KR20210156665A - Acetylene based polymer and preparation method for the same - Google Patents

Abstract

The present invention relates to an acetylene-based polymer having a main chain in which cis and trans double bonds, two repeating structural units, are arranged alternately, and a preparation method thereof. In the main chain of the acetylene-based polymer, the ratio of cis and trans isomers in the double bond structure is 0.9:1.1 to 1.1:0.9.

Description

Acetylene-based polymer and manufacturing method thereof

The present invention relates to an acetylenic polymer, and more particularly, to an acetylenic polymer having a main chain in which a cis-double bond structure and a trans-double bond structure are alternately repeated, and a method for preparing the same.

The acetylene polymer is a polymer having a polyene structure in which double bonds and single bonds are alternately linked. Acetylene polymers form cis-type and trans-type geometric isomers depending on polymerization conditions, and when the cis-type is heated to a high temperature, the trans-type is changed. Acetylene polymers have been studied intensively over the past few decades due to their structural rigidity and semiconducting potential of the conjugated pi-system of the backbone.

If the double bond substituent of the acetylene-based polymer is changed, it may exhibit orientation characteristics while having a specific tertiary structure. For example, in the case of polyphenylacetylene having a phenyl group as a substituent, the polymer chain may exhibit a property of twisting into a helix depending on conditions such as solvent and temperature, and the pitch of the helix is uniquely different. sexual characteristics change.

The helical structure of polymers plays an important role in nature. The main structure of DNA and proteins is the helix, and the dynamic change of the helix structure is one of the most important control mechanisms of molecular recognition in biological systems.

Poly(phenyl acetylene) having a cis-rich structure exhibits strong helicity according to the interaction between phenyl side chains. The double bonds of the polyacetylene backbone maintain primarily the initial geometric cis and trans configurations upon conformational change. On the other hand, due to the rotation of the σ-bond between the two double bonds, the polyacetylene backbone can be interconverted between the cis- and trans-form structures depending on the interaction between the side chain and the solvent molecule. Conventionally, only polyacetylene having cisoidal-cis and transoidal-cis structures is known to form a helical structure, so studies for improving the helicity of polyacetylene have been focused on the synthesis of cis-rich polyacetylene. Few reports have been made on the helical structure of an acetylenic polymer having a trans structure exceeding 10%.

However, the present inventors have discovered that when the cis structure of an acetylenic polymer can be regularly included in the backbone of the polymer, the polymer can form a helical structure despite a high content of trans structure, and accordingly, the novel acetylenic polymer can form a helical structure. An object of the present invention is to provide a polymer and a method for preparing the same.

KR 2007-0056070 A

An object of the present invention is to provide an acetylenic polymer having a main chain in which a cis-double bond structure and a trans-double bond structure are alternately repeated.

Another object of the present invention to be solved is to provide a method for producing the acetylene-based polymer.

In order to solve the above problems, the present invention has a main chain in which a cis-double bond structure and a trans-double bond structure are alternately repeated, and in the main chain of the acetylene-based polymer, the cis-double bond structure and the trans-double bond structure are 0.9 It provides an acetylenic polymer having a ratio of :1.1 to 1.1:0.9.

In order to solve the other problems, the present invention provides a method for producing the acetylene-based polymer comprising the process of cyclization polymerization of a compound of the following formula (9) to form a compound of the following formula (1).

[Formula 9]

[Formula 1]

In Formula 1, A is an arylalkyl group having 7 to 20 carbon atoms and a carbonyl group of an amino acid having an ester bond, and n is an integer of 7 to 1,000.

The acetylene-based polymer according to the present invention has a main chain in which a cis-double bond structure and a trans-double bond structure are alternately repeated, and since the cis-double bond structure is regularly included in the main chain of the polymer, a high trans-double bond structure It may have a helical secondary structure even including.

^{1 is a 1} H NMR spectrum of L-Fmoc-Ala-CP monomer.
^{2 is a 1} H NMR spectrum of L-Fmoc-Ala-CP polymer.
3 is a graph of polymerization of L-Fmoc-Ala-CP with time.
4 is a graph of conversion kinetics of L-Fmoc-Ala-CP.
5 is a selective NOE spectrum in _{CDCl 3} for the polymer of Example 2.
6 is a thermogravimetric analysis (TGA) graph of the polymer of Example 2.
7 is a differential scanning calorimetry (DSC) graph of the polymer of Example 2.
Figure 8 shows the circular dichroism of the polymers of Examples 1 to 3 (L-Fmoc-Ala), the polymer of Example 4 (D-Fmoc-Ala) and the polymer of Comparative Example 1 (L-Boc-Ala) ( circular dichroism (CD) spectrum.
9 is a CD spectrum in chloroform and a CD spectrum in DMF for the polymer of Example 2.
10 is a result of measuring the CD spectrum of the polymer of Example 4 by changing the solvent composition of chloroform/DMF.
11 is a CD spectrum of the polymer of Example 2 in chloroform and DMF, a) after 2 hours of dissolving in a solvent, b) after 1 day of dissolving in a solvent, c) 3 days after dissolving in a solvent is the spectrum
12 is a GPC trace for the polymer of Example 4.
In FIG. 13, a) is chloroform, b) is THF, and c) is an NMR spectrum of L-Fmoc-Ala-monomer in DMF solvent.
In FIG. 14, a) is an NMR spectrum of L-Fmoc-Ala-monomer in chloroform and b) is acetic acid addition.
In FIG. 15, a) is a low-temperature (15°C) NMR spectrum of L-Fmoc-Ala-monomer in chloroform, b) THF, and c) DMF.
16 is a CD spectrum in chloroform and DMF for the polymers of Examples 6 and 7.
17 is an AFM photograph, (a) and (b) are height and phase images of the 2D crystal of the polymer of Example 2 in chloroform, respectively, (c) is a single-stranded height image of spin coating, ( d) and (e) are annealing and phase images of 2D crystal height images through DMF solution, respectively, and f) are double-stranded phase images of spin coating.
18 is a CD and UV-Vis spectrum of the polymer of Example 2 in THF and DMSO.
19 is a CD spectrum showing the difference in optical activity as the ratio of DMF mixed with THF of the polymer of Example 2 increases.
In FIG. 20, a) is a CD and UV-Vis spectrum for the polymer of Example 2 in DMF, DMAc, NMP, DEF, DIPF, and b) is an STD- for confirming the interaction of the polymer with DMF and THF in chloroform. NMR, c) is a schematic diagram of the interaction between the polymer and the solvent.
21 is a result of measuring the CD spectrum after one day (a) and three days (b) after dissolving the polymer of Example 2 in DMF, DEF, and DIPF.
22 is an STD-NMR for observing the interaction between THF in chloroform and the polymer of Example 2.
23 is an STD-NMR for observing the interaction between DMF in chloroform and the polymer of Example 2.

Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.

The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

As used herein, the term "polymer" means a polymer compound prepared by polymerization of monomers of the same or different types. The generic term "polymer" includes the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer". Also, the term “interpolymer” refers to a polymer prepared by polymerization of two or more different types of monomers. The generic term "interpolymer" refers to the term "copolymer" (which is commonly used to refer to polymers prepared from two different monomers), as well as the term "copolymer" (which is commonly used to refer to polymers prepared from three different types of monomers). used) the term "terpolymer". This includes polymers prepared by polymerization of four or more types of monomers.

The acetylenic polymer according to the present invention has a main chain in which a cis-double bond structure and a trans-double bond structure are alternately repeated, and the cis-double bond structure and the trans-double bond structure in the main chain of the acetylenic polymer are 0.9:1.1 to 1.1:0.9 to have a ratio.

In addition, the main chain of the acetylene-based polymer according to an example of the present invention may have a substituent derived from an amino acid, and the secondary structure of the acetylene-based polymer may have a helical structure due to the interaction between the substituents derived from the amino acid. have.

The acetylenic polymer according to the present invention has a cis-transoid form in which a cis-double bond structure and a trans-double bond structure are alternately repeated, and a cis-double bond structure and a trans-double bond structure in the main chain of the acetylenic polymer has a ratio of 0.9:1.1 to 1.1:0.9 based on the number, and the cis-double bond structure and the trans-double bond structure may specifically have a ratio of 0.95:1.05 to 1.05:0.95, more specifically As a result, it may have a ratio of 0.99:1.01 to 1.01:0.99.

In addition, in the acetylene-based polymer according to an example of the present invention, the cis-double bond structure and the trans-double bond structure may have a ratio of 1:1, and more specifically, the acetylene-based polymer according to an example of the present invention has a cis- The number of double bond structures may be one less or more than the number of trans-double bond structures.

The reason that the acetylene-based polymer according to the present invention can have a cis-double bond structure and a trans-double bond structure in the main chain in a similar ratio as in the above range is derived from the structure, and the acetylenic polymer is represented by the following formula (1) It may contain repeating units.

[Formula 1]

In Formula 1, A is an arylalkyl group having 7 to 20 carbon atoms and a carbonyl group of an amino acid having an ester bond, and n is an integer of 7 to 1,000.

The acetylene-based polymer according to an example of the present invention includes a regular pyrrole-based ring as shown in Formula 1, and has a cis double bond in the ring, and the double bond between the rings is a trans double bond depending on steric hindrance between the rings. As a result of the bond, cis and trans structures appear alternately as shown in Formula 1-1 below.

[Formula 1-1]

In Formula 1, A is a substituent derived from an amino acid, and is a carbonyl group of an amino acid having an ester bond with an arylalkyl having 7 to 20 carbon atoms. Specifically, in one example of the present invention, A is represented by the following Formula 2 or 3 can be displayed.

[Formula 2]

[Formula 3]

In Formulas 2 and 3, R ₁ is a substituent derived from α-amino acid, and R ₂ is arylalkyl having 7 to 28 carbon atoms.

Specifically, R ₁ is hydrogen, methyl, hydroxymethyl, carboxymethyl, guanidinepropyl, isopropyl, 1-hydroxyethyl, isobutyl, mercaptomethyl, 1H-imidazol-4-yl, aminobutyl, 1 -Methylpropyl, 4-hydroxyphenylmethyl, 2-amino-2-oxoethyl, 2-methylthioethyl, (1 H -indol-3-yl)methyl, phenylmethyl, or 3-amino-3-oxo It could be a profile.

In addition, R ₂ may be specifically represented by the following formula (4).

[Formula 4]

In Formula 4, R ₃ is alkylene having 1 to 8 carbon atoms, and R ₄ is aryl having 6 to 20 carbon atoms.

Further, in an example of the present invention, R ₃ may be alkylene having 1 to 6 carbon atoms, specifically alkylene having 1 to 4 carbon atoms, and more specifically methylene.

Further, in an example of the present invention, R ₄ may be an aryl having 6 to 18 carbon atoms, specifically fluorenyl.

Further, in an example of the present invention, n may be an integer of 8 to 500, specifically, an integer of 10 to 50.

That is, in one example of the present invention, the acetylene-based polymer may include a repeating unit represented by the following formula (1).

[Formula 1]

In Formula 1, A is represented by Formula 2 or 3, n is an integer of 7 to 1,000,

[Formula 2]

[Formula 3]

In Formulas 2 and 3, R ₁ is a substituent derived from α-amino acid, R ₂ is represented by Formula 4 below,

[Formula 4]

In Formula 4, R ₃ may be alkylene having 1 to 8 carbon atoms, and R ₄ may be aryl having 6 to 20 carbon atoms.

In addition, in one example of the present invention, the acetylene-based polymer may include a repeating unit represented by the following formula (1).

[Formula 1]

In Formula 1, A is any one of Formulas 5 to 8, and n is an integer of 7 to 1,000.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

As shown in Formulas 2, 3, and 5 to 8, A has a chiral carbon, and the acetylenic polymer according to an example of the present invention has optical activity due to spatial interaction of a substituent connected to the chiral carbon. structure can be shown.

In one example of the present invention, the acetylene-based polymer may be prepared by a method comprising a process of cyclizing a compound of Formula 9 to form a polymer having a repeating unit represented by Formula 1 below.

[Formula 9]

[Formula 1]

In Formulas 1 and 9, A is a carbonyl group of an amino acid having an ester bond with an arylalkyl having 7 to 20 carbon atoms, and n is an integer of 7 to 1,000.

In Formulas 1 and 9, A may be represented by Formula 2 or 3 below.

[Formula 2]

[Formula 3]

In Formulas 2 and 3, R ₁ is a substituent derived from α-amino acid, and R ₂ is arylalkyl having 7 to 28 carbon atoms.

The compound of Formula 9 is subjected to cyclization polymerization in the presence of a ruthenium catalyst, specifically, a Grubbs catalyst, more specifically, a third-generation Grubbs catalyst to form a polymer having a repeating unit represented by Formula 1 above.

According to the method for producing an acetylene-based polymer according to an example of the present invention, a ring having a double bond is formed by cyclization according to the metathesis reaction of the compound of Formula 9 in the presence of a ruthenium catalyst, and the acetylene polymer skeleton grows. In addition, double bonds are arranged in cis and trans forms depending on the steric hindrance between adjacent rings. Accordingly, according to the method for producing an acetylene-based polymer of the present invention, an acetylene polymer having a cis/trans ratio of 0.9:1.1 to 1.1:0.9, specifically acetylene having a cis/trans ratio of 0.95:1.05 to 1.05:0.95 Polymers, more specifically acetylene polymers having a ratio of 0.99:1.01 to 1.01:0.99 can be prepared.

In addition, according to the method for producing an acetylene-based polymer according to an example of the present invention, an acetylene-based polymer having the cis-double bond structure and the trans-double bond structure in a ratio of 1:1 can be prepared, and more specifically, the cis- An acetylenic polymer having one less or more double bond structure than the number of trans-double bond structures can be prepared.

In addition, in one example of the present invention, the compound of Formula 9 is prepared by an amide coupling reaction between a compound of Formula 10 and an arylalkyl having 7 to 20 carbon atoms and an amino acid having an ester bond to prepare a compound of Formula 9 can be obtained through

[Formula 10]

[Formula 9]

wherein A is a carbonyl group of an amino acid having an ester bond with an arylalkyl having 7 to 20 carbon atoms,

R ₁ is a substituent derived from α-amino acid, and R ₂ is arylalkyl having 7 to 28 carbon atoms.

In an example of the present invention, when A in the compound of Formula 9 is a compound of Formula 2 or Formula 3, the compound of Formula 9 is obtained by amide coupling reaction between a compound of Formula 10 and a compound of Formula 11 or 12 to obtain Formula 9 It can be prepared by the process of preparing a compound of

[Formula 11]

[Formula 12]

In Formulas 11 and 12, R ₁ is a substituent derived from α-amino acid, and R ₂ is arylalkyl having 7 to 28 carbon atoms.

On the other hand, in the example of the present invention, A in the formula (9) may be as defined as A of Formula 1, R ₁ and R ₂ of Formula 11 and 12 are each of the formula 2 and 3 R _1, and R ₂ may be as defined.

The method for producing an acetylene-based polymer according to an example of the present invention may be represented by the following Reaction Scheme 1.

[Scheme 1]

The Grubbs catalyst may be represented by the following Chemical Formula 13.

[Formula 13]

In Formula 13, X is halogen, and specifically, may be Cl or Br.

In Scheme 1, the nitrogen-linked dipropargyl amine monomer may have a higher tendency to undergo cyclization polymerization than the carbon-linked hepta-1,6-diyne structure. , the amides formed between the main chain backbone and the side chains limit the degree of rotation, facilitating the helical structure. In addition, a substituent derived from the optically active amino acid represented by A may be easily incorporated into the monomer.

As shown in Scheme 1, the monomer used to polymerize the acetylene polymer of the present invention may be prepared by an amino coupling reaction between dipropargyl amine and an amino acid represented by OH-A. For example, when A is any one of the substituents represented by Chemical Formulas 5 to 8, the monomer used for polymerizing the acetylene polymer according to an example of the present invention is dipropargyl amine and fluorenylmethyloxycarbonyl (Fmoc) -Can be prepared by a coupling reaction between protected (protected) amino acids.

The term 'alkyl' as used herein, unless otherwise specified, refers to a straight-chain or branched hydrocarbon residue.

According to an example of the present invention, the aryl group preferably has 6 to 20 carbon atoms, specifically phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, fluorenyl, etc., but limited to these examples it is not going to be

The alkylaryl group means an aryl group substituted by the alkyl group.

The arylalkyl group means an alkyl group substituted by the aryl group.

The amino acid having an ester bond with the arylalkyl means that the amino group of the amino acid is bonded to the arylalkyl by an ester group, and the carbonyl group of the amino acid having the arylalkyl and ester bond is the amino group of the amino acid by an ester group. It is bonded and represents a form in which the hydroxyl group is removed from the carboxy group of the amino acid and the carbon of the carbonyl group is linked. In the present invention, an example of the amino acid having an ester bond with the arylalkyl may be represented by Formula 11 or Formula 12, and an example of a carbonyl group of an amino acid having an ester bond with the arylalkyl is Formula 2 or Formula 3 can be expressed together.

Example

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

Dichloromethane (DCM, anhydrous), n,n-dimethylformamide (DMF, anhydrous), dipropargylamine, n,n-diethylformamide (DEF) and second-generation Grubbs catalysts were obtained from Sigma-Aldrich (USA). ) was purchased from Third-generation Grubbs catalysts are described in Kang, E.-H.; Lee, IS; Choi, T.-L., Ultrafast Cyclopolymerization for Polyene Synthesis: Living Polymerization to Dendronized Polymers. Journal of the American Chemical Society 2011, 133 (31), 11904-11907.] was synthesized from the second-generation Grubbs catalyst. Diisopropylethyleneamine (DIPEA) and n,n-diisopropyl formamide (DIPF) were purchased from TCI (Japan), and NaHCO, HCl and magnesium sulfate (MgSO ₄ ) were purchased from Daejung Chemical (Korea). Chloroform, dichloromethane (DCM), tetrahydrofuran (stabilized by 0.01 % BHT), ethyl acetate (EA) and hexane were purchased from Samcheonsoonyak (Korea). Fmoc-L-Ala-OH, Fmoc-D-Ala-OH, Fmoc-L-Phe-OH and Fmoc-D-Phe-OH were purchased from Novabiochem (San Diego, CA, USA).

Example 1

<Preparation of monomer>

[Scheme 2]

N-protected amino acid (compound 2 of Scheme 2 above) (1.00 mmol) was dissolved in anhydrous DMF (5 mL). To the solution was added (benzotriazol-1-yloxy)tripyrrolidinophosphonium hexafluorophosphate (PyBOP) (624 mg, 1.20 mmol) and diisopropylethylamine (DIPEA) (215 μL, 1.20 mmol) did After the compound was completely dissolved in DMF, dipropargylamine (compound 1 of Scheme 2) (103 μL, 1.00 mmol) was added and stirred at room temperature for 3 hours. After confirming that the reaction was completed by thin layer chromatography (TLC), DIPEA and DMF were removed by evaporation. The remaining mixture was dissolved in dichloromethane (DCM) and washed sequentially with _{0.1M HCl solution twice, saturated NaHCO 3 solution and brine.} The organic phase was _{dried over MgSO 4} and concentrated under reduced pressure. The residue was purified by silica gel chromatography with an eluent of ethyl acetate (EA)/n-hexane. Fmoc-L-Ala-CP monomer (compound 3 of Scheme 2) was obtained as a white powder (isolated yield: ~ 73%)

¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.77 (d, J = 7.4 Hz, 2H; Ar H), 7.60 (d, J = 7.3 Hz, 2H; Ar H), 7.42 (d, J = 7.3 Hz) , 2H; Ar H), 7.32 (t, J = 7.3 Hz, 2H; Ar H), 5.70 (d, J = 7.7 Hz, 1H; -N H COO), 4.87 - 4.66 (m, 1H; NC H C ), 4.56 -4.07 (m, 7H), 2.30 (d, J = 21.7 Hz, 2H; C≡C H ), 1.42 (d, J = 6.8 Hz, 3H; -CHC H ₃ ).

<Production of acetylene-based polymer>

[Scheme 3]

The prepared monomer (0.104 mmol) was dissolved in anhydrous DMF (500 μL) in a glove box. Then, a solution of the third-generation Grubbs catalyst (compound 4 in Scheme 3) was rapidly added to the solution while vigorously stirring. After confirming complete conversion by TLC, an excess of ethylvinyl ether was added to quench the reaction. After repeated precipitation in diethyl ether, it was dried in high vacuum to obtain a polymer (L-Fmoc-Ala-CP, compound 5 of Scheme 3).

[α] _D =+23.5401 (30°C, c=0.5mg/mL, CHCl ₃ )

¹ H-NMR (500 MHz, CDCl ₃ ) δ 7.96-7.01 (8H; Ar H), 6.85-6.08 (2H; H C= CH ), 5.98-5.34 (1H, —N H COO), 5.09-3.72 (8H), 1.54-1.24 (3H -CHC H ₃ ).

Examples 2 and 3

Using the monomer prepared in Example 1, a polymer was prepared in the same manner as in Example 1, except that the amount of the monomer used in the preparation of the acetylene-based polymer was changed to 0.208 mmol and 0.312 mmol, respectively. to obtain this.

Examples 4 to 6

In Example 1, each monomer was obtained in the same manner as in Example 1, except that the compound 2 of Scheme 2 was replaced as an N-protected amino acid and the compound of the second column of Table 1 was used.

Using the prepared monomer, the polymer was prepared in the same manner as in the preparation of the acetylenic polymer of Example 1, except that the amount of the monomer used in the preparation of the acetylenic polymer was changed to 0.208 mmol, respectively. obtained.

Analytical data for Examples 4 to 6 are shown below.

Example 4

<D-Fmoc-Ala-CP polymer>

[α] _D =-18.7129 (30°C, c=0.5mg/mL, CHCl ₃ )

Example 5

<L-Fmoc-Phe-CPm monomer>

¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.77 (d, J = 7.5 Hz, 2H; Ar H), 7.56 (dd, J = 7.2, 3.7 Hz, 2H; Ar H), 7.40 (t, J = 7.4 Hz, 2H; Ar H), 7.32 (d, J = 7.4 Hz, 2H; Ar H), 7.21 (t, J = 7.1 Hz, 2H; Ar H), 5.61 (d, J = 8.4 Hz, 1H; -N H COO), 4.92 (dd, J = 14.8, 6.9 Hz, 1H; NC H C), 4.50-3.85 (m, 7H), 3.07 (qd, J = 13.5, 6.7 Hz, 2H; -CC H ₂ C-), 2.27 (d, J = 9.74 Hz, 2H; C≡C H ).

<L-Fmoc-Phe-CPm Polymer>

[α] _D =+24.6415 (30°C, c=0.5mg/mL, CHCl ₃ )

¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.96-7.01 (13H; Ar H), 7.01-6.11 (2H; H C= CH ), 5.19-3.99 (6H), 4.00-3.50 (5H), 3.48 -3.00 (2H; C CH ₂ C-).

Example 6

<D-Fmoc-Phe-CP Polymer>

[α] _D = -27.1125 (30 ° C, c = 0.5 mg/mL, CHCl ₃ )

Comparative Examples 1 and 2

In Example 1, each monomer was obtained in the same manner as in Example 1, except that the compound 2 of Scheme 2 was replaced as an N-protected amino acid and the compound of the second column of Table 1 was used.

A polymer was prepared in the same manner as in the preparation of the acetylene-based polymer of Example 1 using the prepared monomer to obtain this.

Comparative Example 1

<L-Boc-Ala-CP monomer>

¹ H-NMR (300 MHz, CDCl ₃ ) δ 5.37 (d, J = 7.6 Hz, 1H; -N H COO), 4.76 - 4.58 (m, 1H; NC H C ), 4.33 (dd, J = 18.8, _{16.3 Hz, 4H; -CC H 2} N-), 2.29 (d, J = 25.9 Hz, 2H; C≡C H), 1.44 (s, 9H; -OC (CH 3) 3), 1.36 (d, J = 6.8 Hz, 3H, -CHC H ₃ ).

<L-Boc-Ala-CP polymer>

[α] _D =-4.3104 (30°C, c=0.5mg/mL, CHCl ₃ )

¹ H-NMR (300 MHz, CDCl ₃ ) δ 6.83-5.88 (2H; H C= CH ), 5.30 (s, 10H), 5.73-5.10(1H; -N H COO), 1.77-1.11 (12H; -OC (CH ₃ ) ₃ and -CHC H ₃ ).

Comparative Example 2

<L-Boc-Phe-CP monomer>

¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.21 (d, J = 7.7 Hz, 5H; Ar H), 5.27 (d, J = 8.3 Hz, 1H; -N H COO), 4.83 (d, J = 7.5 Hz, 1H; NC H C), 4.42 - 4.20 (ddd, 4H; -CC H ₂ N-), 3.02 (ddd, J = 19.7, 13.4, 6.9 Hz, 2H; -CC H ₂ C-), 2.26 (d, J = 11.2 Hz, 2H; C≡C H ), 1.39 (s, 9H; -CHC H ₃ ).

<L-Boc-Phe-CP Polymer>

[α] _D =-3.0133 (30℃, c=0.5mg/mL, CHCl ₃ )

¹ H-NMR (500 MHz, CDCl ₃ ) δ 7.61 - 6.83 (5H, Ar H), 6.267-5.79 (2H; H C= CH ), 5.63-5.08 (1H; -N H COO), 4.97-2.85 (7H), 1.57-0.8 (3H;-CHC H ₃ ),

Types of N-protected amino acids Structure of N-protected amino acids The structure of the repeating unit of the prepared polymer Example 1 L-Fmoc-Ala-CP

(n=10) Example 2 L-Fmoc-Ala-CP

(n=20) Example 3 L-Fmoc-Ala-CP

(n=30) Example 4 D-Fmoc-Ala-CP

(n=20) Example 5 L-Fmoc-Phe-CP

(n=20) Example 6 D-Fmoc-Phe-CP

(n=20) Comparative Example 1 L-Boc-Ala-CP

(n=20) Comparative Example 2 L-Boc-Phe-CP

(n=20)

Experimental example

1) Gel permeation chromatography (GPC)

The number average molecular weight (Mn) and the weight average molecular weight (Mw) were respectively measured using gel permeation chromatography (GPC), and the molecular weight distribution (PDI) was calculated by dividing the weight average molecular weight by the number average molecular weight.

The synthesized polymer was analyzed by GPC with Shodex GPC column (GF-510HQ, KF-803 and KD-803, Japan). The polymers prepared in Examples 1 to 4 were diluted in a 90:10 (v:v) mixture of chloroform and methanol as an eluent and analyzed through a GF-510HQ column ^{at 20° C. at a flow rate of 0.3 mL min −1 .} The polymers prepared in Examples 5 to 7 and Comparative Examples 1 and 2 were diluted in THF as an eluent and analyzed through a KF-803 THF column ^{at 50° C. at a flow rate of 0.7 mL min −1 .} For aggregation analysis, the prepared polymer was analyzed through a KD-803 DMF column ^{at 50° C. at a flow rate of 0.7 mL min −1 using a DMF eluent.} Polystyrene (PS) standards (Agilent Technologies, USA) were used to calculate the molecular weight of the polymer. Each sample was detected with a refractive detector (YL9170; Young Lin Instrument Co., Korea). The degree of polymerization was calculated based on the measured molecular weight of the polymer.

2) thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC)

TGA and DSC were performed on the polymer prepared in Example 2 with an N ₂ gas stream (TA Instruments, Model TGA Q50, USA). For TGA, the polymer was heated from 30° C. to 600° C. at a heating rate of ^{10° C. min −1 .} For DSC, the polymer was heated from 25° C. to 135° C. at a heating rate of ^{10° C. min −1 .}

3) Circular dichroism (CD) analysis

CD spectra were recorded using a J-815 spectrometer (JASCO, Japan) using a quartz cell with a 1 mm path length at 30 °C. Each polymer sample was prepared at ^{0.5 mg mL −1 .}

4) atomic force microscopy (AFM)

AFM experiments were performed using Multimode 8 and Nanoscope V controller (Bruker, USA). A thin film of polymer solution was prepared by spin coating a drop of polymer solution (0.001 wt %, spinning speed = 3000 rpm = 30 rpm) on a highly oriented pyrolytic graphite (HOPG) substrate. Samples were annealed with absorption vapor (chloroform or DMF) for 24 h. All images were acquired in soft tapping mode using a non-contact mode tip of Nanoworld (NCHR POINTPROBE® and Super Sharp Silicon (SSS), Force constant: 42 N m ^{−1 ).}

5) Langmuir-Schaefer deposition (Langmuir-Schaefer, LS deposition)

The LS method was performed to prepare the deposition of well-ordered polymers on the HOPG surface. A solution of the polymer of Example 2 (250 μL) in chloroform at a concentration of 0.1 mg mL ^{−1 was sprayed onto the water surface at room temperature.} After evaporation of the chloroform for 15 minutes, the polymer surface was gradually compressed with a barrier at a rate of ^{1 mm min −1 .} When the compression was ^{higher than 40 mN m −1} , the surface pressure π suddenly dropped, and the inclination was changed by the collision between the polymer layers. At a target surface pressure of 39.5 mN m ⁻¹ , the polymer monolith was transferred from the air/water interface to the surface (1 cm ² ) of the HOPG.

Mn (g/mol) Mw (g/mol) PDI (Mw/Mn) Degree of polymerization (DP) Target DP Example 1 3.52×10 ³ 4.18×10 ³ 1.18 9.13 10 Example 2 7.33×10 ³ 8.80×10 ³ 1.20 18.99 20 Example 3 11.5×10 ³ 14.1×10 ³ 1.22 29.81 30 Example 4 7.85×10 ³ 10.1×10 ³ 1.28 20.33 20 Example 5 7.84×10 ³ 13.5×10 ³ 1.72 16.96 20 Example 6 6.84×10 ³ 12.9×10 ³ 1.88 14.80 20 Comparative Example 1 4.69×10 ³ 8.16×10 ³ 1.74 17.75 20 Comparative Example 2 6.21×10 ³ 9.72×10 ³ 1.56 18.26 20

Referring to Example 1, first, an Fmoc-L-alanine-based monomer was prepared, and then a polymer was prepared using the prepared monomer using a third-generation Grubbs catalyst. The ¹ H NMR spectrum of L-Fmoc-Ala-CP monomer in Figure 1, and showing the L-Fmoc-Ala-CP ¹ H NMR spectrum of the polymer is shown in Fig. 1 and 2, in the spectrum of the polymer, it can be confirmed that the alkyne peak at 2.2 ppm of the monomer disappears and the vinyl proton peak appears at around 6.5 ppm.

The polymerization of the monomer was completed within 30 minutes, and the molecular weight distribution of L-Fmoc-Ala-CP was analyzed by gel permeation chromatography (GPC) as an eluent of a methanol/chloroform mixture. 3 shows a graph of polymerization of L-Fmoc-Ala-CP with time, and a graph of conversion kinetics of L-Fmoc-Ala-CP in FIG. 4 is shown. As an internal standard peak, an alanine residue methyl peak (3H , 1.0-1.84 ppm, DMF-d7) was selected. Polymer conversion (%) was calculated by the alkyne peak (3.17-3.27 ppm, DMF-d7) to the alanine residue peak integration value. Examples 2 and 3 are examples of varying degrees of polymerization (DP) by changing the monomer to catalyst ratio in Example 1, and Table 2 shows the results of gel permeation chromatography (GPC).

Meanwhile, referring to FIG. 2 , as a result of geometrical arrangement analysis of the polymer main chain, the vinyl proton of the olefin between the two 5-membered rings exhibited a characteristic chemical shift of the trans-olefin at 6.5 ppm.

_{Fig. 5 shows the selective NOE spectrum in CDCl 3} for the polymer of Example 2, the upper spectrum shows a correlation with 1.42 ppm (methyl residue of alanine), the lower spectrum shows 6.53 ppm (poly(acetylene) backbone) protons). Referring to FIG. 5 , in particular, the selective nuclear overhouser effect (NOE) from vinyl protons did not show a significant correlation with other protons between 5 and 6 ppm. This indicates that the geometry of the double bond between the rings is almost exclusively arranged, thus demonstrating that the polymer of Example 2 has an alternately repeating cis-trans configuration.

The thermal stability of the polymer of Example 2 was confirmed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). As shown in FIG. 6 , the thermal decomposition temperature (Td) for the polymer of Example 2 was measured at 150° C., 215° C. and 288° C., which correspond to the decomposition of carbamate, poly(acetylene) and amide, respectively. In addition, the glass transition temperature (Tg) of the polymer was 89.6°C by DSC analysis.

8 shows the circular dichroism of the polymers of Examples 1 to 3 (L-Fmoc-Ala), the polymer of Example 4 (D-Fmoc-Ala), and the polymer of Comparative Example 1 (L-Boc-Ala). Circular dichroism (CD) spectra were plotted. The polymers of Examples 1 to 3 exhibited a strong positive cotton effect in the visible region of 400 to 600 nm regardless of the difference in the degree of polymerization, indicating that the acetylene skeleton formed a helix. The positive nasal effect in the above range is predicted to mean the right helix (P-helix) of the poly(acetylene) backbone, and a short polymer as in Example 1 containing 50% trans double bonds [degree of polymerization (DP) = 10 )] also shows that helical structures can be effectively formed. The polymer of Example 4 (D-Fmoc-Ala) polymerized using an enantiomer derived from Fmoc-D-alanine is a normal reflection of the CD spectrum of the polymers of Examples 1 to 3 (L-Fmoc-Ala). showed a negative plane effect, which represents the left helix (M-helix) of the skeleton. Through this, it was confirmed that the direction of rotation of the helix is determined by the chirality of amino acids present in the side chain.

Further, the polymer of Comparative Example 1 (L-Boc-Ala) exhibited wavelength absorption almost similar to Examples 1 to 4 in the wavelength range of 400 to 700 nm, but its optical activity was negligibly small. From this, it was found that the interaction between the N-protected Fmoc group, not the aromatic residue in the amino acid, is important for generating the helical structure of the metathesis cyclopolymerized polymer.

Meanwhile, FIG. 9 shows a CD spectrum in chloroform and a CD spectrum in DMF for the polymer of Example 2. Referring to FIG. 9 , the helical direction of the polymer (L-Fmoc-Ala) of Example 1 was changed depending on the solvent, and the nasal effect, which was positive in chloroform, was reversed to be negative in DMF. In addition, the polymer of Example 4 (D-Fmoc-Ala) was also able to observe the solvent-induced spiral reversal in solution. 10 shows the results of measuring the CD spectrum for the polymer of Example 4 by changing the solvent composition of chloroform/DMF. Referring to FIG. 10, the helical structure is reversed while the composition of DMF mixed in chloroform exceeds 40%. started to become

From the UV-Vis spectrum of the polymer, clues could be found for a solvent-dependent change in the backbone structure, and a clear color-chromic red shift was observed when the solvent was changed from chloroform to DMF. As the solution color changed from red to purple, the maximum absorption wavelength at 516 nm in chloroform shifted to 584 nm in DMF. The bathochromic red shift generally results from an increase in the conjugate length in conjugated π-systems such as poly(acetylene). Through the analysis of the results, it could be estimated that the backbones of the polymers of Examples 1 to 4 were further compressed in chloroform, whereas elongated in DMF.

The helical structure was gradually formed and reversed in chloroform and DMF. 11 shows the CD spectrum of the polymer of Example 2 in chloroform and in DMF, a) after 2 hours of dissolving in a solvent, b) after 1 day of dissolving in a solvent, c) after dissolving in a solvent This is the spectrum after 3 days. Referring to FIG. 11 , the optical activity of the polymers of Examples 1 to 3 increased after dissolving in chloroform, but was saturated within 24 hours. On the other hand, the optical activity in DMF increased much more slowly and it required more than 3 days for saturation. The inventors of the present invention hypothesized that this is due to the gradual formation of the helical structure and the rather slow re-orientation of the polymer backbone induced by the reverse transfer solvent-polymer interaction. In particular, the polymer of Example 4 (L-Fmoc-Ala-CP) existed as a separate molecule in chloroform but tended to form aggregates in DMF. 12 a) is a GPC trace result of a polymer (L-Fmoc-Ala-CP) adjusted by [M]/[I] ratio in a solvent of 25° C. methanol:chloroform (90/10/v/v), FIG. 12 b) is a diagram showing the self-aggregation properties of the polymer of Example 4 (L-Fmoc-Ala-CP) in a DMF solution. As shown in Fig. 12, L-Fmoc-Ala-CP existed as a separate molecule in chloroform but tended to form aggregates in DMF. In the GPC traces for the polymer of Example 4, a significant amount of the polymer of Example 4 showed a broad shoulder peak immediately after DMF mixing, and after 20 hours of mixing, the exclusion limit was near the 70 kDa. were observed as large aggregates of Also, after 7 days most of the polymer was present as larger aggregates exceeding the exclusion limit in DMF. The left-helix (M-helix) conformation of the polymer of Example 4 in DMF was predicted to form aggregates due to higher affinity between polymer molecules than the right-helix (P-helix) conformation in chloroform.

The inventors of the present invention inferred the reason for the spiral direction reversal according to the solvent of the polymers of Examples 1 to 4 as follows. Leiras, S.; Freire, F.; Seco, JM; Quiρoα, E.; Riguera, R., Controlled modulation of the helical sense and the elongation of poly(phenylacetylene)s by polar and donor effects. Chemical Science 2013, 4 (7), 2735-2743] discloses that poly(phenylacetylene) having a chiral amide side chain changes the helical direction depending on the solvent. This document explains that the conversion of the helical direction results from structural changes between the cis- and trans-amides in the side chains, depending on the solvent donating ability for hydrogen bonding with the amide hydrogens. In contrast, the polymers of Examples 1 to 4 do not have amide hydrogens with tertiary amides, but substituents derived from amino acids as their respective side chains have NH protons, potential hydrogen bond donors, and carbamate bonds that are analogs of amide bonds. , as shown in Figure 8, the anti-rotamer of carbamate, in which the NH bond is generally opposite to the C=O bond (ω1 = 180°), is that the NH bond is the C=O bond (ω1 = 180°). 0°) is preferred because it has a lower free enthalpy of 1-1.5 kcal·mol ^-1 than that of the syn- rotamer of carbamate on the same side.

However, because the energy difference between the anti-syn rotamers of carbamate is smaller compared to the difference between cis-trans amides (1 to 4 kcal mol ^-1 ), syn-carbamate is often used in solvent molecules, such as DMF as a donor solvent. By strongly interacting with NH protons, the equilibrium can be induced with syn-carbamate, whereas chloroform, a solvent rather than a donor, favors anti-carbamate.

The inventors of the present invention estimated the form of carbamate in both solvents from the chemical shift of the N-H proton in the L-Fmoc-Ala-monomer used in Examples 1 to 4. Fig. 13 shows the NMR spectrum of the L-Fmoc-Ala-monomer. The NMR spectrum of the L-Fmoc-Ala-monomer in a) is chloroform, b) is THF, and c) is a DMF solvent. The N-H proton of carbamate is indicated by a black line, and anti- and syn-rotamers were confirmed by comparison with the chemical shift of the N-H proton of 2-oxazolidinone.

In addition, as shown in FIG. 15, the difference in chemical shift (NH δ shift) through low-temperature (15° C.) NMR spectrum in a) chloroform, b) THF, and c) DMF of L-Fmoc-Ala-monomer Confirmed.

Referring to the NMR data of the L-Fmoc-Ala-monomer in chloroform in FIG. 14 a), the NH proton peak in chloroform was observed at 5.5 ppm, which is a characteristic chemical shift of the anti-rotatory isomer, as shown in FIG. 14 b). The syn-rotomer was detected via hydrogen bonding by addition of acetic acid as shown. On the other hand, referring to FIG. 13 c), in DMF, the peak is significantly down-shifted to 7.8 ppm corresponding to the syn-rotomer.

As such, it was clearly observed that the L-Fmoc-Ala-monomer had the same preference for anti-carbamate in chloroform and syn-carbamate in DMF solution. Therefore, we predicted that syn-anti-carbamate rotation could induce rearrangement of the Fmoc pendant group of the side chain, which is an essential element for helix formation to reverse the helix structure of the main chain.

To this end, the polymers of Example 5 (L-Fmoc-Phe-CP) and Example 6 (D-Fmoc-Phe-CP) and Comparative Example 2 (L-Boc-Phe-CP) were prepared, and Example 5 and 6 each showed strong optical activity similar to the polymers of Examples 1 to 4 in chloroform, but the polymer of Comparative Example 2 showed negligible optical activity similar to Comparative Example 1. The result can be confirmed in the CD spectrum in chloroform and DMF of FIG. 16 .

On the other hand, the optical activity of the polymers of Examples 5 and 6 and Comparative Example 2 was decreased in DMF, indicating that the interaction of Fmoc groups was interrupted by phenylalanine residues due to carbamate rotation. When the carbamate rotation occurs in the anti-rotary to syn-rotamer direction, the phenyl residue of phenylalanine interferes with the interaction of the Fmoc group because the distance between the Fmoc group and the residue is geometrically closer. The polymer of Comparative Example 2 (L-Boc-Phe-CP) exhibited negligible optical activity by reducing the aromatic-aromatic interaction between Fmoc groups. That is, it can be seen that the phenyl moiety cannot produce a structure with aromatic-aromatic interactions, but only affects the interactions between Fmoc groups.

Atomic force microscopy (AFM) experiments were performed to study the secondary structure of the polymers of Examples 1 to 3, that is, L-Fmoc-Ala CP. 2D crystals and single strands of L-Fmoc-Ala CP were prepared by Langmuir Schaefer deposition or spin coating on HOPG surfaces. 17 shows the AFM scan, (a) and (b) are height and phase images of 2D crystals of the polymer of Example 2 in chloroform, respectively, (c) are single-stranded height images of spin coating, , (d) and (e) are annealing and phase images of 2D crystal height images through DMF solution, respectively, and f) are double-stranded phase images of spin coating.

17(a) and (b) show the morphology of the packed L-Fmoc-Ala CP chain, the alignment of the external Fmoc pendant group is left-helix (M-helix), and the chain height of each polymer is 1.5 nm it was In particular, as shown in Fig. 17 (c), the single strand exhibits a left-handed pendant disposition (M -helix) with an oblique strip angle of -57.8 ° and a spiral pitch of 5 nm. it was On the other hand, it was confirmed that the packing structure of the polymer was changed by DMF solvent annealing, as shown in (d) and (e) of FIG. 17 . As the polymer strands stretched, they aggregated with each other. When spin-coated on the surface of Highly Oriented Pyoytic Graphite (HOPG) at a low concentration in DMF, a double helix structure was observed as M-helix. As shown in Fig. 17(f), the polymer has a strip inclination angle of -28.3° and a helical pitch of 10 nm or less. These results are consistent with the compressed form in chloroform and the elongated form in DMF of the poly(acetylene) backbone as described above for the UV-Vis spectrum. In addition, it explains the increase in CD signal over time in DMF and self-aggregation in GPC.

On the other hand, as shown in FIG. 13 b), when the L-Fmoc-Ala CP monomer and the polymer prepared using it were dissolved in THF, a donor solvent, an N-H proton peak was observed at 7.0 ppm. In addition, as shown in Fig. 15b), carbamate syn-rotamers were identified by NMR peak shift through low-temperature NMR studies. Figure 18 shows the CD and UV-Vis spectra of the polymer of Example 2 in THF and DMSO. Although it exhibited excellent solubility in THF and a red shift toward the long wavelength was observed, it was confirmed through the CD spectrum of FIG. 18 that the polymer had negligible optical activity in THF.

However, as shown in FIG. 19 , as the ratio of DMF mixed with THF increased, the optical activity of the polymer gradually increased. Accordingly, it could be confirmed that the structure of the polymer was affected by other solvent properties except for the solvent donating ability.

On the other hand, as can be seen in FIG. 18 , the CD spectrum of the polymer in DMSO showed negligible optical activity even though DMSO had solvent properties similar to those of DMF. Through this, it was confirmed that although the syn- and anti-rotatory isomer structures can be changed from the solvent donating ability, DMF contributes to the special polymer structure by forming a complex with the side chain.

We observed additional CD spectra through various solvents based on the DMF structure to demonstrate the specific interaction of the polymer with DMF. First, by dividing DMF into two parts, the CD spectrum of N,N-dimethylacetamide (DMAc) or N-methyl-2-pyrrolidone (NMP) having a methyl group instead of a formyl group was confirmed. CD spectra of N,N-diethyl formamide (DEF) and N,N,-diisopropyl formamide (DIPF) with increased amide group volume were observed.

CD and UV-Vis spectra of the polymer of Example 2 in DMF, DMAc, NMP, DEF, and DIPF in FIG. 20 a), and in b) STD- A schematic diagram of the interaction between the polymer and the solvent is shown in NMR, c), and the CD spectrum after one day (a) and 3 days (b) by dissolving the polymer of Example 2 in DMF, DEF, and DIPF in FIG. 21 The measurement results are shown.

Referring to the left diagram of FIG. 20 a), DMAc and NMP showed negligible optical activity, like THF and DMSO. On the other hand, referring to the right side view of a) of FIG. 20 and FIG. 21 , due to the difference in solubility of the polymer, the CD signal of DEF showed that the signal increased similarly to that of DMF over time, but it was more bulky. There was no significant difference in DIPF, a bulky solvent, and no structure was formed due to the low solubility of DIPF. The formyl group is predicted to directly interact with the side chain of the polymer and form a complex with a specific structure, and referring to the NMR of FIG. 20 b) shows a relative interaction between the solvent and the polymer. When equal amounts of THF and DMF were added to chloroform, the relative interaction of the solvents could be calculated from the integral value using an internal standard. Equal amounts (316.15 equivalents of polymer repeat units) of THF and DMF were added to chloroform based on the structure change point of the CD spectrum (~20% (v/v)). 22 shows STD-NMR for observing the interaction between THF in chloroform and the polymer of Example 2, with different saturation peaks (1.4 ppm, methyl group of the polymer, left side) and 4.6 ppm (5 membered ring protons of the polymer backbone, STD on and off spectra in right) are shown separately. In addition, STD-NMR for observing the interaction between DMF in chloroform and the polymer of Example 2 is shown in FIG. 23, with different saturation peaks (1.4 ppm, methyl group of the polymer, left side) and 4.6 ppm (5-membered ring of the polymer main chain) STD on and off spectra in protons, right) were shown separately.

0.03% TMS in chloroform d -solvent was chosen as the internal standard and formed integral values, and DMF was calculated to have a strong interaction with the polymer about 3 times higher than THF.

The saturation transfer difference, STD (saturation transfer difference) experiment was performed in the following way to study the solvent-polymer relative interaction.

1.5 mg of L-Fmoc-Ala-CP polymer (3.884×10 ⁻³ mmol of repeat units) were placed in 500 μl of d − solvent. As described above, a d -solvent composition with 1.23 mmol (~20% v/v) of THF _d8 or DMF _{d7 in CDCl 3} was selected as the THF and DMF composition of the d -solvent according to the CD-signal and deuterated. 0.03% trimethyl silane (TMS) in CDCl ₃ was selected and calculated according to Equation 1 below to calculate the non-removable ratio (THF _d8 of THF or DMF _{d7 of DMF d7).}

The normalized signal value of Equation 2 below was determined by the integral value of STD in the spectrum. From the normalized signal values, DMF exhibited a stronger interaction than THF by 2.5 (THF 1.42 ppm (OCH ₂ CH ₂ )) times to 8.6 (THF 3.70 ppm (OCH ₂ CH _{2 )) times.}

[Equation 1]

[Equation 2]

20 c) shows a schematic diagram of the interaction between the polymer and the solvent. Referring to this, not only the change of syn-, anti-rotomers due to the donating ability of the solvent, but also the strong interaction between DMF and the pendant helical structure It can be seen that a new structural stabilization between the pendants leading to inversion occurs.

Claims (16)

having a main chain in which a cis-double bond structure and a trans-double bond structure are alternately repeated,
In the main chain of the acetylenic polymer, the cis-double bond structure and the trans-double bond structure have a ratio of 0.9:1.1 to 1.1:0.9.
The method of claim 1,
The main chain of the acetylene-based polymer is an acetylene-based polymer having a substituent derived from an amino acid.
The method of claim 1,
In the main chain of the acetylenic polymer, the cis-double bond structure and the trans-double bond structure have a ratio of 1:1.
The method of claim 1,
The acetylene-based polymer is an acetylene-based polymer comprising a repeating unit represented by the following Chemical Formula 1:
[Formula 1]

In Formula 1, A is an arylalkyl group having 7 to 20 carbon atoms and a carbonyl group of an amino acid having an ester bond, and n is an integer of 10 to 10,000.
5. The method of claim 4,
Wherein A is an acetylene-based polymer represented by the following Chemical Formula 2 or 3:
[Formula 2]

[Formula 3]

In Formulas 2 and 3, R ₁ is a substituent derived from α-amino acid, and R ₂ is arylalkyl having 7 to 28 carbon atoms.
6. The method of claim 5,
In Formulas 2 and 3, R ₁ is hydrogen, methyl, hydroxymethyl, carboxymethyl, guanidinepropyl, isopropyl, 1-hydroxyethyl, isobutyl, mercaptomethyl, 1H-imidazol-4-yl, Aminobutyl, 1-methylpropyl, 4-hydroxyphenylmethyl, 2-amino-2-oxoethyl, 2-methylthioethyl, (1 H -indol-3-yl)methyl, phenylmethyl, or 3-amino -3-oxopropyl acetylenic polymer.
6. The method of claim 5,
In Chemical Formulas 2 and 3, R ₂ is an acetylene-based polymer represented by the following Chemical Formula 4:
[Formula 4]

In Formula 4, R ₃ is alkylene having 1 to 8 carbon atoms, and R ₄ is aryl having 6 to 20 carbon atoms.
8. The method of claim 7,
In Chemical Formula 4, R ₄ is fluorenyl, an acetylenic polymer.
The method of claim 1,
The acetylene-based polymer is an acetylene-based polymer comprising a repeating unit represented by the following Chemical Formula 1:
[Formula 1]

In Formula 1, A is represented by Formula 2 or 3, n is an integer of 10 to 10,000,
[Formula 2]

[Formula 3]

In Formulas 2 and 3, R ₁ is a substituent derived from α-amino acid, R ₂ is represented by Formula 4 below,
[Formula 4]

In Formula 4, R ₃ is alkylene having 1 to 8 carbon atoms, and R ₄ is aryl having 6 to 20 carbon atoms.
The method of claim 1,
The acetylene-based polymer is an acetylene-based polymer comprising a repeating unit represented by the following Chemical Formula 1:
[Formula 1]

In Formula 1, A is any one of Formulas 5 to 8, and n is an integer of 10 to 10,000.
[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

The method of claim 1,
The acetylene-based polymer is an acetylene-based polymer having a helical secondary structure.
12. The method of claim 11,
The acetylene-based polymer is an acetylenic polymer in which the rotational direction of the helical secondary structure in a solvent is reversed (helical inversion).
The method of claim 1,
The acetylene-based polymer is an acetylene-based polymer exhibiting optical activity in a solvent.
A method for producing the acetylene-based polymer of claim 1, comprising the process of cyclization polymerization of a compound of formula (9) to form a compound of formula (1):
[Formula 9]

[Formula 1]

In Formula 1, A is an arylalkyl group having 7 to 20 carbon atoms and a carbonyl group of an amino acid having an ester bond, and n is an integer of 10 to 10,000.
15. The method of claim 14,
In Chemical Formulas 1 and 9, A is a method for producing an acetylene-based polymer represented by the following Chemical Formula 2 or 3:
[Formula 2]

[Formula 3]

In Formulas 2 and 3, R ₁ is a substituent derived from α-amino acid, and R ₂ is arylalkyl having 7 to 28 carbon atoms.
16. The method of claim 15,
A method for preparing an acetylene-based polymer, further comprising preparing a compound of Formula 9 by amide coupling reaction between a compound of Formula 10 and a compound of Formula 2 or 3:
[Formula 10]

[Formula 2]

[Formula 3]

[Formula 9]

A is represented by Formula 2 or 3,
R ₁ is a substituent derived from α-amino acid, and R ₂ is arylalkyl having 7 to 28 carbon atoms.

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