WO2017146456A1 - Crystalline polymer and preparation method therefor - Google Patents

Abstract

A crystalline polymer and a preparation method therefor are provided. The crystalline polymer preparation method comprises a step of forming a two-monomers-connected precursor comprising a pair of monomers and one connector connecting the monomers to each other. Afterward, a crystalline polymer is obtained by polymerizing the two-monomers-connected precursor. The crystalline polymer comprises a plurality of polymer backbones formed by coupling monomers provided within the different two-monomers-connected precursors, and the connector connects a pair of monomers provided in polymer backbones adjacent to each other.

Description

Crystalline polymer and preparation method thereof

The present invention relates to a polymer, and more particularly to a crystalline polymer.

Recently, polymers require more than just flexibility. In one example, the polymer requires to deliver or store particles such as electrons, ions, or gases. To satisfy this, numerous attempts have been made to introduce functional groups on the main or side chains of polymers. However, this method has an unsatisfactory result of poor particle transport as large amorphous regions are formed due to the inherent morphological limitations of the polymer, that is, random entanglement of one-dimensional chains.

Accordingly, researches on crystalline polymers having a well-organized structure such as covalent bond organic frameworks have recently been conducted. However, in the case of such a covalent organic skeleton structure, a large amount of pores are distributed in the three-dimensional structure formed, and is being developed to adsorb gas through such pores. It doesn't seem to be.

Accordingly, an object of the present invention is to provide an organic crystalline polymer having conductivity.

Technical problems of the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the above technical problem, two aspects of the present invention provide a crystalline polymer and a method of manufacturing the same.

The method for producing a crystalline polymer comprises forming a two-monomer-linked precursor having a pair of monomers and one linker connecting these monomers to each other. Thereafter, the 2-monomer-linked precursor is polymerized to obtain a crystalline polymer.

The crystalline polymer includes a plurality of polymer backbones formed by combining monomers provided in the different 2-monomer-linked precursors, and the linker connects a pair of monomers provided in adjacent polymer backbones. do. The polymer backbone may be, for example, polypyrrole, polythiophene, polyaniline, or poly (3,4-ethylenedioxythiophene) as a conductive polymer. The linker may be an oxidative dopant for adding holes to the polymer backbone or a reducing dopant for adding electrons to the polymer backbone.

The crystalline polymer may have a repeating pattern of unit cells having lattice constants having lattice points in a molecular unit.

The one linker and the pair of monomers may be bonded by ionic bonds, hydrogen bonds, coordination bonds, or covalent bonds. The polymerization may be performed using oxidative polymerization, C-C coupling, condensation polymerization, photopolymerization, or electrochemical polymerization.

As described above, according to the present invention, monomers provided in different 2-monomer-linked precursors are sequentially connected to form a polymer backbone in a state in which the monomers form 2-monomer-linked precursors fixed with a linker during polymerization. As it is formed, the backbone of the polymer can be greatly reduced and thus partially not entangled at all and can be arranged in a regular arrangement, that is, regularly. In other words, the spacing between the backbones can be constant due to the linkage. Accordingly, the polymer crystallinity can be greatly improved.

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 is a schematic view showing a method for producing a crystalline polymer according to an embodiment of the present invention.

2 is a schematic view showing a method of manufacturing a crystalline polymer thin film according to an embodiment of the present invention.

3A to 3D show intermediates obtained during the processes of Comparative Polymer Synthesis Example 1 and Polymer Synthesis Examples 1 to 3, respectively, Py: MSA, TMCP (Py: BDSA: Py), TMCP (Py: BDSA: Py), And FT-IR spectra of TMCP (Py: BPDSA: Py).

4 shows optical pictures of a poly (Py: EDSA: Py) film formed on various substrates obtained through Polymer Synthesis Example 1. FIG.

5 shows ultraviolet-visible light absorption spectra of polymer films obtained in Comparative Polymer Synthesis Example 1 and Polymer Synthesis Examples 1 to 3;

6 shows crystal properties of a poly (Py: EDSA: Py) film according to Polymer Synthesis Example 1, FIG. 7 shows crystal properties of a poly (Py: BPDSA: Py) film according to Polymer Synthesis Example 3, and FIG. 8. Shows crystal properties of the poly (Py: BDSA: Py) film according to the polymer synthesis example 2, Figure 9 shows the crystal properties of the poly (Py: MSA) film according to the polymer synthesis Comparative Example 1.

10 is a poly (Py: EDSA: Py) film, a poly (Py: BPDSA: Py) film, a poly (Py: BDSA: Py) film, and polymers according to Polymer Synthesis Examples 1 to 3 and Polymer Synthesis Comparative Example 1 The conductivity and sheet resistance of the poly (Py: MSA) film are shown.

FIG. 11 is a schematic diagram illustrating the chemical arrangement of poly (Py: EDSA: Py) and poly (Py: BPDSA: Py) according to Polymer Synthesis Examples 1 and 3. FIG.

12 shows the properties of the polymer film according to the polymer synthesis examples 4 and 5, and Comparative Example 1 of the polymer synthesis.

13 shows crystal properties of a polymer film according to Polymer Synthesis Example 4. FIG.

14 is an X-ray diffraction graph of a poly (EDOT: BPDSA: EDOT) film according to Polymer Synthesis Example 6. FIG.

15 is an HRTEM image of a poly (EDOT: BPDSA: EDOT) film according to Polymer Synthesis Example 6. FIG.

16 shows crystal properties of a polymer film according to Polymer Synthesis Example 7.

17 shows crystal properties of a polymer film according to Polymer Synthesis Example 8. FIG.

18 shows crystal properties of a polymer film according to Polymer Synthesis Example 9. FIG.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings in order to describe the present invention in more detail. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. In the figures, where a layer is said to be "on" another layer or substrate, it may be formed directly on the other layer or substrate, or a third layer may be interposed therebetween.

In the present specification, when " carbon number X to carbon number Y ", the carbon number corresponding to all integers between X and Y should be interpreted as being described together.

As used herein, "alkyl" or "alkylene" may mean an aliphatic hydrocarbon unless it is clearly stated otherwise. "Alkyl" may be a saturated alkyl group having no double bond or triple bond, or may be an unsaturated alkyl group having double bond or triple bond. Saturated alkyl groups can be branched, linear, or cyclic alkyl groups. Unless defined otherwise, alkyl groups can be C1 to C4 alkyl groups, and C1 to C4 alkyl groups can be methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, or t-butyl .

As used herein, "aryl" or "arylene" may be a monocyclic aromatic group or a polycyclic aromatic group unless clearly stated otherwise.

As used herein, "heteroaryl" or "heteroarylene" includes at least one of nitrogen, phosphorus, oxygen, sulfur, and selenium as ring members in the ring and carbon as another ring member, unless expressly stated otherwise. It may be a monocyclic aromatic group or a polycyclic aromatic group containing.

As used herein, "cycloalkane" or "cycloalkylene" may be monocyclic saturated hydrocarbon or polycyclic saturated hydrocarbon unless it is clearly stated otherwise.

Crystalline polymer

1 is a schematic view showing a method for producing a crystalline polymer according to an embodiment of the present invention.

Referring to FIG. 1, first, a two-monomer-connected precursor (TMCP) obtained by reacting two monomers with a connector may be obtained. Two monomers in TMCP can be linked via a linker.

Although the two monomers are shown to be the same as each other, in some cases, they may be different kinds. The monomer may be a monomer that may exhibit conductivity when TMCP is polymerized as described below. Specifically, the monomer may have a multiple bond or a non-covalent electron pair in the molecule, and may have a structure in which electrons are delocalized. Furthermore, the linker may also have a structure in which electrons are delocalized.

On the other hand, each monomer may have one reaction site (# 1) for the connection with the linker, and may also have two polymerization sites (*) for the polymerization reaction with the monomers. In addition, each linker may have a pair of reaction sites (# 2) capable of binding to the reaction site (# 1) of the monomer at both ends thereof. The one linker and the pair of monomers may be linked by various bonding methods, for example, ionic bonds, hydrogen bonds, coordination bonds, and covalent bonds. Specifically, the reaction site (# 1) of the monomer and the reaction site (# 2) of the linker may be modified to be suitable for ionic bonds, hydrogen bonds, coordination bonds, or covalent bonds.

Thereafter, TMCP may be polymerized to obtain a crystalline polymer. Specifically, monomers provided in TMCPs adjacent to each other may be polymerized. For example, one side polymerization site (*) of the first monomer (M _A1 ) provided in the first TMCP in the polymerization process is one side polymerization of one second monomer (M _B1 ) provided in the adjacent second TMCP. The other polymerization site (*) of the first monomer (M _A1 ) provided in the first TMCP connected to the site (*) is one side of the polymerization site (*) of the third monomer (M _C1 ) provided in the adjacent third TMCP. ) May form a first polymer backbone (PB1) in which the monomers are bonded in turn.

As a result, the crystalline polymer has a plurality of backbones in which the monomers are bonded in a row, and the first monomer M _A1 provided in the first backbone PB1 is adjacent to one side of the first backbone PB1. It is connected to the fifth monomer (M _A2 ) provided in the second backbone (PB3) and the first connecting member (CA), and is provided in the first backbone (PB1) and is adjacent to the first monomer (M _A1 ). The second monomer M _B1 may be connected to the sixth monomer M _B2 provided in the third backbone PB2 adjacent to the other side of the first backbone PB1 through the second connector CB.

As described above, as the monomers are formed in the TMCP in which the monomers are fixed as a linker in the polymerization process, the monomers included in the different TMCPs are sequentially connected to form a polymer backbone, thereby causing the entanglement of the backbone of the polymer to be greatly reduced. Can be arranged in a regular array, that is, without any entanglement. In other words, the spacing between the backbones can be constant due to the linkage. Accordingly, the polymer crystallinity can be greatly improved. In addition, FIG. 1 illustrates a unit layer of a crystalline polymer, and a plurality of such unit layers may be stacked in the crystalline polymer layer.

Such crystalline polymers may exhibit crystal structures commonly found in metal or metal oxide crystals. Specifically, the crystalline polymer may have a repeating pattern of unit cells having a lattice constant defined by a spacing d between adjacent lattice planes and angles between the faces. As an example, the crystal structure of the crystalline polymer may be hexagonal close packed lattice (HCP), face centered cubic (FCC), or orthorhombic (orthorhombic). In this case, the vertex of each unit cell, that is, the lattice point, may be a molecular unit, not an atomic unit.

The backbone of the crystalline polymer may be, for example, polypyrrole, polythiophene, polyaniline, poly (3,4-ethylenedioxythiophene), or polyphenylene. However, it is not limited to this. The crystalline polymer may exhibit metallic conductivity or semiconducting conductivity. Meanwhile, the linker may be an oxidative dopant for adding holes to the polymer backbone or a reducing dopant for adding electrons to the polymer backbone. In this case, the conductivity of the crystalline polymer may be improved.

2-monomer-linked precursor (TMCP)

As described above, the TMCP may have a pair of monomers and one linker connecting these monomers to each other.

Each of the pair of monomers included in the TMCP may be any one of monomers represented by the following Chemical Formulas 1 or 2.

[Formula 1]

In Formula 1, Y may be NR ₁ , S, O, Se, or (CH) ₂ . In this case, R ₁ may be hydrogen or an alkyl group of C1 to C3. Ring G may be a pentagonal heteroaromatic ring when Y is NR ₁ , S, O, or Se, and ring G may be a hexagonal aromatic ring, benzene ring, when Y is (CH) ₂ .

The site (*) to which A ₁ and A ₂ are bonded may be a polymerization site for polymer reaction. A ₁ and A ₂ may be functional groups for coupling or polymerization reactions. As an example any one of A ₁ and A ₂ may be hydrogen, —B (OR _A ) ₂ , —Sn (R _A ) ₃ , or X _A , and the other may be hydrogen, or X _A. At this time, R _A is H or an alkyl group of C1 to C4, X _A may be Cl, Br, I, or pseudohalogen (pseudohalogen) irrespective of each other. The pseudohalide may be, for example, -CN, -CNO, -NCO, or -OTf (trifluoromethanesulfonate). In an embodiment, A ₁ and A ₂ are both hydrogen, A ₁ and A ₂ are both X _A, or one of A ₁ and A ₂ is -B (OR _A ) ₂ or -Sn (R _A ) ₃ and the other One may be X _A.

B ₁ and B ₂ are independently of each other hydrogen, a hydroxyl group, a C1 to C4 alkyl group, a C1 to C4 alkyl alcohol group, a C1 to C4 alkoxy group, a C1 to C4 (alkyl) carboxylic acid, a C1 to C4 A (alkyl) carboxylate, an amine group, or a C1 to C4 alkylamine group, or B ₁ and B ₂ are joined together to form a carboxylic acid anhydride, an ethylenedioxy group, or 5 to _{1 with} B ₁ and B ₂ linked carbon atoms; A 6 membered aromatic ring can be formed. B ₁ and B ₂ are combined B ₁ and B ₂ is an aromatic ring of five or six members formed together with the attached carbon atom may be a hetero aromatic ring. Wherein heteroatoms may be from 1 to 3, and may be nitrogen, phosphorus, oxygen, sulfur, or selenium irrespective of each other. As one example, the heteroaromatic ring may be imidazole, pyrazole, triazole, thiazole, isothiazole, or thiadiazole. .

In Formula 1, at least one of Y or B ₂ of B ₁ may be a reaction site capable of binding to the linker.

The monomer represented by Formula 1 may be represented by the following Formula 1-1 or 1-2 depending on the type of Y.

[Formula 1-1]

In Formula 1-1, Y ₁ may be NR ₁ , S, O, or Se. In this case, R ₁ may be hydrogen or an alkyl group of C1 to C3, and ring G ₁ may be a pentagonal heteroaromatic ring. A ₁ , A ₂ , *, B ₁ and B ₂ may be as defined in Formula 1.

In particular, B ₁ and B ₂ are independently of each other hydrogen, hydroxyl group, C1 to C4 alkyl group, C1 to C4 alkyl alcohol group, C1 to C4 alkoxy group, C1 to C4 (alkyl) carboxylic acid, C1 to It may be a (alkyl) carboxylate of C4, an amine group, or an alkylamine group of C1 to C4, or B ₁ and B ₂ may be combined with each other to be a carboxylic anhydride or ethylenedioxy group.

[Formula 1-2]

In Formula 1-2, A ₁ , A ₂ , *, B ₁ and B ₂ may be as defined in Formula 1.

Specifically, at least one of B ₁ and B ₂ may be a functional group that can be bonded to the linker, or B ₁ and B ₂ may be combined to form a functional group that may be bound to the linker. When one of B ₁ and B ₂ is a functional group capable of bonding to the linking group, it is a hydroxyl group, a C1 to C4 alkylalcohol group, C1 to C4 (alkyl) carboxylic acid, C1 to C4 (alkyl) carboxyl It may be a rate, an amine group, or an alkylamine group of C1 to C4, and the other of B ₁ and B ₂ may be hydrogen or an alkyl group of C1 to C4. When B ₁ and B ₂ are combined to form a functional group capable of bonding to the linker, B ₁ and B ₂ are joined together to form a carboxylic anhydride, or 5 to 6 together with the carbon atoms to which B ₁ and B ₂ are linked Heteroaromatic rings of members can be formed. In the heteroaromatic ring, heteroatoms may be 1 to 3, and may be nitrogen, phosphorus, oxygen, sulfur, or selenium regardless of each other. As one example, the heteroaromatic ring may be imidazole, pyrazole, triazole, thiazole, isothiazole, or thiadiazole. .

The monomer represented by Chemical Formula 1 may be represented by the following Chemical Formulas 1A, 1B, 1C, 1D, 1E, 1F, and 1G.

[Formula 1A]

In Formula 1A, Y ₁ , A _1, and A ₂ may be as defined in Formula 1-1, and B ₃ and B ₄ may be hydrogen or an alkyl group of C1 to C4 regardless of each other.

[Formula 1B]

In Formula 1B, Y, A ₁ , A ₂ , and B ₁ may be as defined in Formula 1. R _B may be a bond, an alkyl group of C1 to C4, or a (alkyl) carbonyl group of C1 to C4. B ₁ may specifically be hydrogen or an alkyl group of C1 to C4.

[Formula 1C]

In Formula 1C, Y, A ₁ , A ₂ , and B ₁ may be as defined in Formula 1. L _B may be a carboxylic acid, a carboxylate, or an amine group, and R _B may be a bond or an alkyl group of C1 to C4. B ₁ may specifically be hydrogen or an alkyl group of C1 to C4.

[Formula 1D]

In Formula 1D, Y, A ₁ and A ₂ may be as defined in Formula 1.

[Formula 1E]

In Formula 1E, Y, A ₁ and A ₂ may be as defined in Formula 1.

[Formula 1F]

In Formula 1F, A ₁ and A ₂ may be as defined in Formula 1, and Ring B is a 5-6 membered heteroaromatic ring, and may have n hetero atoms Y _a . n may be an integer from 1 to 3. Y _a may be N, NH, O, S, P, PH, or Se regardless of each other.

[Formula 1G]

Formula 1G represents when Ring B of Formula 1F is a 5-membered heteroaromatic ring, Y _a1 , Y _a2 , and Y _a3 At least one of which is a heteroatom, and the other may be carbon. The heteroatoms may be selected from the group consisting of N, NH, O, S, P, PH, and Se, and when two or more are heteroatoms, they may be selected independently of each other. As an example, at least Y _a1 Or Y _a2 may be heteroatom more specifically N or NH. In embodiments, the heteroaromatic ring may be imidazole, pyrazole, triazole, thiazole, isothiazole, or thiadiazole. .

Specific examples of Formula 1G may be as follows.

 [Formula 2]

In Formula 2, Y may be NH ₂ or SH. The site marked * may be a polymerization site for polymer reaction.

Meanwhile, the linker may be represented by any one of the following Formulas 5A to 5F.

[Formula 5A]

In Formula 5A, R ₁ ^- and R ₂ ^- may be an anionic functional group. Specifically, R ₁ ^- and R ₂ ^- may be COO ⁻ , SO ₃ ⁻ , or PO (OH) O ⁻ , regardless of each other. As X ₁ ⁺ and X ₂ ⁺ is a counter cations, it may be independently selected hydrogen ion or alkali metal ion. The alkali metal ion may be Na ⁺ or K ⁺ . R is C2 to C4 alkanediyl, C2 to C4 alkenediyl, C2 to C4 alkyndiyl, C6 to C20 arylenediyl, C2 to C20 heteroarylenediyl, C6 to C20 Arylene alkenediyl or cycloalkanediyl of C6 to C20. As an example, R is 1, 2-ethanediyl, 1, 3- propanediyl, 1,4-butanediyl, 1,4-butenediyl, para-biphenyldiyl, para-phenyldiyl , 2,6-naphthalenediyl, 2,6-anthracenediyl, 2,6-anthraquinonediyl, 2,2'-bithiophen-5,5'-diyl, or para-phenyleneethyleneyl Can be.

[Formula 5B]

In Formula 5B, X ₁ and X ₂ are halogen and may be Br, Cl, or I regardless of each other. In addition, R may be as defined in Formula 5A.

The linkers shown in Formulas 5A and 5B can act as oxidative dopants that add holes to the polymer backbone, as can be seen in Schemes 1, 2, and 10-13 and Formulas 30, 31, and 39-42, described below. .

[Formula 5C]

In Formula 5C, R ₁ , R ₂ , R ₃ , and R ₄ may be hydrogen or an alkyl group of C1 to C2, regardless of each other. In addition, R may be as defined in Formula 5A.

 [Formula 5D]

In Formula 5D, the rings D ₁ and D ₂ may be a 5-membered or 6-membered unsaturated heterocyclic compound having at least one N, specifically N of 1 to 3 as a hetero member. In addition, R may be as defined in Formula 5A. Meanwhile, n may be an integer of 1 or 0.

 [Formula 5E]

In Formula 5E, M is Zn, Cu, Pd, Ru, or a metal ion such as Pt, L is H ₂ O, NH _3, or an ethylene-a-diamine, X _a is a counter ion OH ^-, NO ₃ ^- , CO ₃ ^- can be a ^-, CN ^-, or Cl. However, it is not limited to this. On the other hand, n may be determined so that the compound is neutral in consideration of the oxidation number of the metal ion and the oxidation number of the counter ion.

 [Formula 5F]

In the TMCP, the monomer and the linker may be linked by various chemical bonds such as 1) ion bond, 2) hydrogen bond, 3) coordination bond, and 4) covalent bond. As an example, at least one of Y, B1, and B2 of the monomer represented by Formula 1 may participate in a chemical bond with the linker.

The reaction for forming the TMCP may be any one of the following Schemes 1-13. Specifically, Schemes 1, 2, 10 to 13 are by ionic bonds, Schemes 3 and 4 are by hydrogen bonding, Schemes 5 and 6 are by coordination bonds, and Schemes 7, 8, and 9 are covalently bonded to TMCP. Indicates that is formed.

Scheme 1

In the above scheme _{1, Y 1, A 1,} A 2, B 1, and B ₂ are as defined in the formula ^{_{1-1, R, R 1 -,}} R 2 -, X 1 +, ₂ ^+, and X is And as defined in Formula 5A. As an example, the monomer represented by Formula 1-1 may be a monomer represented by Formula 1A.

In addition, TMCP represented by Chemical Formula 10 may be obtained through Scheme 1. Specific examples of TMCP represented by Formula 10 may be represented by the following Formulas 10A and 10B. However, it is not limited to this.

Scheme 2

In Scheme 2, A ₁ , A ₂ , B ₁ , and B ₂ may be as defined in Formula 1-1, and R, X ₃ , and X ₄ may be as defined in Formula 5B. As an example, the monomer represented by Formula 1-1 may be a monomer represented by Formula 1A. Y ₁ may be NH. At this time, N may be tetravalent.

In addition, TMCP represented by Chemical Formula 11 may be obtained through Scheme 2. Specific examples of the TMCP represented by Formula 11 may be represented by the following Formula 11A. However, it is not limited to this.

Scheme 3

In Scheme 3, Y, A ₁ , A ₂ , B ₁ , and R _B are as defined in Formula 1B, and R, R ₁ , R ₂ , R ₃ , and R ₄ may be as defined in Formula 5C. have.

In addition, TMCP represented by Chemical Formula 12 may be obtained through Scheme 3. Specific examples of the TMCP represented by Formula 12 may be represented by the following Formulas 12A, 12B, and 12C. However, it is not limited to this.

Scheme 4

In Scheme 4, Y, A ₁ , A ₂ , B ₁ , and R _B are as defined in Formula 1B, and R, D ₁ , D ₂ and n may be as defined in Formula 5D.

In addition, TMCP represented by Chemical Formula 13 may be obtained through Scheme 4. Specific examples of the TMCP represented by Formula 13 may be represented by the following Formula 13A and Formula 13B. However, it is not limited to this.

Scheme 5

In Scheme 5, Y ₁ , A ₁ , A ₂ , B ₁ , and B ₂ may be as defined in Formula 1-1, and M, L, X _a , and n may be as defined in Formula 5E. . As an example, the monomer represented by Formula 1-1 may be a monomer represented by Formula 1A. In addition, TMCP represented by Chemical Formula 14 may be obtained through Scheme 5.

Scheme 6

In Scheme 6, Y, A ₁ , A ₂ , B ₁ , R _B and L _B may be as defined in Formula 1C, and M, L, X _a , and n may be as defined in Formula 5E. In addition, TMCP represented by Chemical Formula 15 may be obtained through Scheme 6.

Specific examples of TMCP represented by Formula 14 may be represented by the following Chemical Formula 14A, and specific examples of TMCP represented by Formula 15 may be represented by the following Chemical Formulas 15A and 15B. However, it is not limited to this.

Scheme 7

In Scheme 7, Y, A ₁ , and A ₂ may be as defined in Formula 1D, and R may be as defined in Formula 5C. In addition, TMCP represented by Chemical Formula 16 may be obtained through Reaction Scheme 7.

Scheme 8

In Scheme 8, Y, A ₁ , and A ₂ may be as defined in Formula 1E. In addition, TMCP represented by Chemical Formula 17 may be obtained through Scheme 8.

Specific examples of the TMCP represented by the formula (16) may be represented by the following formula (16A) and 16B, specific examples of the TMCP represented by the formula (17) may be represented by the formula (17A). However, it is not limited to this.

Scheme 9

In Scheme 9, A ₁ , A ₂ , Y _a1 , and Y _a3 Is as defined in Formula 1G, and R, X ₃ , and X ₄ may be as defined in Formula 5B. Specifically, Y _a1 and Y _a3 May be N, O, S, P, Se, or CH irrespective of each other. The reaction represented by Scheme 9 may be performed using a base such as calcium carbonate. In addition, TMCP represented by Chemical Formula 18 may be obtained through Reaction Scheme 9.

Scheme 10

In Scheme 10, A ₁ , A ₂ , Y _a2 , and Y _a3 Is as defined in Formula 1G, and R, X ₃ , and X ₄ may be as defined in Formula 5B. Specifically, Y _a2 and Y _a3 may be N, O, S, P, Se, or CH irrespective of each other. In this case, unlike Scheme 9, the reaction may be performed in a state where no base is used. In addition, TMCP represented by Chemical Formula 19 may be obtained through Scheme 10.

Scheme 11

In Scheme 11, A ₁ , A ₂ , Y _a1 , Y _a2 , and Y _a3 Are as defined in Formula ^{_{1G, R, R 1 -,}} R 2 -, X 1 +, ₂ ^+, and X may be the same as defined in Formula 5A. Specifically, Y _a1 may be N, O, S, P, or Se, and Y _a2 and Y _a3 May be N, NH, O, S, P, PH, Se, or CH irrespective of each other. Through the scheme 11 it can be obtained a TMCP represented by the formula (20).

Specific examples of the TMCP represented by the formula (18) may be represented by the formula (18A), specific examples of the TMCP represented by the formula (19) may be represented by the formula (19A), and specific examples of the TMCP represented by the formula (20) may be represented by the formula (20A) have. However, it is not limited to this.

Scheme 12

In Reaction Scheme 12, Y are as defined in Formula ^{_{2, R, R 1 -,}} R 2 -, X 1 +, ₂ ^+, and X may be the same as defined in Formula 5A. In addition, TMCP represented by Chemical Formula 21 may be obtained through Scheme 12.

Scheme 13

In Scheme 13, the monomer aniline is when Y in Formula 2 is NH ₂ , and R, X ₃ , and X ₄ may be as defined in Formula 5B. In addition, TMCP represented by Chemical Formula 22 can be obtained by performing Scheme 13.

Specific examples of the TMCP represented by Formula 21 may be represented by the following Chemical Formula 21A, and specific examples of the TMCP represented by Formula 22 may be represented by the following Chemical Formula 22A. However, it is not limited to this.

Crystalline Polymer Examples

The crystalline polymer may be formed by polymerizing the TMCP described above. Such polymerisation may be oxidative coupling, C-C coupling, condensation polymerization, photopolymerization, or electrochemical polymerization. The C-C coupling can be, for example, Suzuki coupling, Stiletto coupling, CH-arlation, or CH-CH arlation. This polymerisation reaction may occur between the polymerization sites (* of Formulas 1 and 2) of the monomers included in the TMCP.

Examples of such crystalline polymers may be as follows.

Polymers represented by Chemical Formulas 30 to 42 are polymerized polymerized reactions of TMCP represented by Chemical Formulas 10 to 22, respectively. In Formulas 30 to 42, m may be an integer of 10 to 10,000. However, it is not limited to this.

As described above with reference to FIG. 1, as the polymers form a TMCP in which monomers are fixed as a linker, monomers included in different TMCPs are sequentially connected to form a polymer backbone. Significantly reduced, in part, a regular arrangement can be achieved without being intertwined at all.

Method for manufacturing crystalline polymer thin film

2 is a schematic view showing a method of manufacturing a crystalline polymer thin film according to an embodiment of the present invention.

Referring to FIG. 2, a mixed solution may be obtained by dissolving an appropriate amount of monomer and a linker in a solvent in a reactor. In this case, the solvent may be a co-solvent capable of dissolving the monomer and the linker at the same time. The solvent may be water, an organic solvent, or a mixed solvent thereof. The organic solvent may be alcohol (ex. Methanol, ethanol, propanol, butanol, etc.), chloroform, tetrahydrofuran (THF), or a mixed solvent of two or more thereof. However, the present invention is not limited thereto, and the co-solvent may be another solvent, which is not exemplified depending on the type of the monomer and the linker. On the other hand, when there is no co-solvent, the monomer and the linker in each of the different solvents are dissolved, and then dispersed in an emulsion form to obtain a mixed solution. The mixed solution can be stirred to obtain TMCP in which two monomers are bonded to both ends of one linker (A).

Thereafter, the substrate can be immersed in the mixed solution (B). Before immersing the substrate in the mixed solution, the substrate surface may be washed and then exposed to ultraviolet light and / or ozone to pretreat the substrate surface. The substrate may be glass, a polymer substrate such as polyethylene terephthalate (PET), a metal substrate, or a graphite foil. However, the present invention is not limited thereto, but in some cases, a light transmissive substrate may be used.

Thereafter, the initiator can be placed in the mixed solution containing the substrate (C). The initiator may vary depending on the type of monomer or the type of polymerization method. As an example, in the case of oxidative polymerization, the initiator may be ammonium persulfate. Polymerization of TMCP may be initiated by the initiator to produce a polymer in the reaction solution.

Thereafter, the substrate can be slowly removed from the mixed solution (D). In this case, a polymer film may be formed on the surface of the substrate, and the polymer film may have a regular arrangement, that is, improved crystallinity, as described with reference to FIG. 1. Thereafter, the substrate on which the polymer film is formed may be washed to remove residual materials and then dried.

The polymer film thus formed may be used as an electrode, for example, a transparent electrode, or may be used as a charge conductive layer, for example, a hole transport layer. The device using the polymer film may be an organic thin film transistor, an organic light emitting diode, an organic solar cell, or the like.

Method for preparing crystalline polymer particle slurry

According to another embodiment of the present invention, crystalline polymer particles can be obtained. The crystalline polymer particles can be obtained as a precipitate by dissolving an appropriate amount of monomer and linker in a solvent to prepare a mixed solution, and then adding an initiator therein, followed by stirring. Such crystalline polymer particles can be obtained in various sizes ranging from nanometers to micrometers.

The slurry may be prepared by mixing the polymer particle precipitate, the binder and the solvent. In this case, the binder is polytetrafluoroethylene (PTFE), polyvinylidene fluoride (Fluoride, PVDF), polyvinyl alcohol (PVA), polybutadiene rubber (Rubber, PBR), carboxymethyl cellulose (Carboxy Methyl Cellulose, CMC), or modified polymers of any of these, two or more co-polymers or mixtures thereof. For example, the slurry may further include carbon black, graphite, carbon fiber, carbon nanotube, or graphene.

Such a slurry can be applied onto a substrate using various methods to form an electrode layer. The electrode layer may be provided in a supercapacitor or pseudocapacitor, and in this case, charge and discharge operations may be implemented by adsorbing or desorbing ions. Specifically, ions may be adsorbed or desorbed due to heteroatoms of the crystalline polymer. Meanwhile, the electrode layer may be provided in a battery, in which case ions, for example, lithium ions are intercalated or decalated into the crystalline polymer, or heteroatoms of the crystalline polymer are oxidized or reduced. As a result, the charging or discharging operation may be implemented.

Hereinafter, preferred examples are provided to aid the understanding of the present invention. However, the following experimental examples are only for helping understanding of the present invention, and the present invention is not limited to the following experimental examples.

<Polymer Synthesis Examples  1 to 3

Scheme 21

Polymer Synthesis Example  One : Of poly (Py: EDSA: Py)  synthesis

First, 9.50 mg of EDSA (1,2-ethanedisulfonic acid, Tokyo Chemical Industry) was dissolved in 5 ml of deionized water in a 20 ml capped vial. Thereafter, 7.00 ml of Py (pyrrole, Tokyo Chemical Industry) was added to the vial to obtain a mixed solution of Py and EDSA. The mixed solution was stirred at ˜0 ° C. for 2 hours to prepare (Py: EDSA: Py), which is a two-monomer-connected precursor (TMCP) in which two Py units were connected by ionic bonding using one EDSA.

Glass slides (76 × 26 mm, Marienfeld-Superior), ITO (Indium tin oxide) coated glass slides (15 to 25 μsq ^-1 , 75 × 25 mm, Aldrich), flexible PET (Poly (ethylene) terephthalate)) film (thickness: 100 mu m, Film Bank), and flexible graphite foil (thickness: 130 mu m, Dongbang Carbon) were prepared.

Each substrate was sequentially ultrasonically cleaned with deionized water, acetone (Sigma-Aldrich) and isopropyl alcohol (Aldrich) for 15 minutes, then heated in an oven to 60 ° C. and dried, and the surface of the substrate was exposed to UV and ozone. It was exposed and surface treated. After immersing the surface-treated substrate vertically in the mixed solution, 5 ml of 0.10 mmol of ammonium persulfate (Aldrich) aqueous solution was added to the mixed solution, and TMCP (Py: EDSA: Py) at ˜0 ° C. Chemical oxidative polymerization of was induced on the substrate. After about 12 hours, the substrate was removed from the mixed solution, which resulted in a uniform poly (Py: EDSA: Py) film on the substrate. The film was washed with deionized water and ethanol (Aldrich) to remove residual salts and unreacted monomers. The washed film was dried overnight at 80 ° C. in a vacuum oven.

Polymer Synthesis Example  2 : Of poly (Py: BDSA: Py)  synthesis

TMCP (Py: BDSA: Py) was obtained using the same method as in Synthesis Example 1, except that 11.8 mg of BDSA (1,4-butanedisulfonic acid, Ark Pharm) was used instead of EDSA. : BDSA: Py) film was obtained.

Polymer Synthesis Example  3: Of poly (Py: BPDSA: Py)  synthesis

TMCP (Py: BPDSA: Py) was obtained using the same method as Polymer Synthesis Example 1, except that 15.7 mg of BPDSA (4,4'-biphenyldisulfonic acid, Tokyo Chemical Industry) was used instead of EDSA. (Py: BPDSA: Py) film was obtained.

Polymer Synthesis Comparative example  One : Of poly (Py: MSA)  synthesis

Scheme 22

Except for using 9.80 mg of MSA (methanesulfonic acid, Sigma-Aldrich) in place of EDSA, a precursor Py: MSA was obtained using the same method as in Synthesis Synthesis Example 1 to obtain a poly (Py: MSA) film. .

Evaluation example

<Evaluation Method>

FT-IR spectra were measured using a Perkin-Elmer FT-IR spectrometer (Spectrum System 2000) with potassium bromide pellets (Fluka). UV-visible spectra were obtained using a Perkin Elmer Lambda 750 UV-VIS-NIR spectrometer in the range from 300 to 1,000 nm. For X-ray diffraction measurements, thick polymer films (> 1 μm) were prepared via multiple polymerization on glass slides and Rigaku D / max-2500 with Cu-Kα radiation (λ = 1.54 μs) at 40 kV and 100 mA. It was performed using a diffractometer. HRTEM images were recorded using high voltage (1250 kV) electron beams (Gatan Inc., SP-US1000HV). To this end, samples were manufactured according to the synthesis examples using a carbon coated copper grid (200 mesh, EM Science) as a substrate, but formed in a very thin thickness so that the electron beam can be transmitted. Conductivity of the synthesized polymer film was measured by van der Pauw method at room temperature using the van der Pauw measurement system of Bio-Rad. The bar graph shows the average conductivity measured for three samples of each polymer. In addition, the sheet resistance of the PPy film (˜150 nm) formed through in-situ polymerization on a glass substrate (1 × 1 cm ² square) was measured.

3A to 3D show intermediates obtained during the processes of Comparative Polymer Synthesis Example 1 and Polymer Synthesis Examples 1 to 3, respectively, Py: MSA, TMCP (Py: BDSA: Py), TMCP (Py: BDSA: Py), And FT-IR spectra of TMCP (Py: BPDSA: Py). Specifically, in all of the FT-IR spectra a, b, c, and d, the upper black lines are the FT-IR spectra of Py, and the lower purple lines are Py: MSA (a) and TMCP (Py: BDSA: Py) (b, respectively. ), TMCP (Py: BDSA: Py) (c), and TMCP (Py: BPDSA: Py) (d).

3A-3D, a strong broad peak at 3375 cm ⁻¹ related to NH stretching vibration and a peak at 1673 cm ⁻¹ corresponding to C = C stretching are observed in the FT-IR spectrum of the Py ring. However, for Py salts that are Py: MSA, TMCP (Py: BDSA: Py), TMCP (Py: BDSA: Py), and TMCP (Py: BPDSA: Py), the NH band is reduced and shifted, in the Py ring. C = C stretching is not observed. In contrast, vibration bands in the 1675-1650 cm ⁻¹ region believed to be related to NH ²⁺ modified bands are observed in the spectra of all Py salt samples. The strong peak of 1644 cm ⁻¹ observed in the spectrum of TMCP (Py: BPDSA: Py) (d) corresponds to C = C stretching due to the biphenyl ring of BPDSA. The peak observed at 1500 cm ^-1 1200 cm ^-1 and 1050 cm ^-1 or less vicinity is due to the stretching vibration of each -SO ₃ group, and S = O.

As such, the absence of N-H and C═C stretching in all precursors may mean that ionic bonds formed as a result of acid-base interactions were formed in the precursors.

4 shows optical pictures of a poly (Py: EDSA: Py) film formed on various substrates obtained through Polymer Synthesis Example 1. FIG. Specifically, (a) is a photograph of in-situ polymerized poly (Py: EDSA: Py) films on a glass slide and an ITO-coated glass slide, and (b) is a phosphorus on a flexible PET film. -Photographed polymerized poly (Py: EDSA: Py) films in situ, and (c) photographed polymerized poly (Py: EDSA: Py) films polymerized in-situ on a flexible graphite foil. to be.

Referring to Figure 4, it can be seen that the poly (Py: EDSA: Py) film was produced in a size of 4.5 × 2.5 cm. Meanwhile, poly (Py: EDSA: Py) films were formed on both sides of the substrates, and the thickness thereof was about 150 nm. It can also be seen that the poly (Py: EDSA: Py) film polymerized in-situ in the presence of an oxidant on the substrate forms a uniform film.

5 shows ultraviolet-visible light absorption spectra of polymer films obtained in Comparative Polymer Synthesis Example 1 and Polymer Synthesis Examples 1 to 3;

Referring to FIG. 5, each polymer film was successfully synthesized on a glass substrate to exhibit an absorption peak at ˜430 nm, which is due to the polaron band of p-doped polypyrrol (PPy) in the polymer film. Interestingly, the poly (Py: EDSA: Py), poly (Py: BDSA: Py) and poly (Py: BPDSA: Py) films showed a red shifted absorption spectrum compared to poly (Py: MSA). Red displacement absorption indicates the presence of electronic interactions between the stacked polymer chains and can make the energy bandgap smaller than the energy bandgap of amorphous polymers having the same polymer backbone structure.

6 shows crystal properties of a poly (Py: EDSA: Py) film according to Polymer Synthesis Example 1, FIG. 7 shows crystal properties of a poly (Py: BPDSA: Py) film according to Polymer Synthesis Example 3, and FIG. 8. Shows crystal properties of the poly (Py: BDSA: Py) film according to the polymer synthesis example 2, Figure 9 shows the crystal properties of the poly (Py: MSA) film according to the polymer synthesis Comparative Example 1.

Referring to FIG. 6, it can be seen that the poly (Py: EDSA: Py) film exhibits a high crystal structure. Furthermore,

direction,

Direction, and

From the HRTEM and FFT (fast Fourier transform) images measured in the direction, it can be seen that the poly (Py: EDSA: Py) film exhibits an HCP crystal structure with a space group of P6 ₃ / mmc . Specifically, all HRTEM images

Having a plane in common, the interplanar spacing (d spacing) is ˜0.41 nm, from which the lattice parameter a of 0.47 nm for poly (Py: EDSA: Py) can be easily calculated. From the lattice parameter a the (0002) d interval, which is the second order reflection of the lattice parameter c, was calculated, which corresponds to the X-ray diffraction peak at 2θ = 23.8 ° and coincides with the calculated length (0.37 nm) between repeat units. . Given the packing order of the HCP crystals, it was estimated that poly (Py: EDSA: Py) grew in the [0001] direction because the lattice parameter c is twice the distance between two repeat units. The dark contrast region of the HRTEM image shows clusters of ionic bonds between ammonium and sulfonate having an electron density higher than the electron density inside the carbon. Therefore, ammonium-sulfonate clusters are hexagonally packed on the (0001) plane, and in typical HCP crystals the unit cell with the lattice parameter a = 0.47 nm and c = 0.74 nm corresponding to the c / a ratio of the raw unit cell. It can be reasonably estimated that it exists.

Referring to FIG. 7, the poly (Py: BPDSA: Py) film also showed a high crystal structure. Specifically,

direction,

Direction, and

From the HRTEM and FFT images measured in the direction, it can be seen that the poly (Py: BPDSA: Py) film exhibits the FCC crystal structure. Specifically, the (400) d interval, which is the fourth order reflection of the d interval (1.48 nm), is consistent with the calculated length (0.37 nm) between repeat units. X-ray diffraction spectra were used to investigate the d interval in the [100] direction, with peaks 2θ = 6.1 ° (1.48 nm), 12.2 ° (0.74 nm), 18.2 ° (0.49 nm), 24.4 ° (0.37 nm) ) And 30.4 ° (0.29 nm). Considering the crystal stacking order of the FCC structure along the [111] direction, it was assumed that a BPDSA connector having a length of 1.05 nm between sulfonate groups was packed at an angle between the PPy chains. The d spacing of poly (Py: BPDSA: Py) is an ammonium-sulfonate ionic cluster with different ionic bond angles and lengths (and thus slightly different electron densities) due to the BPDSA connectors obliquely packed between the PPy chains. Because there are two different forms of the field, they are relatively long. Therefore, the molecular crystal structure of poly (Py: BPDSA: Py), in terms of the order of the different ammonium-sulfonate clusters, is known as

Similar to). In addition, the unit cells of poly (Py: BPDSA: Py) with lattice parameters a = 1.48 nm and 2r = 1.05 nm have an a / 2r ratio consistent with typical FCC crystals.

Referring to FIG. 8, it can be seen that in the poly (Py: BDSA: Py) film, the X-ray diffraction pattern shows two characteristic peaks and some crystal structures in the HRTEM. However, it can be seen that the crystal domain is small and the crystallinity is relatively low. This can be reasonably interpreted to indicate that the rotational degrees of freedom of the butyl group of BDSA as compared to EDSA (FIG. 5) and BPDSA (FIG. 6) interfere with crystal packing.

Referring to FIG. 9, poly (Py: MSA) showed amorphous in HRTEM and X-ray diffraction analysis.

Referring to FIGS. 6-9 at the same time, unlike in covalent bonds, in the case of ionic bonds in solution, the bond length and angle between the polymer chain and the connector may vary during self-assembly by factors of the surrounding environment such as relative ions and steric hindrance May be affected. However, in the present experimental examples, although the polymer may be somewhat different depending on the type of the connector, a polymer aligned at the molecular level having a thermodynamically stable structure as a whole was obtained. These polymers, in particular, for Polymer Synthesis Examples 1 and 3, formed the most stable crystal structures (HCP and FCC) possible in each case.

10 is a poly (Py: EDSA: Py) film, a poly (Py: BPDSA: Py) film, a poly (Py: BDSA: Py) film, and polymers according to Polymer Synthesis Examples 1 to 3 and Polymer Synthesis Comparative Example 1 The conductivity and sheet resistance of the poly (Py: MSA) film are shown.

Referring to Figure 10, poly (Py: EDSA: Py) electrical conductivity of (8.94 ^Scm-1) is poly (Py: MSA) electrical conductivity ^of-the nearly three times higher than that (3.04 Scm ^1). For poly (Py: BDSA: Py), the conductivity was higher than poly (Py: MSA) but lower than poly (Py: EDSA: Py). This may be due to their relative crystallinity. In particular, poly-formed using the aromatic connector (Py: BPDSA: Py) conductivity in (103.7 Scm ^{- 1)} is poly: I was significantly increased as compared to the conductivity of the (Py MSA), these results crystal structure is in electrical conduction path In addition to strongly affecting, it was understood that the aromatic structure of the biphenyl group in the connector suggests that it enhances charge transfer along the connector by its p-conjugated system.

FIG. 11 is a schematic diagram illustrating the chemical arrangement of poly (Py: EDSA: Py) and poly (Py: BPDSA: Py) according to Polymer Synthesis Examples 1 and 3. FIG. Prediction of this chemical arrangement was inferred based on the experimental results of TEM, XRD, and XPS.

Referring to FIG. 11, a top view and a side view of the crystal structure of poly (Py: EDSA: Py) are shown in (a), and poly (Py: EDSA: Py) is ammonium sulfate It can be seen that the ion clusters are hexagonally packed within the (0001) plane.

In addition, the front and side views of the crystal structure of poly (Py: BPDSA: Py) are shown in (b), and poly (Py: BPDSA: Py) shows that ammonium-sulfate ion clusters were packed into a cube with a layered rock salt structure. Able to know.

<Polymer Synthesis Examples  4 to 9>

Polymer Synthesis Example  4 : Of poly (Py: AqDSA: Py)  synthesis

Scheme 23

Except for using AqDSA (2,6-anthraquinonedisulfonic acid) 0.005M instead of EDSA, TMCP (Py: AqDSA: Py) was obtained using the same method as Polymer Synthesis Example 1, and poly (Py: AqDSA: Py) was used. ) Film.

Polymer Synthesis Example  5: Of poly (Py: AqDSNa: Py)  synthesis

Scheme 24

Except for using AqDSNa (2,6-anthraquinonedisulfonate sodium salt) 0.005M instead of EDSA, TMCP (Py: AqDSNa: Py) was obtained using the same method as in Polymer Synthesis Example 1, and the poly (Py: AqDSNa: Py) film.

12 shows the properties of the polymer film according to the polymer synthesis examples 4 and 5, and Comparative Example 1 of the polymer synthesis.

Referring to FIG. 12, a poly (Py: AqDSA: Py) film polymerized in-situ in the presence of an oxidant on a substrate from an optical photograph taken of a poly (Py: AqDSA: Py) film according to Polymer Synthesis Example 4 It can be seen that a uniform film is formed.

In addition, the poly (Py: AqDSA: Py) film according to the polymer synthesis example 4, the poly (Py: AqDSNa: Py) film according to the polymer synthesis Example 5, and the poly (Py: MSA) film according to the polymer synthesis Comparative Example 1 According to the ultraviolet-visible absorption spectrum, it can be seen that each polymer film was successfully synthesized on the glass substrate to exhibit absorption peaks at 470 nm, 462 nm, and 434 nm, respectively.

13 shows crystal properties of a polymer film according to Polymer Synthesis Example 4. FIG.

Referring to FIG. 13, when the sharp peaks appear in the XRD graph of the poly (Py: AqDSA: Py) film according to Polymer Synthesis Example 4, and also the linear structure appears in the HRTEM, the FFT transform diffraction pattern appears. It can be seen that the Py: AqDSA: Py) film has a good crystal structure.

Polymer Synthesis Example  6: Of poly (EDOT: BPDSA: EDOT)  synthesis

Scheme 25

Instead of Py and EDSA, 2 equivalents of EDOT (3,4-ethylenedioxythiophene) was used as a monomer, 1 equivalent of BPDSA (4,4'-biphenyldisulfonic acid) as a linker, and 0.015 mol of FeCl3 as an initiator instead of ammonium persulfate. Except that except using the same method as Polymer Synthesis Example 1 TMCP (EDOT: BPDSA: EDOT) to obtain a poly (EDOT: BPDSA: EDOT) film.

Polymer Synthesis Comparative example  2 : Of poly (EDOT: BPDSA)  synthesis

A poly (EDOT: BPDSA) film was obtained in the same manner as in Synthesis Example 6 except that 1 equivalent of EDOT (3, 4-ethylenedioxythiophene) was used.

14 is an X-ray diffraction graph of a poly (EDOT: BPDSA: EDOT) film according to Polymer Synthesis Example 6. FIG.

Referring to FIG. 14, the poly (EDOT: BPDSA: EDOT) film according to Polymer Synthesis Example 6 may or may not show peaks depending on the type of solvent used in the synthesis process, and is a cosolvent capable of dissolving both EDOT and BPDSA. In the case of using a mixed solvent of methanol and chloroform, crystallinity was best.

15 is an HRTEM image of a poly (EDOT: BPDSA: EDOT) film according to Polymer Synthesis Example 6. FIG.

Referring to FIG. 15, analysis of HRTEM images of poly (EDOT: BPDSA: EDOT) film showed that the poly (EDOT: BPDSA: EDOT) film had an orthorhombic structure.

As such, the electrical conductivity of the poly (EDOT: BPDSA: EDOT) film, which is a crystalline polymer, is significantly improved compared to the electrical conductivity of 0.055 Scm ^-1 , which is a polymer (EDOT: BPDSA) film, which does not form crystals at 0.208 Scm ^-1 . The results are shown.

Polymer Synthesis Example  7: Of poly (Py: Zn: Py)  synthesis

Scheme 26

Except for using Zn (NO ₃ ) ₂ 0.005M instead of EDSA, TMCP (Py: Zn: Py) formed by coordinating two Py and one Zn was obtained using the same method as in Synthesis Example 1 of the polymer. This was used to obtain a poly (Py: Zn: Py) film.

16 shows crystal properties of a polymer film according to Polymer Synthesis Example 7.

Referring to FIG. 16, when the sharp peaks appear in the XRD graph of the poly (Py: Zn: Py) film according to Polymer Synthesis Example 7 and also the linear structure appears in the HRTEM image, the poly (Py: Zn: Py) film It turns out that silver has a favorable crystal structure.

Polymer Synthesis Example  8 : Of poly (spiroBiProDOT)  synthesis

Scheme 27

Pentaerythritol and 3,4-dimethoxythiophene were dissolved in a toluene solvent (250 mL) at a molar ratio of 8: 2 (0.08: 0.02 mol) to obtain a mixed solution. After adding 0.015 mmol of pTSA (p-toluenesulfonic acid) into the mixed solution, the mixed solution was stirred for 24 hours in an argon atmosphere. After 24 hours, the black mixture was purified and dried to give a yellow solid TMCP (Spiropropylenedioxythiophene; SprioBiproDOT). 0.1 mmol of SprioBiproDOT obtained was dissolved in 30 ml anhydrous dimethylformamide solvent, and 0.18 mmol of tetra-n-butylammonium bromide, 0.5 mmol of potassium acetate, and palladium acetate 0.018 mmol was added. The resulting mixture was stirred at least 12 hours at room temperature. When the substrate is used as in Polymer Synthesis Example 1, a polymer film may be obtained on the substrate, and the polymerized in the liquid phase may be obtained as a precipitate. The polymer film and precipitate contain poly (spirobipropylenedioxythiophene; SprioBiproDOT).

17 shows crystal properties of a polymer film according to Polymer Synthesis Example 8. FIG.

Referring to FIG. 17, when the linear structure is shown in the HRTEM image of the poly (SprioBiproDOT) film according to Polymer Synthesis Example 8, it can be seen that the poly (SprioBiproDOT) film has a good crystal structure.

Polymer Synthesis Example  9

Scheme 28

1 g of benzotriazole (Sigma-Aldrich), 0.9 g of trans-1,4-dibromo-2-butene (Sigma-Aldrich), 1.74 g of K ₂ CO ₃ (Sigma-Aldrich) in a 100 ml two-necked flask Put it. One inlet of the flask was placed in a reflux condenser and then dissolved in 30 ml of n-MP (N-Methyl-2-pyrrolidone, Sigma-Aldrich). After stirring for 30 minutes at room temperature under argon gas injection, the temperature was raised to 800 ° C. The solution was stirred for 48 hours and then detilated to remove solvent n-MP. The material remaining in the solid state was dissolved in MC (Methylene Chloride) and purified and extracted. The solid material obtained here was dissolved in MC again and then recrystallized by adding hexane (Sigma-Aldrich). The material obtained by recrystallization was then separated by chromatography using a 2: 1 ratio of hexane and EA (ethyl acetate) as eluent. Through the above process, two monomers of benzotriazole were connected to each other by covalent bonding using one trans-1,4-dibromo-2-butene.

In a 100 ml two-necked flask, 30 mg of TMCP and 60 mg of initiator FeCl 3 were covalently linked. The flask was placed in a reflux condenser and dissolved in 10 ml of DMF (Sigma-Aldrich). After stirring for 30 minutes at room temperature under argon gas injection the temperature was raised to 120 ° C. After about 72 hours, the precipitated product was separated and washed with deionized water and ethanol (Aldrich) to remove residual salts and unreacted monomers.

18 shows crystal properties of a polymer film according to Polymer Synthesis Example 9. FIG.

Referring to FIG. 18, when the linear structure is shown in the HRTEM image of the polymer film according to Polymer Synthesis Example 9, it can be seen that the polymer film has a good crystal structure at least in part.

In the above, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications and changes by those skilled in the art within the spirit and scope of the present invention. This is possible.

Claims (27)

1. Forming a two-monomer-linked precursor having a pair of monomers and one linker connecting these monomers to each other; And

   A method of producing a crystalline polymer comprising polymerizing the 2-monomer-linked precursor.
2. The method of claim 1,

   The crystalline polymer prepared in the polymerization step is

   Preparation of crystalline polymers comprising a plurality of polymer backbones formed by combining monomers provided in the different two-monomer-linked precursors, wherein the linker connects a pair of monomers provided in adjacent polymer backbones. Way.
3. The method of claim 2,

   The polymer backbone is a crystalline polymer manufacturing method is a conductive polymer.
4. The method of claim 3,

   The polymer backbone is polypyrrole, polythiophene, polyaniline, poly (3,4-ethylenedioxythiophene), or polyphenylene.
5. The method of claim 2,

   The linker is a crystalline polymer manufacturing method of the linker is an oxidative dopant to add holes to the polymer backbone or a reducing dopant to add electrons to the polymer backbone.
6. The method of claim 1,

   The crystalline polymer has a lattice point of the molecular unit having a repeating pattern of the unit cell having a lattice constant.
7. The method of claim 1,

   The one linker and the pair of monomers are crystalline polymers are bonded by ionic bonds, hydrogen bonds, coordination bonds, or covalent bonds.
8. The method of claim 1,

   The polymerization is a method for producing a crystalline polymer that is carried out using oxidation polymerization, C-C coupling, condensation polymerization, photopolymerization, or electrochemical polymerization.
9. The method of claim 1,

   The monomer is a crystalline polymer manufacturing method of the monomer represented by the following formula (1):

   [Formula 1]

   

   In Chemical Formula 1,

   Y is NR ₁ , S, O, Se, or (CH) ₂ , R ₁ is hydrogen or an alkyl group of C1 to C3,

   One of A ₁ and A ₂ is hydrogen, —B (OR _A ) ₂ , —Sn (R _A ) ₃ , or X _A , the other is hydrogen, or X _A , and R _A is H or C1 to C4 Is an alkyl group, X _A is independently of each other Cl, Br, I, or pseudohalogen,

   B ₁ and B ₂ are independently of each other hydrogen, a hydroxyl group, a C1 to C4 alkyl group, a C1 to C4 alkyl alcohol group, a C1 to C4 alkoxy group, a C1 to C4 (alkyl) carboxylic acid, a C1 to C4 (Alkyl) carboxylate, an amine group, or an alkylamine group of C1 to C4, or B ₁ and B ₂ are joined together to form a carboxylic anhydride, ethylenedioxy group, or B ₁ and B ₂ are joined together to B ₁ and B and ₂ form a heterocyclic ring of 5 to 6 members together with the attached carbon atom,

   * Is the polymerization site in the polymerization step.
10. The method of claim 9,

    The monomer represented by the formula (1) is a crystalline polymer production method is a monomer represented by the formula (1-1):

    [Formula 1-1]

    

    In Formula 1-1, Y ₁ is NR ₁ , S, O, or Se, R ₁ is hydrogen or an alkyl group of C1 to C3, ring G ₁ is a pentagonal heteroaromatic ring, A ₁ , A ₂ , * , B ₁ and B ₂ are as defined in the formula (1).
11. The method of claim 10,

    The monomer represented by Formula 1-1 is a crystalline polymer manufacturing method of the monomer represented by Formula 1A:

    [Formula 1A]

    

    In Formula 1A, Y ₁ , A _1, and A ₂ are as defined in Formula 1-1, and B ₃ and B ₄ are hydrogen or an alkyl group of C1 to C4 irrespective of each other.
12. The method of claim 9,

    The monomer represented by the formula (1) is a crystalline polymer production method is a monomer represented by the formula 1-2:

    [Formula 1-2]

    

    In Formula 1-2, A ₁ , A ₂ , *, B ₁ and B ₂ are as defined in Formula 1.
13. The method of claim 12,

    The monomer represented by Formula 1-2 is a crystalline polymer production method is a monomer represented by the formula 1F:

    [Formula 1F]

    

    In Formula 1F, A ₁ and A ₂ are as defined in Formula 1, Ring B is a 5-6 membered heteroaromatic ring, Y _a is irrespective of each other N, NH, O, S, P, PH, or Se, n is an integer of 1 to 3.
14. The method of claim 13,

    The monomer represented by Formula 1F is a crystalline polymer manufacturing method of the monomer represented by Formula 1G:

    [Formula 1G]

    

    Formula 1G is Y _a1 , Y _a2 , and Y _a3 At least one is a heteroatom, the rest is carbon, each heteroatom may be selected from the group consisting of N, NH, O, S, P, PH, and Se.
15. The method of claim 14,

    Y _a1 above Or Y _a2 is N or NH.
16. The method of claim 9,

    The monomer represented by Chemical Formula 1 is any one of the monomers represented by the following Chemical Formulas 1B, 1C, 1D, and 1E:

    [Formula 1B]

    

    In Formula 1B, Y, A ₁ , A ₂ , and B ₁ are as defined in Formula 1, R _B is a bond, an alkyl group of C1 to C4, or a (alkyl) carbonyl group of C1 to C4,

    [Formula 1C]

    

    In Formula 1C, Y, A ₁ , A ₂ , and B ₁ are as defined in Formula 1, L _B is a carboxylic acid, a carboxylate, or an amine group, R _B is a bond or an alkyl group of C1 to C4. ,

    [Formula 1D]

    

    In Formula 1D, Y, A ₁ and A ₂ are the same as defined in Formula 1,

    [Formula 1E]

    

    In Formula 1E, Y, A ₁ and A ₂ are as defined in Formula 1.
17. The method of claim 1,

    The monomer is a crystalline polymer production method is a monomer represented by the formula (2):

    [Formula 2]

    

    In Formula 2, Y is NH ₂ or SH, and * is a polymerization site in the polymerization step.
18. The method of claim 1,

    The connector is a method of producing a crystalline polymer is a linker represented by any one of the formulas 5A to 5F:

    [Formula 5A]

    

    And, ^- in the formula 5A, R ₁ ^- and R ₂ ^- is a COO, regardless of each other ^-, SO ₃ ^-, or PO (OH) O X ₁ ⁺ and X ₂ ⁺ are each independently a hydrogen ion or an alkali metal ion, R is an alkanediyl of C2 to C4, an alkenediyl of C2 to C4, an alkyndiyl of C2 to C4, of C6 to C20 Arylene, C2 to C20 heteroarylene, C6 to C20 arylene alkenediyl or C6 to C20 cycloalkylene,

    [Formula 5B]

    

    In Formula 5B, X ₁ and X ₂ are Br, Cl, or I regardless of each other, R is as defined in Formula 5A,

    [Formula 5C]

    

    In Formula 5C, R ₁ , R ₂ , R ₃ , and R ₄ may be hydrogen or an alkyl group of C1 to C2, irrespective of each other, R is as defined in Formula 5A,

     [Formula 5D]

    

    In Formula 5D, Rings D ₁ and D ₂ are 5-membered or 6-membered unsaturated heterocyclic compounds having N of 1 to 3 as heteromembers, R is as defined in Formula 5A, and n is 1 or Is an integer of 0,

     [Formula 5E]

    

    In Formula 5E, M is Zn, Cu, Pd, Ru, or a metal ion such as Pt, L is H ₂ O, NH _3, or an ethylene-a-diamine, X _a is a counter ion OH ^-, NO ₃ ^- , CO ₃ ^-, CN ^-, or Cl ^-, n is a number determined this compound in consideration of the oxidation state of the ion and the oxidation number of the metal ion relative to neutral.

     [Formula 5F]

    
19. The method of claim 1,

    The crystalline polymer is a crystalline polymer manufacturing method represented by any one of the following formulas 30 to 42:

    

    

    

    

    

    

    

    

    

    

    

    

    

    In Formulas 30 to 42, m is an integer of 10 to 10,000.
20. A crystalline polymer obtained by polymerizing a two-monomer-linked precursor having a pair of monomers and one linker connecting the monomers to each other.
21. The method of claim 20,

    The crystalline polymer includes a plurality of polymer backbones formed by combining monomers provided in the different 2-monomer-linked precursors, and the linker connects a pair of monomers provided in adjacent polymer backbones. Crystalline polymer.
22. The method of claim 20,

    The polymer backbone is a crystalline polymer that is a conductive polymer.
23. The method of claim 22,

    The polymer backbone is polypyrrole, polythiophene, polyaniline, poly (3,4-ethylenedioxythiophene), or polyphenylene.
24. The method of claim 20,

    The linker is a crystalline polymer, wherein the linker is an oxidative dopant for adding holes to the polymer backbone or a reducing dopant for adding electrons to the polymer backbone.
25. The method of claim 20,

    The crystalline polymer has a repeating pattern of a unit cell having a lattice constant by having lattice points in a molecular unit.
26. The method of claim 20,

    Wherein said one linker and said pair of monomers are bonded by ionic bonds, hydrogen bonds, coordination bonds, or covalent bonds.
27. The method of claim 20,

    The crystalline polymer is a crystalline polymer represented by any one of the following formulas 30 to 42:

    

    

    

    

    

    

    

    

    

    

    

    

    

    In Formulas 30 to 42, m is an integer of 10 to 10,000.

Images