.

[0107] The above-mentioned production method provides an elastomer containing vicinal amino alcohol units represented by formula (1), but-1-ene-1,4-diyl units represented by formula (2), and 1,2-butadiene units represented by formula (16), the elastomer having a molecular weight of 10,000 or more. In a specific embodiment, an elastomer represented by the above-mentioned formula (IV) is also provided.

[0108] In another embodiment, there is provided a method for producing an elastomer, comprising reacting a copolymer comprising epoxy units represented by formula (3), but-1-ene-1,4-diyl units represented by formula (4), styrene units represented by formula (15), and 1,2-butadiene units represented by formula (16) with an amine in a solvent in the presence of a Lewis acid catalyst.

[0109] The above-mentioned production method provides an elastomer containing vicinal amino alcohol units represented by formula (1), but-1-ene-1,4-diyl units represented by formula (2), styrene units represented by formula (15), and 1,2-butadiene units represented by formula (16), the elastomer having a molecular weight of 10,000 or more. In a specific embodiment, an elastomer represented by the above-mentioned formula (V) is provided.

[0110] ZnCl is used as a Lewis acid catalyst. 2、 Examples of suitable antimicrobial agents include, but are not limited to, EtAlCl2, SnCl4, and the like.

[0111] Solvents include, but are not limited to, tetrahydrofuran (THF), toluene, and the like.

[0112] The amines may be primary amines, secondary amines, tertiary amines, or combinations thereof.

[0113] Amines are, for example, NHR 1 R 2 It can be expressed as R 1 and R 2 is R in Eq. (1). 1 and R 2This is as explained above.

[0114] In some embodiments, the amine comprises a primary amine. Examples of primary amines include aliphatic monoamines such as ethylamine, propylamine, butylamine, hexylamine, octylamine, laurylamine, and 2-ethylhexylamine; alicyclic monoamines such as cyclopentylamine, cyclohexylamine, and norbornylamine; aliphatic diamines such as ethylenediamine, propylenediamine, and hexamethylenediamine; alicyclic diamines such as isophoronediamine; and aromatic amines such as toluidine, xylidine, isopropylaniline, benzylamine, and phenethylamine. The method may further include reacting the conjugated diene polymer with m-chloroperoxybenzoic acid to form a copolymer comprising an epoxy unit represented by formula (3) and a but-1-ene-1,4-diyl unit represented by formula (4).

[0115] In some embodiments, the conjugated diene polymer comprises a butadiene-based polymer, an isoprene-based polymer, or an aromatic vinyl-conjugated diene copolymer.

[0116] In another aspect, a composition comprising any one of the above elastomers is provided.

[0117] In another aspect, there is provided a rubber modifier comprising any one of the above elastomers.

[0118] The synthesis procedure of vicinal amino alcohol (VAA)-containing polymers is shown in Scheme 1. Examples of amines (also called amine compounds) that can be used in this method are shown in Example 1 below. The polymers represented by formula (5), (7), and (9) are polybutadiene (PB), styrene-butadiene-styrene copolymer (SBS), and polyisoprene (PI), respectively. The polymers after epoxidation are named PB-EX, SBS-EX, and PI-EX, where E represents a block having an epoxy group, and X represents the molar ratio of the epoxy group. The polymers represented by formula (6), (8), and (10) are examples of polymers PB-EX, SBS-EX, and PI-EX, respectively. After epoxidation, the resulting polymers undergo a ring-opening reaction to obtain polymers PB-AX, SBS-AX, and PI-AX, respectively, where A represents the type of amino group (e.g., butylamine (Bu), diethylamine (DE)), and X (%) represents the molar ratio of these amino groups. The range of X (%) is, for example, preferably 1 to 99, more preferably 1 to 40, and further preferably 1 to 20. The polymer represented by formula (I-1), the polymer represented by formula (II-1), and the polymer represented by formula (III-1) are examples of polymers PB-AX, SBS-AX, and PI-AX, respectively.

[0119] In scheme 1, the molar ratio of x:y in each of the polymer represented by formula (6) and the polymer represented by formula (I-1) is preferably 99:1 to 1:99, more preferably 99:1 to 60:40, and even more preferably 99:1 to 80:20. The ratio of x:y:z in the polymer represented by formula (7) is preferably 1:98:1 to 49:2:49 on a molar basis. The ratio of x:y in each of the polymer represented by formula (8) and the polymer represented by formula (II-1) is preferably 50:50 to 1:99 on a molar basis. The ratio of m:n in each of the polymer represented by formula (8) and the polymer represented by formula (II-1) is preferably 1:99 to 40:60 on a molar basis. The molar ratio of x:y in the polymer represented by formula (10) is preferably 99:1 to 1:99, more preferably 99:1 to 60:40, and even more preferably 99:1 to 80:20. The molar ratio of x:y in the polymer represented by formula (IV) is preferably from 99:1 to 1:99, more preferably from 99:1 to 60:40, and further preferably from 99:1 to 80:20.

[0120] In each of the polymer represented by formula (I-1), the polymer represented by formula (II-1), and the polymer represented by formula (III-1), R 1 and R 2 is independently hydrogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted phenylalkyl, or -OTMS.

[0121] [ka]

[0122] [ka]

[0123] The synthesis procedure for further vicinal amino alcohol (VAA)-containing polymers is shown in Scheme 2. The same amines as those used in Scheme 1 can be used in this method. The polymers represented by formula (11) and formula (13) have 1,2-butadiene units. After epoxidation, the polymers represented by formula (12) and formula (14) are obtained, respectively. After epoxidation, the obtained polymers undergo ring-opening reaction to obtain the polymers represented by formula (IV-1) and formula (V-1) having amino groups, respectively.

[0124] The molar ratio (%) of amino groups in the polymer represented by formula (IV-1) and the polymer represented by formula (V-1) is preferably in the range of 1 to 99, more preferably 1 to 40, and further preferably 1 to 20, for example.

[0125] In scheme 2, the molar ratio of (x+y):z in each of the polymer represented by formula (12) and the polymer represented by formula (IV-1) is preferably 99:1 to 1:99, more preferably 99:1 to 60:40, and even more preferably 99:1 to 80:20. The ratio of x:y is preferably 99:1 to 1:99, more preferably 99:1 to 80:20, for example, 80:20 to 95:5, on a molar basis. The ratio of x:z in each of the polymer represented by formula (12) and the polymer represented by formula (IV-1) is preferably 1:99 to 40:60 on a molar basis. The ratio of m:(x+y):n in the polymer represented by formula (13) is preferably 1:98:1 to 49:2:49 on a molar basis. The ratio of (x+y):z in each of the polymer represented by formula (14) and the polymer represented by formula (V-1) is preferably 99:1 to 60:40 on a molar basis. The ratio of x:z in each of the polymer represented by formula (14) and the polymer represented by formula (V-1) is preferably 99:1 to 60:40 on a molar basis.

[0126] [ka]

[0127] The following examples are intended for illustrative purposes only and are not intended to limit the scope of the present invention in any way. Unless otherwise specified, reagents are commercially available or are obtained or prepared according to conventional techniques or procedures known in the art. EXAMPLES

[0128] Working Example reagent Polybutadiene (M w =200k) from Bridgestone Corporation, Styrene-Butadiene-Styrene (M w = 84k) was purchased from Asahi Kasei Corporation, and butylamine (purity 98% or more), diethylamine (purity 99% or more), and m-chloroperbenzoic acid (purity 69.0 to 75.0%) were purchased from Wako Pure Chemical Industries, Ltd. The reaction solvent, tetrahydrofuran, was purchased from Wako Pure Chemical Industries, Ltd. Reagents and solvents were used as received.

[0129] Synthesis Example 1: Preparation of PB-E12 In a Schlenk flask equipped with a magnetic stirrer, polybutadiene (M w A solution of mCPBA (1 g, approx. 18.5 mmol of butadiene repeat units) dissolved in 100 mL of THF was added. To this, a solution of 0.55 g of mCPBA (purity 69.0-75.0% in water) dissolved in 20 mL of THF was added dropwise within 30 min. The resulting mixture was then stirred at room temperature for 2 h. The solvent was removed by vacuum evaporation. After filtration, a small amount of dichloromethane (3 mL) was added and the polymer was reprecipitated in cold MeOH. The precipitate was collected and dried in vacuum at 60 °C (0.89 g, 84 %).

[0130] Synthesis Example 2: Preparation of PB-E20 In a Schlenk flask equipped with a magnetic stirrer, polybutadiene (M wA solution of mCPBA (1 g, approx. 18.5 mmol of butadiene repeat units) dissolved in 100 mL of THF was added. To this was added dropwise a solution of 1.1 g of mCPBA (purity 69.0-75.0% in water) dissolved in 20 mL of THF within 30 min. The resulting mixture was then stirred at room temperature for 2 h. The solvent was removed by vacuum evaporation. After filtration, a small amount of dichloromethane (3 mL) was added and the polymer was reprecipitated in cold MeOH. The precipitate was collected and dried in vacuum at 60 °C (0.86 g, 81 %).

[0131] Synthesis Example 3: Preparation of PB-E23 In a Schlenk flask equipped with a magnetic stirrer, polybutadiene (M w A solution of mCPBA (1 g, approx. 18.5 mmol of butadiene repeat units) was added. To this, a solution of 1.3 g of mCPBA (purity 69.0-75.0% in water) dissolved in 20 mL of THF was added dropwise within 30 min. The resulting mixture was then stirred at room temperature for 2 h. The solvent was removed by vacuum evaporation. After filtration, a small amount of dichloromethane (3 mL) was added and the polymer was reprecipitated in cold MeOH. The precipitate was collected and dried in vacuum at 60 °C.

[0132] Synthesis Example 4: Preparation of PB-E33 In a Schlenk flask equipped with a magnetic stirrer, polybutadiene (M w A solution of mCPBA (1 g, approx. 18.5 mmol of butadiene repeat units) was added. To this, a solution of 1.8 g of mCPBA (purity 69.0-75.0% in water) dissolved in 20 mL of THF was added dropwise within 30 min. The resulting mixture was then stirred at room temperature for 2 h. The solvent was removed by vacuum evaporation. After filtration, a small amount of dichloromethane (3 mL) was added and the polymer was reprecipitated in cold MeOH. The precipitate was collected and dried in vacuum at 60 °C.

[0133] Synthesis Example 5: Preparation of PPB-E40 In a Schlenk flask equipped with a magnetic stirrer, polybutadiene (M w A solution of mCPBA (1 g, approx. 18.5 mmol of butadiene repeat units) was added. To this, a solution of 2.2 g of mCPBA (purity 69.0-75.0% in water) dissolved in 20 mL of THF was added dropwise within 30 min. The resulting mixture was then stirred at room temperature for 2 h. The solvent was removed by vacuum evaporation. After filtration, a small amount of dichloromethane (3 mL) was added and the polymer was reprecipitated in cold MeOH. The precipitate was collected and dried in vacuum at 60 °C.

[0134] Synthesis Example 6: Preparation of SBS-E12 In a Schlenk flask equipped with a magnetic stirrer, styrene-butadiene-styrene polymer (M w A solution of mCPBA (mCPBA = 84k, 1 g, butadiene repeat unit ca. 14.5 mmol) dissolved in 50 mL of THF was added. To this, a solution of 0.53 g of mCPBA (purity 69.0-75.0% in water) dissolved in 20 mL of THF was added dropwise within 30 min. The resulting mixture was then stirred at room temperature for 2 h. The solvent was removed by vacuum evaporation. After filtration, a small amount of dichloromethane (3 mL) was added and the polymer was reprecipitated in cold MeOH. The precipitate was collected and dried in vacuum at 60 °C (0.88 g, 85 %).

[0135] Synthesis Example 7: Preparation of SBS-E20 In a Schlenk flask equipped with a magnetic stirrer, styrene-butadiene-styrene polymer (M w A solution of mCPBA (mCPBA = 84k, 1 g, butadiene repeat unit approx. 14.5 mmol) dissolved in 50 mL of THF was added. To this, a solution of 0.88 g of mCPBA (purity 69.0-75.0% in water) dissolved in 20 mL of THF was added dropwise within 30 min. The resulting mixture was then stirred at room temperature for 2 h. The solvent was removed by vacuum evaporation. After filtration, a small amount of dichloromethane (3 mL) was added and the polymer was reprecipitated in cold MeOH. The precipitate was collected and dried in vacuum at 60 °C (0.87 g, 84 %).

[0136] Synthesis Example 8: Preparation of PI-E12 In a Schlenk flask equipped with a magnetic stirrer, polyisoprene (M w A solution of mCPBA (mCPBA = 200k, 1 g, approximately 14.71 mmol of isoprene repeat units) dissolved in 100 mL of THF was added. To this, a solution of 0.55 g of mCPBA (purity 69.0-75.0% in water) dissolved in 20 mL of THF was added dropwise within 30 min. The resulting mixture was then stirred at room temperature for 2 h. The solvent was removed by evaporation in vacuum. After filtration, a small amount of dichloromethane (3 mL) was added and the polymer was reprecipitated in cold MeOH. The precipitate was collected and dried at 60 °C under vacuum. (0.77 g, 74.6 %) In addition, the polybutadiene (PB) polymer and styrene-butadiene-styrene (SBS) of the synthesis examples The molar ratio of the repeating units in the polymer was as shown in Table 1.

[0137] [Table 1]

[0138] Example 1: Preparation of PB-Bu12 A sealable vial (pressure resistance: 2 MPa) equipped with a magnetic stirrer was charged with 0.5 g of PB-E12 (Ca. 1.2 mmol epoxy group, 1 equiv.), 0.16 g of zinc chloride (1.15 mmol, 1 equiv.), and 3 mL of dry THF. Then, butylamine (1.5 mL, 15.16 mmol, 12.6 equiv.) was added dropwise to the mixture. The vial was sealed and the mixture was stirred at 110 °C for 24 h. The polymer was precipitated twice into ice-cold methanol, and the precipitate was collected and dried in vacuum at 60 °C to obtain the polymer (0.48 g, 96 %).

[0139] Example 2: Preparation of PB-Bu20 A sealable vial (pressure resistance: 2 MPa) equipped with a magnetic stirrer was charged with 0.5 g of PB-E20 (Ca. 1.92 mmol epoxy group, 1 equiv.), 0.26 g of zinc chloride (1.911 mmol, 1 equiv.), and 3 ml of dry THF. Then, butylamine (3 mL, 30.35 mmol, 15.8 equiv.) was added dropwise to the mixture. The vial was sealed and the mixture was stirred at 110 °C for 24 h. The polymer was precipitated twice into ice-cold methanol, and the precipitate was collected and dried in vacuum at 60 °C to obtain the polymer (0.41 g, 82%).

[0140] Example 3: Preparation of PPB-Bu23 A sealable vial (pressure resistance: 2 MPa) was equipped with a magnetic stirrer and charged with 0.5 g of PB-E23 (Ca. 2.21 mmol epoxy group, 1 eq), 0.26 g of zinc chloride (1.911 mmol, 1 eq), and 3 ml of dry THF. Then, butylamine (3 mL, 30.35 mmol, 15.8 eq.) was added dropwise to the mixture. The vial was sealed and the mixture was stirred at 110 °C for 24 h. The polymer was precipitated twice in ice-cold methanol, and the precipitate was collected and dried in vacuum at 60 °C to obtain the polymer.

[0141] Example 4: Preparation of PPB-Bu33 A sealable vial (pressure resistance: 2 MPa) was equipped with a magnetic stirrer and charged with 0.5 g of PB-E33 (Ca. 3.17 mmol epoxy group, 1 eq), 0.26 g of zinc chloride (1.911 mmol, 1 eq), and 3 ml of dry THF. Then, butylamine (3 mL, 30.35 mmol, 15.8 eq.) was added dropwise to the mixture. The vial was sealed and the mixture was stirred at 110 °C for 24 h. The polymer was precipitated twice in ice-cold methanol, and the precipitate was collected and dried in vacuum at 60 °C to obtain the polymer.

[0142] Example 5: Preparation of PPB-Bu40 A sealable vial (pressure resistance: 2 MPa) was equipped with a magnetic stirrer and charged with 0.5 g of PB-E40 (Ca. 3.84 mmol epoxy group, 1 eq), 0.26 g of zinc chloride (1.911 mmol, 1 eq), and 5 ml of dry THF. Then, butylamine (3 mL, 30.35 mmol, 15.8 eq.) was added dropwise to the mixture. The vial was sealed and the mixture was stirred at 110 °C for 36 h. The polymer was precipitated twice in ice-cold methanol, and the precipitate was collected and dried in vacuum at 60 °C to obtain the polymer.

[0143] Example 6: Preparation of PB-DE12 A sealable vial (pressure resistance: 2 MPa) equipped with a magnetic stirrer was charged with 0.5 g of PB-E12 (Ca. 1.2 mmol epoxy group, 1 equiv.), 0.26 g of zinc chloride (1.911 mmol, 1 equiv.), and 3 mL of dry THF. After this, diethylamine (1.5 mL, 14.6 mmol, 12.15 equiv.) was added dropwise to the mixture. The vial was sealed and the mixture was stirred at 100 °C for 24 h. The polymer was precipitated twice into ice-cold methanol, and the precipitate was collected and dried in vacuum at 60 °C to obtain the polymer (0.41 g, 82%).

[0144] Example 7: Preparation of PB-DE20 A sealable vial (pressure resistance: 2 MPa) equipped with a magnetic stirrer was charged with 0.5 g of PB-E20 (Ca. 1.92 mmol epoxy group, 1 equiv.), 0.26 g of zinc chloride (1.911 mmol, 1 equiv.), and 3 mL of dry THF. Diethylamine (3 mL, 29.17 mmol, 15.2 equiv.) was then added dropwise to the mixture. The vial was sealed and the mixture was stirred at 110 °C for 24 h. The polymer was precipitated twice into ice-cold methanol, and the precipitate was collected and dried in vacuum at 60 °C to obtain the polymer (0.45 g, 90 %).

[0145] Example 8: Preparation of PB-Et12 A sealable vial (pressure resistance: 2 MPa) equipped with a magnetic stirrer was charged with 0.5 g of PB-E12 (Ca. 1.2 mmol epoxy group, 1 eq), 0.26 g of zinc chloride (1.911 mmol, 1 eq), and 3 mL of dry THF. After this, 3 mL of ethylamine THF solution (~10% in THF, ~2 mol / L) was added dropwise to the mixture. The vial was sealed and the mixture was stirred at 110 °C for 24 h. The polymer was precipitated twice into ice-cold methanol, and the precipitate was collected and dried in vacuum at 60 °C to obtain the polymer (0.43 g, 80 %).

[0146] Example 9: Preparation of PB-Et20 A sealable vial (pressure resistance: 2 MPa) equipped with a magnetic stirrer was charged with 0.5 g of PB-E20 (Ca. 1.92 mmol epoxy group, 1 eq.), 0.26 g of zinc chloride (1.911 mmol, 1 eq.) and 5 ml of dry THF. After this, 4 mL of ethylamine THF solution (~10% in THF, ~2 mol / L) was added dropwise to the mixture. The vial was sealed and the mixture was stirred at 110 °C for 24 h. The polymer was precipitated twice into ice-cold methanol, the precipitate was collected and dried in vacuum at 60 °C to obtain the polymer (0.40 g, 71 %).

[0147] Example 10: Preparation of SBS-Bu12 A sealable vial (pressure resistance: 2 MPa) equipped with a magnetic stirrer was charged with 0.5 g of SBS-E12 (Ca. 0.87 mmol epoxy group, 1 equiv.), 0.118 g of zinc chloride (0.87 mmol, 1 equiv.), and 3 ml of dry THF. Then, butylamine (1.5 mL, 15.16 mmol, 12.6 equiv.) was added dropwise to the mixture. The vial was sealed and the mixture was stirred at 110 °C for 24 h. The polymer was precipitated twice into ice-cold methanol, and the precipitate was collected and dried in vacuum at 60 °C to obtain the polymer (0.43 g, 86 %).

[0148] Example 11: Preparation of SBS-Et12 A sealable vial (pressure resistance: 2 MPa) equipped with a magnetic stirrer was charged with 0.5 g of SBS-E12 (Ca. 0.87 mmol epoxy group, 1 eq), 0.118 g of zinc chloride (0.87 mmol, 1 eq) and 3 ml of dry THF. After this, 3 mL of ethylamine THF solution (~10% in THF, ~2 mol / L) was added dropwise to the mixture. The vial was sealed and the mixture was stirred at 110 °C for 24 h. The polymer was precipitated twice into ice-cold methanol, the precipitate was collected and dried in vacuum at 60 °C to give the polymer (0.42 g, 78 %).

[0149] Example 12: Preparation of SBS-DE12 A sealable vial (pressure resistance: 2 MPa) was equipped with a magnetic stirrer and charged with 0.5 g of SBS-E12 (Ca. 0.87 mmol epoxy group, 1 eq), 0.118 g of zinc chloride (0.87 mmol, 1 eq), and 3 mL of dry THF. Diethylamine (1.5 mL, 14.6 mmol, 12.1 eq.) was then added dropwise to the mixture. The vial was sealed and the mixture was stirred at 110 °C for 24 h. The polymer was precipitated twice into ice-cold methanol, and the precipitate was collected and dried in vacuum at 60 °C to obtain the polymer (0.37 g, 66%).

[0150] Example 13: Preparation of PB-AEOTMS12 A sealable vial (pressure resistance: 2 MPa) equipped with a magnetic stirrer was charged with 0.5 g of PB-E12 (Ca. 1.2 mmol epoxy group, 1 eq), 0.26 g of zinc chloride (1.911 mmol, 1 eq), and 3 ml of dry THF. After this, 2 g of 2-((trimethylsilyl)oxy)ethan-1-amine (15.0 mmol, 12.5 eq.) was added dropwise to the mixture. The vial was sealed and the mixture was stirred at 110 °C for 24 h. The polymer was precipitated twice into ice-cold methanol, and the precipitate was collected and dried in vacuum at 60 °C to obtain the polymer (0.48 g, 78 %).

[0151] [ka]

[0152] Example 14: Preparation of PB-AEOH12 A solution of 0.25 g of PB-AEOTMS12 in 10 mL of THF was placed in a two-neck flask equipped with a magnetic stirrer. To this was added a solution of 100 mg of NaOH and 2 mL of H2O in 5 mL of THF. The resulting mixture was stirred at room temperature for 12 hours. After precipitation twice into ice-cold methanol, the precipitate was collected and dried under vacuum at 60°C to give the polymer (0.17 g, 71%).

[0153] Example 15: Preparation of PB-AE2OTMS12 A sealable vial (pressure resistance: 2 MPa) equipped with a magnetic stirrer was charged with 0.5 g of PB-E12 (Ca. 1.2 mmol epoxy group, 1 eq), 0.26 g of zinc chloride (1.911 mmol, 1 eq), and 3 ml of dry THF. After this, 3.5 g of 2,2,8,8-tetramethyl-3,7-dioxa-2,8-disilanonan-5-amine (14.8 mmol, 12.5 eq.) was added dropwise to the mixture. The vial was sealed and the mixture was stirred at 110 °C for 24 h. The polymer was precipitated twice in ice-cold methanol, the precipitate was collected, and dried in vacuum at 60 °C to obtain the polymer (0.40 g, 46%).

[0154] [ka]

[0155] Example 16: Preparation of PB-B12 A sealable vial (pressure resistance: 2 MPa) equipped with a magnetic stirrer was charged with 0.5 g of PB-E12 (Ca. 1.2 mmol epoxy group, 1 eq), 0.26 g of zinc chloride (1.911 mmol, 1 eq), and 3 ml of dry THF. After this, 1.3 g (12.4 mmol, 10.0 eq.) of phenylmethanamine was added dropwise to the mixture. The vial was sealed and the mixture was stirred at 110 °C for 24 h. The polymer was precipitated twice in ice-cold methanol, and the precipitate was collected and dried in vacuum at 60 °C to obtain the polymer (0.39 g, 74 %).

[0156] [ka]

[0157] Example 17: Preparation of PI-Bu12 A sealable vial (pressure resistance: 2 MPa) equipped with a magnetic stirrer was charged with 0.5 g of PI-E12 (Ca. 0.88 mmol epoxy group, 1 eq), 0.12 g of zinc chloride (0.88 mmol, 1 eq), and 3 mL of dry THF. Then, butylamine (2 mL, 20.22 mmol, 10 eq.) was added dropwise to the mixture. The vial was sealed and the mixture was stirred at 110 °C for 48 h. The polymer was precipitated twice into ice-cold methanol, and the precipitate was collected and dried in vacuum at 60 °C to obtain the polymer (0.19 g, 35%).

[0158] Comparative Example 1: Synthesis of PB-Bu20 (without catalyst) A solution of PB-E20 in 10 mL of THF was added to a Schlenk flask equipped with a magnetic stirrer under a dry nitrogen atmosphere. To this was added a solution of 3 mL of butylamine dropwise. The resulting mixture was then refluxed at 70°C for 12 hours. The product was analyzed by NMR, but no reaction had occurred.

[0159] Comparative Example 2: Synthesis of PB-Bu20 (catalyst: LiBr) In a Schlenk flask equipped with a magnetic stirrer, 0.2 g of LiBr and a solution of PB-E20 in 10 mL of THF were added under a dry nitrogen atmosphere. To this was added a solution of 3 mL of butylamine dropwise. The resulting mixture was then refluxed at 70°C for 12 hours. The product was analyzed by NMR, but no reaction had occurred.

[0160] Figure 1A shows the polymer formation data of PB, PB-E20, PB-Bu20, and PB-DE20 obtained by NMR. Figure 1B shows the NMR data of elastomers SBS, SBS-Bu12, and SBS-DE12. Figure 1C shows the NMR data of elastomers PB-AEOTMS12 and PB-AEOH12. Figure 1D shows the NMR data of elastomer PB-AE2OTMS12. Figure 1E shows the NMR data of elastomer PB-B12. Figure 1F shows the NMR data of elastomer PI-Bu12.

[0161] The formation of PB-E12, PB-E23, PB-E33, PB-E40, SBS-E12, SBS-E20, PI-E12, PB-Bu12, PPB-Bu23, PPB-Bu33, PPB-Bu40, PB-DE12, PB-Et12, PB-Et20, SBS-Et12, and SBS-PB-AEOTMS12 was also confirmed by NMR (data not shown).

[0162] Determination of molecular weight of modified polymer The results of gel permeation chromatography for Examples 1, 2, 6, 8 and 9 are shown in Table 2.

[0163] [Table 2]

[0164] Mechanical properties of modified polymers In the examples herein, tensile tests were performed on elastomer specimens (1.33 mm (width) * 8 mm (length) * Ca. 0.2 mm (thickness)) at a nominal strain rate of 0.10 s -1 The elongation was carried out at a rate of 50 mm / min, which corresponds approximately to the elongation rate of 50 mm / min.

[0165] In the tensile tests of the polymers PB-Bu12, PB-Bu20, PB-DE12, PB-DE20, and PB, pure PB showed a breaking stress of about 0.1 MPa and an elongation at break (also called elongation at break) of about 440%, as shown in Figures 2A and 2B. The elastomers after VAA incorporation showed good tensile performance, as shown in Figures 2A and 2B.

[0166] As shown in Figure 2A, PB-Bu12 and PB-Bu20 showed significant toughness improvement with break stress of 3.3 MPa and 6.5 MPa, respectively. Compared to pure PB elastomers, PB-Bu elastomers showed about 30-70 times improvement in toughness. In addition, the elastomeric behavior was also improved, with PB-Bu12 showing about 1200% elongation to break and PB-Bu20 showing about 800% elongation to break. PB-Bu23, PB-Bu33, and PB-Bu40 also showed improved toughness and break elongation compared to PB.

[0167] Figure 3A shows the results of cyclic uniaxial elongation testing of PB-Bu12 at 300%. After 1 min of recovery, the elastomer showed approximately 50% recovery, and after over 1 h of recovery, it had recovered over 70%, demonstrating the excellent recovery of PB-Bu12.

[0168] Figure 3B shows the hysteresis recovery calculated from cyclic uniaxial extension tests of PB-Bu12.

[0169] As shown in Figure 4, the mechanical properties were excellent even after the incorporation of diethylamine. PB-DE12 showed high performance in both elongation and stress. Furthermore, PB-DE20 showed the best elastomeric behavior with an elongation at break of about 4500%.

[0170] As shown in Figure 5, PB-Et12 and PB-Et20 exhibited significant toughness improvement with break stresses of 13.0 Mpa and 7.0 Mpa, respectively. Compared to the pure PB elastomer, the PB-Bu elastomer showed approximately 60-150 times toughness improvement. Furthermore, PB-Et12 showed approximately 1000% break elongation.

[0171] Tensile tests were performed on the styrene-butadiene-styrene (SBS) polymer SBS and the elastomers SBS-Bu12, SBS-Et12, and SBS-DE12 before and after VAA modification, and the results are shown in Figure 6B. The SBS elastomer without VAA modification showed a breaking stress of about 12 MPa and a breaking elongation of about 1500%. In addition, SBS-Bu12, which contains 12% vicinal butylamine alcohol, showed excellent toughness of about 32 MPa and a breaking elongation of about 1200%. SBS-Et12 and SBS-DE12 also showed increased toughness, similar to SBS-Bu12.

[0172] In the tensile test shown in FIG. 7, PB-AEOTMS12 had increased breaking stress and breaking elongation compared to PB-AEOH12.

[0173] In the tensile test shown in FIG. 8, PB-AE2OTMS12 exhibited a breaking stress of about 200 MPa and a breaking elongation of about 1700%.

[0174] In the tensile test of FIG. 9, PB-E12 reached a yield point of about 0.35 MPa and exhibited a high breaking elongation of about 3800%.

Claims

1. A vicinal amino alcohol unit represented by formula (1) 【Chemistry 1】 (In the formula, R 1 and R 2 are independently hydrogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted phenylalkyl, or -OTMS. But-1-en-1,4-diyl unit represented by formula (2) 【Chemistry 2】 (In the formula, R 3 and R 4 are independently hydrogen or substituted or unsubstituted C1-C5 alkyl.

2. An elastomer comprising:

2. R 1 and R 2 The elastomer of claim 1, wherein one of is hydrogen.

3. 2. The elastomer according to claim 1, wherein the proportion of vicinal amino alcohol units represented by formula (1) is 1 to 20 mol % and the proportion of but-1-en-1,4-diyl units represented by formula (2) is 80 to 99 mol % relative to all units constituting the elastomer.

4. An elastomer represented by formula (I): 【Chemistry 3】 (In the formula, R 1 and R 2 are independently hydrogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted phenylalkyl, or -OTMS; R 3 and R 4 are independently hydrogen or substituted or unsubstituted C1-C5 alkyl; The molar ratio of x:y is 99:1 to 60:

40.

5. An epoxy unit represented by formula (3), 【Chemistry 4】 But-1-en-1,4-diyl unit represented by formula (4) 【Chemistry 5】 (In the formula, R 3 and R 4 are independently hydrogen or substituted or unsubstituted C1-C5 alkyl.

1. A method for producing an elastomer, comprising reacting a copolymer comprising:

6. 6. The method of claim 5, wherein the amine comprises a primary amine.

7. 6. The method of claim 5, further comprising reacting the conjugated diene polymer with m-chloroperoxybenzoic acid to form a copolymer comprising epoxy units represented by formula (3) and but-1-ene-1,4-diyl units represented by formula (4).

8. The method of claim 7, wherein the conjugated diene-based polymer comprises a butadiene-based polymer, an isoprene-based polymer, or an aromatic vinyl-conjugated diene copolymer.

9. A composition comprising the elastomer according to any one of claims 1 to 4.

10. A rubber modifier comprising the elastomer according to any one of claims 1 to 4.

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