WO2017073927A1

WO2017073927A1 - Hydrochromic polydiacetylene polymer patch and manufacturing method therefor

Info

Publication number: WO2017073927A1
Application number: PCT/KR2016/011399
Authority: WO
Inventors: 김종만; 서민정; 박동훈
Original assignee: 한양대학교 산학협력단
Priority date: 2015-10-30
Filing date: 2016-10-12
Publication date: 2017-05-04

Abstract

Provided are a hydrochromic polydiacetylene polymer patch and a manufacturing method therefor. The hydrochromic polymer patch comprises: a polymer matrix; and a polydiacetylene located in the polymer matrix. The polydiacetylene includes an ionic functional group in a repeating unit. The ionic functional group is represented by R^-M⁺ or R⁺X^-, wherein R^- is a carboxylate anion; M⁺ is an alkali metal cation; R⁺ is a quaternary ammonium group; and X^- is F^-, Cl^-, Br^-, I^-, PF₆ ^-, BF₄ ^-, bis(trifluoromethane)sulfonimide (Tf₂N^-), trifluoromethanesulfonate (TfO^-), SCN^-, or CH₃COO^-.

Description

Hydrochromic polydiacetylene polymer patch and preparation method thereof

The present invention relates to polydiacetylene, and more particularly to a hydrochromic polydiacetylene polymer patch.

Polydiacetylene is a polymer of diacetylene monomers, and is a conjugated polymer having characteristics that are produced through photopolymerization such as ultraviolet or gamma irradiation when the diacetylene monomers are arranged through self-assembly. . Such polydiacetylenes have alternating double and triple bonds in the polymer main chain, and generally have a maximum absorption wavelength at about 640 nm, which is blue, and exhibits external conditions (heat, solvent, pH, force, molecular recognition, etc.). As a result, the maximum absorption wavelength shifts to about 540 nm and turns red. Various kinds of sensors have been researched and developed by using the discoloration feature of the polydiacetylene.

The prior art has the disadvantage that the base material used in the production of hydrochromic polydiacetylene thin film is glass, PET film and OHP film, and the film is easily peeled off or peeled off after the production of the thin film. The amount of the die acetylene complex required a large amount and may be generated unevenly, there was a disadvantage that the sensor function may be lost by sensitively reacting to moisture in the atmosphere when the thin film is manufactured and stored.

Accordingly, an object of the present invention is to provide a polydiacetylene-containing polymer patch which suppresses detachment of polydiacetylene from a base material and decreases sensitivity to humidity.

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.

One aspect of the present invention to achieve the above technical problem provides a hydrochromic polymer patch. The hydrochromic polymer patch may include a hydrophilic polymer matrix; And a polydiacetylene having a repeating unit represented by the following Chemical Formula 5 located in the hydrophilic polymer matrix.

[Formula 5]

In Formula 5, a is an integer of 1 to 20, b is an integer of 1 to 20,

L ₁ is

,

,

,

, or

E, E ₁ , and E ₂ are each independently O or S, c is an integer of 0 to 2, L ₂ is an alkylene having 1 to 10 carbon atoms or an arylene group having 5 to 12 carbon atoms, d is an integer from 0 to 1, IG is an ionic functional group, R ^- and, R ^- ^- M ^+, or R ⁺ X is an anion carboxylate, M ⁺ is an alkali metal cation, R ⁺ is a quaternary ammonium group, and , X ^- is ^{^{^{F -, Cl -, Br -}}} , I -, PF 6 -, BF 4 -, Tf 2 N - (bis (trifluoromethane) sulfonimide), TfO - (trifluoromethanesulfonate), SCN -, or CH ₃ COO ^- to be.

The polymer may be polyethylene oxide, polyvinyl alcohol or polyvinylpyrrolidone. The polymer may be contained in an amount of about 1.5 to 3.5 parts by weight based on 1 part by weight of the polydiacetylene. The hydrochromic polymer patch may further include a hydrophilic oligomer or a plasticizer.

In one example, the polydiacetylene having a repeating unit of Formula 5 may be a polydiacetylene having a repeating unit represented by the following formula (6).

[Formula 6]

In Formula 6, a, b, R ^-, and M ⁺ is the a, b, R Formula ^5, and each may be the same as M ^+. M ⁺ may be cesium ions or rubinium ions. In this case, the polymer may be polyethylene oxide, polyvinyl alcohol or polyvinylpyrrolidone.

In another example, the polydiacetylene having a repeating unit represented by Formula 5 may be a polydiacetylene having a repeating unit represented by the following Formula 7.

[Formula 7]

Of Formula _{7 a, b, L 1,} c, e, R +, and X ^- is of Formula _{5 a, b, L 1,} c, e, R +, and X ^- may be the same with each. Specifically, R ⁺ may be N ⁺ -R ₁ -heterocyclic quaternary ammonium represented by the following Chemical Formula 2a.

[Formula 2a]

In Formula 2a, * is a bond, and ring B is a 5-membered or 6-membered heterocyclic compound having N of 1 to 3 and O of 0 to 1 as a hetero member. ) Is a saturated or unsaturated heterocyclic compound, and R ₁ may be cyanoalkyl having 1 to 16 carbon atoms, haloalkyl having 1 to 16 carbon atoms, hydroxyalkyl having 1 to 16 carbon atoms, or aminoalkyl having 1 to 16 carbon atoms. .

N ⁺ -R ₁ of formula 2a - heterocyclic quaternary ammonium is N ⁺ -R ₁ shown in the following formula 2b or 2c to the formula - may be a heterocyclic ring quaternary ammonium.

[Formula 2b]

[Formula 2c]

In Formula 2b, Ring C is a 5-membered or 6-membered unsaturated heterocyclic compound having N of 2 to 3 as a hetero member, and in Formula 2c, Ring D has N of 2 to 3 as heteromember Is a 5-membered or 6-membered unsaturated heterocyclic compound, R ₁ and R ₁ ′ are each independently a cyanoalkyl having 1 to 16 carbon atoms, a haloalkyl having 1 to 16 carbon atoms, or a hydroxyl having 1 to 16 carbon atoms. Alkyl, or aminoalkyl having 1 to 16 carbon atoms.

The N ⁺ -R ₁ -heterocyclic quaternary ammonium is N ⁺ -R ₁ -azolium, N ⁺ -R ₁ -azinium, or N ⁺ -R ₁ R ₂ -piperazini It may be piperazinium. The N ⁺ -R ₁ - Ah sleepiness is N ⁺ -R ₁ - can be a tri-O sleepiness (triazolium) - imidazolium diamond (diazolium) or N ⁺ -R _1. The N ⁺ -R ₁ - imidazolium diamond is to N ⁺ -R ₁ represented by formula 2-1 may be a pyrazolyl imidazolium-imidazolidin N ⁺ -R ₁ represented by the following Formula 2-2 or sleepiness.

In Formulas 2-1 and 2-2, R _a may be an alkylene group having 1 to 16 carbon atoms, and Y _a may be a cyan group, a halogen, a hydroxy group, or an amine group.

The hydrochromic polymer patch may exhibit blue color. The hydrochromic polymer patch may be a pore mapping patch.

Another aspect of the present invention to achieve the above technical problem provides a method for producing a hydrochromic polymer patch. First, the diacetylene monomer solution represented by Formula 1 below is mixed with the diacetylene monomer solution contained in the first solvent and the polymer solution containing the polymer in the second solvent. The mixture is molded into a film. The film is dried to form a polymer patch including the matrix of the polymer and the diacetylene monomers self-assembled therein. Ultraviolet or gamma radiation is applied to the polymer patch to photopolymerize the diacetylene monomers to form polydiacetylene.

[Formula 1]

In Formula 1, a, b, c, d, L 1, L 2, and IG is the same and each of Formula 5 a, b, c, d , L 1, L 2, and IG.

The first solvent and the second solvent may be a volatile solvent mixed with each other. Further, the first solvent and the second solvent may be a nonpolar solvent having an amphiphilic solvent or a dipole moment irrespective of each other.

In one example, the diacetylene monomer represented by Formula 1 may be a diacetylene monomer represented by Formula 3 below.

[Formula 3]

Of Formula 3 a, b, R ^-, and M ⁺ is the a, b, R the general formula (1) ^-, and each may be the same as M ^+.

In another example, the diacetylene monomer represented by Formula 1 may be a diacetylene monomer represented by Formula 4 below.

[Formula 4]

Of _{a, b, L 1, c} , e, R +, and the general formula X 4 ^- is of _{a, b, L 1, c} , e, R +, and the general formula X 1 ^- may be the same with each.

As described above, according to the present invention, the polymer patch including the hydrochromic polydiacetylene in the hydrophilic polymer may be suppressed from detachment of the polydiacetylene from the base material and the sensitivity to humidity may be reduced.

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 diagram showing a polydiacetylene-containing polymer patch production method and a water discoloration reaction of the polymer patch according to an embodiment of the present invention.

Fig. 2 is a photograph of a PEO film (a) containing DA-Im obtained according to Hydrochromic patch Preparation Example 1-1b and a PEO film (b) containing PDA-Im obtained by light irradiation on the film.

FIG. 3 is a graph showing Raman spectra of a PEO film containing DA-Im obtained according to Preparation Example 1-1b and a PEO film containing PDA-Im obtained by light irradiation of the film.

4 is a) photograph, b) backbone modification of polydiacetylene, c) UV-vis absorption spectrum, before and after adding water to a PEO film containing PDA-Im obtained according to Preparation Example 1-1b of hydrochromic patch. And d) Raman spectrum.

FIG. 5 is a photograph showing an optical image after a finger is touched on a PEO film containing PDA-Im obtained according to hydrochromic patch Preparation Examples 1-1a to 1-1f.

FIG. 6 is a photograph showing an optical image after contacting the nose, the entire palm, and the sole of the foot on a PEO film containing PDA-Im obtained in Preparation Example 1-1b.

Figure 7 is a photograph showing the degree of water discoloration according to the relative humidity of the PEO film containing PDA-Im obtained according to the hydrochromic patch Preparation Example 1-1b.

8 is a photograph (a) of a polymer film containing PDA-Im obtained according to hydrochromic patch preparation examples 1-1b, 1-2, 1-3, and 1-4, and an optical image after contact with a finger (b ), And a fluorescence microscope image (c).

9 is a photograph of a polymer film containing PDA-Cs obtained according to the hydrochromic patches Preparation Examples 2-1 to 2-4.

10 is a photograph showing the degree of water discoloration according to the relative humidity of the polymer film containing the PDA-Cs obtained according to the hydrochromic patch Preparation Examples 3-1 to 3-4.

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 embodiments, "first", "second", or "third" is not intended to impose any limitation on the components, but should be understood as a term for distinguishing the components.

As used herein, unless otherwise defined, "alkyl" refers to an aliphatic hydrocarbon group and may be "saturated alkyl" that does not include a double bond or a triple bond. Saturated alkyl groups can be linear.

As used herein, unless otherwise defined, "alkylene" refers to a divalent group which is a radical of an alkane which is saturated hydrocarbon, and may be linear alkylene.

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

As used herein, "halogen" or "halo" is an element belonging to Group 17, specifically, it may be a fluorine, chlorine, bromine, or iodine group.

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

Diacetylene Monomer-containing polymer patch

Referring to FIG. 1, a polymer patch (A) having a polymer matrix and diacetylene monomers having ionic functional groups at ends thereof self-assembled may be formed.

As an example, the polymer patch (A) may mix the diacetylene monomer solution containing the diacetylene monomers in the first solvent and the polymer solution containing the polymer in the second solvent, and then shape the mixed solution into a film form. Can be formed. The molding in the form of a film may be selected from the group consisting of drop-casting, injection, spin coating on a substrate, ink jet printing, doctor blade and immersion-impression method.

The polymer patch (A) comprising the diacetylene monomers may be dried to remove at least some or substantially the solvent (s). Such drying may proceed at about 1-5 ° C. and may proceed for about 10-14 hours. During this drying process, the self-assembly of the die acetylene monomers is maintained may be in a semi-crystalline or crystalline state. The polymer patch (A) may be a colorless opaque film.

The die acetylene monomer may be a compound represented by the following formula (1).

[Formula 1]

In Formula 1, a may be an integer of 1 to 20. As an example, a may be an integer of 6 to 18, specifically 10 to 12. b may be an integer from 1 to 20. As an example, b may be an integer of 2 to 12, specifically 2 to 8.

L ₁ is

,

,

,

, or

And E, E ₁ , and E ₂ may be O or S irrespective of each other. c may be an integer from 0 to 2. As an example, c may be 1.

L ₂ is an alkylene having 1 to 10 carbon atoms or an arylene group having 5 to 12 carbon atoms,

(Wherein e may be an integer of 1 to 10, as an example 1 to 5, more specifically 2 to 4) or benzenediyl and specifically 1,3 benzenediyl. d may be an integer from 0 to 1.

IG is an ionic functional group, R ^- may be ^- M ^+, or R ⁺ X.

In R ^- M ⁺ , R ^- may be a carboxylate anion as an anionic functional group. M ⁺ may be an alkali metal cation as a counter cation, specifically a cation of one or more metals selected from the group consisting of cesium, rubidium, potassium, sodium and lithium. As an example, M ⁺ may be cesium ion or rubinium ion.

R ⁺ X ^- be a heterocyclic ring quaternary ammonium (heterocyclic quarternary ammonium) - In, R ⁺ is a cationic functional group and a quaternary ammonium group, it said quaternary ammonium is one example, to N ⁺ -R ₁ represented by Formula 2a as have.

[Formula 2a]

In Formula 2a, Ring B may be a 5-membered or 6-membered heterocyclic compound, a saturated or unsaturated heterocyclic compound, at least one N, specifically 1 to N of 3 and 0 of 0 may be provided as a hetero member. In addition, in Formula 2a, R ₁ may be cyanoalkyl having 1 to 16 carbon atoms, haloalkyl having 1 to 16 carbon atoms, hydroxyalkyl having 1 to 16 carbon atoms, or aminoalkyl having 1 to 16 carbon atoms. Specifically, R ₁ may be represented by * -R _a -Y _a , wherein * is a bond, and R _a is an alkylene group having 1 to 16 carbon atoms as an example, 1 to 6 carbon atoms specifically, 1 to 3 carbon atoms May be an alkylene group, and Y _a may be _a cyan group, a halogen, a hydroxy group, or an amine group.

[Formula 2b]

[Formula 2c]

Formula 2b is * -N ⁺ -R ₁ -heterocyclic quaternary ammonium, ring C is a 5-member or 6-membered unsaturated heterocyclic compound, it may be provided with N of 2 to 3 as a hetero member.

In Formula 2c, Ring D is a 5-membered or 6-membered unsaturated heterocyclic compound, and may have N of 2 to 3 as a hetero member. In addition, R ₁ and R ₁ ′ may be cyanoalkyl having 1 to 16 carbon atoms, haloalkyl having 1 to 16 carbon atoms, hydroxyalkyl having 1 to 16 carbon atoms, or aminoalkyl having 1 to 16 carbon atoms, irrespective of each other. And * -R _a -Y _a . R _a and Y _a may be as defined above.

The N ⁺ -R ₁ -heterocyclic quaternary ammonium is, for example, N ⁺ -R ₁ -azolium, N ⁺ -R ₁ -azinium, or N ⁺ -R ₁ R ₂ It may be piperazinium.

The N ⁺ ₁ -R - N ⁺ O sleepiness is -R ₁ - can be a tri-O sleepiness (triazolium) - diamond sleepiness (diazolium) or N ⁺ -R _1. N ⁺ -R ₁ - imidazolium diamond is N ⁺ -R ₁ - imidazolium (imidazolium), or N ⁺ -R ₁ - pyrazol may be sleepiness (pyrazolium), the N ⁺ -R ₁ - imidazolium has the formula It may be represented by 2-1, the N ⁺ -R ₁ -pyrazolium may be represented by the formula 2-2. On the other hand, N ⁺ -R ₁ -triazolium can be represented by the following formula 2-3.

The N ⁺ -R ₁ - Ah Genie Titanium is N ⁺ -R ₁ - can be a help pyrazol Genie (pyrazinium) - pyrimidinyl minyum (pyridiminium) or N ⁺ -R _1. N ⁺ -R ₁ -pyrimidinium may be represented by the following Chemical Formula 2-7 or 2-8, and N ⁺ -R ₁ -pyrazinium may be represented by the following Chemical Formula 2-9.

N ⁺ -R ₁ R ₂ -piperazinium may be * -N ⁺ -R ₁ R ₂ -piperazinium, which may be represented by the following formula (2-14).

In Formulas 2-1 to 2-3, 2-7 to 2-9, and 2-14, R _a and Y _a are as described above, and R _a1 and R _a2 have 1 to 16 carbon atoms regardless of each other. Alkylene group as an example may be an alkylene group having 1 to 6 carbon atoms specifically, Y _a1 and Y _a2 may be a cyan group, a halogen, a hydroxyl group, or an amine group irrespective of each other. R _b may be an alkylene group having 1 to 16 carbon atoms, for example, an alkylene group having 1 to 6 carbon atoms, and Y _b may be hydrogen, a cyan group, a halogen, a hydroxyl group, or an amine group. .

X ^- is a counter anion (counter anion) Specifically, ^{^{^{F -, Cl -, Br -}}} , I -, PF 6 -, BF 4 -, Tf 2 N - (bis (trifluoromethane) sulfonimide), TfO - (trifluoromethanesulfonate) , SCN ^-, or CH ₃ COO ^- it can be.

As such, the diacetylene monomer may exhibit amphiphilic by containing an ionic functional group at one end of an aliphatic hydrocarbon chain. These diacetylene monomers may be self-assembled between the polymer chains of the matrix polymer. Specifically, aliphatic hydrocarbon chains including the diacetylene groups of the diacetylene monomers may be disposed adjacent to each other by van der Waals interaction, and ionic functional groups may be disposed adjacent to each other on one side thereof.

The matrix polymer may be a polar polymer having a dipole moment (ie, having a dipole moment greater than zero) or a polar polymer. Specifically, the matrix polymer has a polar functional group or an electron withdrawing group (or electron donating group) in the main chain or side chain, for example, an ether group, a carboxyl group, an alcohol group, an amine group, an imine group, an amide group, a blood group in the main chain or side chain. Polyethylene oxide, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl chloride which has a rollidone group, a chloride group, or a benzene group. Polyacrylates, polystyrenes, or copolymers thereof. Furthermore, the matrix polymer may have a hydrophilic functional group in its main chain or side chain, and the hydrophilic functional group may be a polarized or charged functional group. Such hydrophilic polymers may be polyethylene oxide, polyvinyl alcohol or polyvinylpyrrolidone.

The polymer may be contained in an amount of about 1.5 to 3.5, specifically about 2 to 3 parts by weight, based on 1 part by weight of the diacetylene monomer. The first solvent and the second solvent may be mixed with each other, and may be volatile solvents. As an example, the first solvent and the second solvent may be the same volatile organic solvent. Specifically, the first solvent and the second solvent may be a polar, amphiphilic solvent, or a nonpolar solvent having a dipole moment (non-zero dipole moment) irrespective of each other. These solvents may vary depending on the type of diacetylene monomer.

The polymer patch (A) having the diacetylene monomers may further include a hydrophilic oligomer or a plasticizer. In this case, the hydrophilicity or flexibility of the polymer patch (A) can be further improved. The hydrophilic oligomer may be polyethylene glycol having a molecular weight (Mn) of 100 to 1000. Such polyethylene glycol may be contained in an amount of about 0.125 to 0.5 parts by weight based on 1 part by weight of the diacetylene monomer.

In one example, the diacetylene monomer represented by Formula 1 may be represented by the following formula (3).

[Formula 3]

A, b, R ⁻ , and M ⁺ of Formula 3 may be the same as a, b, R ⁻ , and M ⁺ described in Formula 1, respectively. The diacetylene monomer may be an alkali metal salt of PCDA (10,12-pentacosadiynoic acid), an alkali metal salt of TCDA (10,12-tricosadiynoic acid), or an alkali metal salt of HCDA (8,10-heneicosadiynoic acid).

When using the diacetylene monomer represented by Formula 1, the first solvent may be a polar or amphiphilic solvent. The second solvent may be an amphiphilic solvent or water. In one example, the first solvent is an amphiphilic solvent and the second solvent is water, and in another example, both the first solvent and the second solvent may be an amphiphilic solvent or the same solvent. Amphiphilic solvents include, for example, acetone; Alcohol, such as methanol, ethanol, isopropanol, dimethyl ether, or tetrahydrofuran (THF). On the other hand, the matrix polymer may be polyethylene oxide, polyvinyl alcohol, polyvinyl chloride or polyvinylpyrrolidone.

As the diacetylene monomer represented by Formula 1, an alkali metal hydroxide solution and a diacetylene carboxylic acid monomer solution are prepared as an example of an alkali metal salt solution, and the alkali metal hydroxide aqueous solution is used as the diacetylene carboxylic acid monomer solution. It can be prepared by mixing while dropping drops. The alkali metal salt may be mixed in the range of 0.1 to 3 moles with respect to the diacetylene carboxylic acid monomer, and preferably in 0.5 to 2 moles. In addition, the alkali metal hydroxide and the diacetylene carboxylic acid monomer may form the diacetylene monomer represented by Chemical Formula 1 by an acid-base reaction.

In another example, the diacetylene monomer represented by Formula 1 may be represented by the following Formula 4.

[Formula 4]

Of Formula _{4 a, b, L 1,} c, e, R +, and X ^- is described _{a, b, L 1, c} , e, R +, and X in the formula ⁽¹⁾ may be the same, respectively and.

When the diacetylene represented by Formula 4 uses a monomer, the first solvent may be a nonpolar solvent. The second solvent may also be a nonpolar solvent. In one example, the first solvent and the second solvent may be the same solvent. The nonpolar solvent may be, for example, chloroform as a nonpolar solvent having a dipole moment. On the other hand, the matrix polymer may be polyethylene oxide.

Polydiacetylene Containing polymer patch

Referring back to FIG. 1, the polymer patch (A) is irradiated with light to photopolymerize the diacetylene monomers to form polydiacetylene, thereby forming a polymer patch (B) having polydiacetylene in the polymer matrix. have.

The light may be ultraviolet rays, specifically, 250-260 nm ultraviolet rays, specifically 254 nm ultraviolet rays, or gamma rays, and may be irradiated for 1 to 300 seconds. As a result, polyacetylene can be formed by photopolymerizing self-assembled and adjacently disposed diacetylene monomers.

The polydiacetylene may have a repeating unit represented by the following Formula 5.

[Formula 5]

In Formula 5, a, b, c, d, L ₁ , L ₂ , and IG may be the same as each of a, b, c, d, L ₁ , L ₂ , and IG of Formula 1.

The polymer patch (B) containing such polydiacetylene exhibits a maximum absorption wavelength at about 600 nm to 680 nm, specifically about 620 nm to 660 nm, for example about 640 nm, which indicates blue color. This is because it is a conjugated polymer with a highly π-conjugated backbone due to alternating double and triple bonds.

In one example, the polydiacetylene may have a repeating unit represented by the following formula (6). It may be a polydiacetylene polymerized diacetylene monomer represented by the formula (3).

[Formula 6]

In Formula 6, a, b, R ⁻ , and M ⁺ may be the same as each of a, b, R ⁻ , and M ⁺ of Formula 1 above.

In an example, the polydiacetylene may have a repeating unit represented by the following Chemical Formula 7. It may be polydiacetylene polymerized diacetylene monomer represented by the formula (4).

[Formula 7]

The formula (7) of _{a, b, L 1, c} , e, R +, and ^X-is the _{a, b, L 1, c} , e, R +, and the general formula X 1 ^- may be the same with each.

Polydiacetylene Containing polymer patches Water discoloration reaction

Referring back to FIG. 1, when moisture is applied to the polydiacetylene-containing polymer patch (B), the polydiacetylene in contact with moisture is geometrically deformed to exhibit a reddish color through π-conjugated main chain structure breakdown. (C). In other words, it may show a hydrochromic reaction. Specifically, in case of contact with moisture, polydiacetylene has a maximum absorption wavelength of about 490 to about 590 nm, specifically, 520 to about 570 nm, for example, blue shifted to 540 nm. Can change. At the same time, the hydrochromic polydiacetylene may generate fluorescence. Accordingly, the polymer patch (B) containing the polydiacetylene may also be referred to as a hydrochromic patch.

This water discoloration is supposed to form voids as the diacetylene monomer which remained as a monomer without forming a polymer is dissolved in water, and this causes polydiacetylene to exhibit geometric deformation, but is not limited to this theory.

As described above, the polydiacetylene-containing polymer patch (B) exhibits a color change by contact with moisture (liquid or gas), and thus, may function sufficiently as a moisture sensor, specifically, a hydrochromic patch. Specifically, humidity may be sensed using the hydrochromic patch, or moisture in an organic solvent may be sensed. Further, the hydrochromic patch may be discolored from blue to red even by a very small amount of water (nano litres) coming out of the pores, and thus may be used as a fingerprint recognition application or a pores mapping paper. Specifically, it is possible to effectively map the pores of the entire body area, such as palms, soles, back, face, as well as fingers, thereby expanding the application field of the existing technology. In this way, it is possible to analyze the biological information such as the distribution of the pores of the body, it can be used in the medical field, beauty field, or criminal investigation field. Specifically, it may be used in the medical field, such as active pores distribution analysis or analysis of age-specific pores activity of hyperhidrosis patients, the cosmetic field for the development of deodorant or sweat inhibitors, and the field of criminal investigation through analysis of the pores map of fingerprints. In addition, the elution position can be accurately identified through color or fluorescence changes in response to moisture eluted from various water pipes, microcracked buildings, and experimental equipment, and thus can be widely used for commercial purposes. In addition, the polymer patch (B) can produce not only hard hydrochromic patches, but also improved hydrochromic patches with improved ductility, by adjusting the physical properties of the matrix polymer. It can be usefully used for detecting moisture of the skin.

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.

<< 다이아세틸렌Diacetylene 단량체 Monomer 합성예들Synthesis Examples >>

Synthesis Example 1: DA- Im [3- ( Cyanomethyl ) -1- (3- ( pentacosa -10,12- diynamido ) propyl) -1H-imidazol-3-ium bromide]

In 20 mL of methylene chloride, PCDA (10,12-pentacosadiynoic acid, 0.75 g, 2 mmol), N-hydrosuccinimide (NHS, 0.35 g, 3 mmol), EDC (1-ethyl-3- (3-dimethylaminopropyl) ) carbodiimide, 0.77 g, 4 mmol) was dissolved at room temperature overnight. Thereafter, the mixture was concentrated in vacuo, and the residue was dissolved in ethyl acetate again, and the solution was separated with a separatory funnel with water to obtain an organic solution layer. The organic solution was dehydrated and concentrated in vacuo to give white powdery PCDA-NHS (2,5-dioxopyrrolidin-1-yl pentacosa-10,12-diynoate). The PCDA-NHS (0.94 g, 2 mmol) and triethylamine (TEA, 0.51 g, 5 mmol) were dissolved in 10 ml of methylene chloride to obtain a first solution, and in 10 ml of methylene chloride in the first solution. A second solution obtained by dissolving 1- (3-aminopropyl) imidazole (1- (3-aminopropyl) imidazole, 0.38 g, 3.00 mmol) was added thereto, followed by stirring at room temperature overnight. After that, it was concentrated in vacuo to give a residue, which was put into silica gel column chromatography (methylene chloride / methanol, 96/4) to give N- (3- (1H-imidazole) as a white solid. -1-yl) propyl) pentacosa-10,12-diyneamide (N- (3- (1H-imidazol-1-yl) propyl) pentacosa-10,12-diynamide, 0.77 g, 80%) was obtained. .

N- (3- (1H-imidazol-1-yl) propyl) pentacosa-10,12-diyneamide (0.70 g, in 20 ml of acetonitrile containing bromoacetonitrile (0.28 g, 2.32 mmol) 1.45 mmol) was added and refluxed with stirring overnight. After that, it was concentrated in vacuo to give a solid, which was washed three times with hexane to give DA- Im (0.75 g, 86%) as a yellowish powder. mp: 89 ° C., IR (KBr, cm −1): ν max 611, 624, 652, 719, 757, 860, 927, 1022, 1168, 1382, 1423, 1453, 1467, 1538, 1642, 1651, 2267, 2849, 2919, 3070, 3094, 3255, 3358. 1 H NMR (600 MHz, dimethyl sulfoxide- d 6, δ): 9.39 (s, 1H), 7.96 (t, J = 6 Hz, 1H), 7.95 (t , J = 1.8 Hz, 1H), 7.93 (t, J = 1.8 Hz, 1H), 5.63 (s, 2H), 4.22 (t, J = 6.6 Hz, 2H), 3.05 (q, J = 6 Hz, 2H ), 2.26 (t, J = 7.2 Hz, 4H), 2.06 (t, J = 7.8 Hz, 2H), 1.92 (quint, J = 6.6 Hz, 2H), 1.50-.40 (m, 6H), 1.30- .23 (m, 26H), 0.85 (t, J = 7.2 Hz, 3H); 13 C NMR (75 MHz, CDCl 3, δ): 174.82, 137.88, 123.53, 123.22, 114.08, 65.50, 65.44, 48.29, 38.71, 36.70, 35.77, 32.14, 29.88, 29.86, 29.72, 29.58, 29.34, 29.24, 29.11 , 28.60, 26.04, 22.92, 19.44, 14.37.

Synthesis Example 2: DA-Cs [Cesium salt of 10,12- pentacosadiynoic acid] synthesis

0.187 g of CsOH was dissolved in 0.4 mL of Di-deionized water, 0.4658 g of PCDA (10,12-pentacosadiynoic acid) was dissolved in 10 mL of THF (tetrahydrofuran, tetrahydrofuran), and the aqueous CsOH solution was dissolved in PCDA solution. Drop by drop into and mix (5 wt% solution). It was stirred for 1 hour at room temperature to mix evenly to prepare a transparent homogeneous solution DA-Cs solution.

<수변색 패치 제조예>Hydrochromic patch manufacturing example

Hydrochromic patch preparation example 1

DA-Im was dissolved in chloroform to prepare a chloroform solution (hereinafter referred to as DA-Im solution) containing 2wt% of DA-Im. On the other hand, PEO (poly (ethylene oxide), MW = 100K, 200K, 300K, 600K, 1000K, 4000K), PVP (poly (vinyl pyrrolidone), MW = 360K), PMMA (poly (methyl methacrylate), MW = ca. 120K), PVC (poly (vinyl chloride), MW = ca. 43,000, average MW = ca. 22,000), and PS (polystyrene, MW = 280,000) dissolved in chloroform containing 5wt% of polymer A chloroform solution (hereinafter referred to as polymer solution) was prepared. The DA-Im solution and the polymer solution were mixed at a volume ratio of 1: 1, sonicated for 20 minutes, and then cast on a glass petri dish. Thereafter, the film obtained by drying at 2 ° C. for 12 hours was peeled off to obtain a polymer film containing DA-Im. Thereafter, DA-Im was polymerized into a polymer film containing DA-Im by UV irradiation (254 nm, 1 mWcm-2) for 10 seconds to obtain a polymer film containing PDA-Im.

Hydrochromic patch preparation example 2

PEO (poly (ethylene oxide), MW = 200K), PVP (poly (vinyl pyrrolidone), MW = 360K), PVA (poly (vinyl alcohol), MW = 89K), and PVC (poly (vinyl chloride), MW = 43 K, average MW = ca. 22 K) was dissolved in the solvent described to prepare a 5 wt% polymer solution. Meanwhile, the DA-Cs solution, which is a 5 wt% transparent homogeneous solution obtained in the diacetylene monomer synthesis example 2, and the polymer solution were mixed at a volume ratio of 1: 1, sonicated for 20 minutes, and then cast on a glass petri dish. It was. Thereafter, the film obtained by drying at 2 ° C. for 12 hours was peeled off to obtain a polymer film containing DA-Cs. Thereafter, the polymer film containing DA-Cs was polymerized with DA-Cs by UV irradiation (254 nm, 1 mWcm-2) for 10 seconds to obtain a polymer film containing PDA-Cs.

Hydrochromic patch preparation example 3

0.20 ml of PEG (MW = 0.6K), 0.15 ml (Preparation 3-2), 0.10 ml (Preparation Example) 3-3) or a polymer film containing PDA-Cs was obtained in the same manner as in Preparation Example 2 except that the polymer solution was prepared by mixing 0.05 ml (Preparation Example 3-4).

수변색 패치 제조예Hydrochromic patch manufacturing example		다이아세틸렌 단량체 용액Diacetylene Monomer Solution		고분자 용액Polymer solution
수변색 패치 제조예Hydrochromic patch manufacturing example		다이아세틸렌 단량체Diacetylene Monomer	용매menstruum	고분자Polymer	용매menstruum
1One	1-1a1-1a	DA-ImDA-Im	클로로포름chloroform	PEO (MW = 100K)PEO (MW = 100K)	클로로포름chloroform
	1-1b1-1b			PEO (MW = 200K)PEO (MW = 200K)
	1-1c1-1c			PEO (MW = 300K)PEO (MW = 300K)
	1-1d1-1d			PEO (MW = 600K)PEO (MW = 600K)
	1-1e1-1e			PEO (MW = 1000K)PEO (MW = 1000K)
	1-1f1-1f			PEO (MW = 4000K)PEO (MW = 4000K)
	1-21-2			PMMA (MW = 120K)PMMA (MW = 120K)
	1-31-3			PS (MW= 280K)PS (MW = 280K)
	1-41-4			PVC (MW = 430K)PVC (MW = 430K)
22	2-12-1	DA-CsDA-Cs	THF, H2OTHF, H2O	PEO (MW = 200K)PEO (MW = 200K)	H2OH2O
	2-22-2			PVP (MW = 360K)PVP (MW = 360K)	H2OH2O
	2-32-3			PVA (MW = 89K)PVA (MW = 89K)	H2OH2O
	2-42-4			PVC (MW = 430K)PVC (MW = 430K)	THFTHF
33	3-13-1			PVP (MW = 360K) +PEG (MW = 0.6K)PVP (MW = 360K) + PEG (MW = 0.6K)	H20H20
	3-23-2
	3-33-3
	3-43-4

Referring to FIG. 2, the PEO film (a) containing DA-Im was a film containing DA-Im and PEO in a weight ratio of 1: 2.5 and having a colorless opaque thickness of about 10 μm. On the other hand, the film (b) irradiated with UV showed blue color. The blue color may mean that diacetylene (DA-Im) is polymerized to form polydiacetylene (PDA-Im). In addition, it can be seen that both the PEO film (a) containing DA-Im and the PEO film (b) containing PDA-Im are flexible films and do not produce visible cracks by bending.

Referring to FIG. 3, the PEO film (PEO + PDA) containing PDA-Im compared with the PEO film itself (PEO) and the PEO film (PEO + DA) containing DA-Im conjugated with a 1453 cm ⁻¹ peak representing the conjugated alkenes. It can be seen that the 2080 cm ^-1 peak representing the gated alkyne is characteristically represented. From this, it can be seen that the polydiacetylene in the PEO film containing PDA-Im has a highly π-conjugated backbone by alternating double bonds and triple bonds.

Referring to FIG. 4, the PEO film containing PDA-Im obtained according to Hydrochromic patch Preparation Example 1-1b shows water-promoted blue-to-red color change by water (a) After the moisture had dried, it did not return to blue again. On the other hand, in the UV-vis absorption spectrum, the maximum absorption wavelength before exposure to moisture is about 636 nm, the maximum absorption wavelength is shifted to about 537 nm after exposure to moisture (c). In addition, the Raman spectrum shows that the 2080 and 1453 cm ^-1 bands corresponding to the alkyne-alkene bands were shifted to 2120 and 1515 cm ^-1 bands, respectively, after hydration compared to before hydration. Can be. These results may mean that the distortion occurs in the main chain of the polydiacetylene due to moisture, so that some distortion is generated in the superposition of the π-orbital array (b).

<땀구멍 매핑(sweat pore mapping)예><Sweat pore mapping example>

The degree of mapping of the pores was observed by gently contacting the fingertips on the PEO film containing PDA-Im obtained in Preparation Example 1-1b.

FIG. 5 is a photograph showing an optical image after a finger is touched on a PEO film containing PDA-Im obtained according to hydrochromic patch Preparation Examples 1-1a to 1-1f. Fluorescence microdots showing sweat-secreting active pores were analyzed using a fluorescence spectrometer (510-550 nm excitation).

Referring to FIG. 5, a red fluorescence image expressed by sweat at the pore position may be confirmed. This is evident throughout the PEO films containing PDA-Im formed using PEOs with different molecular weights of 100K to 4000K. From this it can be seen that it is possible to implement a flexible yet moisture-sensitive hydrochromic patch irrespective of the molecular weight of the matrix polymer. However, when a low molecular weight (eg 100 K) matrix polymer is used, there may be a slight possibility that the hydrochromic film is torn, and when a high molecular weight (eg 300 K or more) matrix polymer is used, Due to the viscosity, there may be some difficulties in obtaining a film of uniform thickness.

FIG. 6 is a photograph showing an optical image after contacting the nose, the entire palm, and the sole of the foot on a PEO film containing PDA-Im obtained in Preparation Example 1-1b. Fluorescence microdots showing sweat-secreting active pores were analyzed using a fluorescence spectrometer.

Referring to FIG. 6, the PEO film containing PDA-Im may be in contact with the nostril (a), the entire palm (b) including the depression (d) of the palm, and the depression (c) of the sole. In addition, its flexibility allows almost perfect contact with the curved parts of the human body, greatly improving the pores mapping efficiency.

Figure 7 is a photograph showing the degree of water discoloration according to the relative humidity of the PEO film containing PDA-Im obtained according to the hydrochromic patch Preparation Example 1-1b. Specifically, it shows the degree of water discoloration in a state exposed for 5 minutes at a specific relative humidity.

Referring to FIG. 7, the PEO film containing PDA-Im obtained according to the hydrochromic patch Preparation Example 1-1b did not discolor even when exposed for 5 minutes at a relative humidity of 20 to 95%. However, when exposed to 100% relative humidity, it immediately turned red. From this, it can be seen that the hydrochromic patch according to the present embodiment is hydrochromic only when directly exposed to water without being greatly affected by the humidity of the surrounding environment.

Referring to FIG. 8, when PEO, PMMA, PS, and PVC are used as the matrix polymer, all of them show a blue film, indicating that DA-Im is polymerized by UV to form PDA-Im. This may mean that DA-Im may self-assemble in the polymers. In addition, when PS and PVC were used as the matrix polymer, it was observed that cracking or cracking occurred when a bending force was applied, but there was no problem in indicating water discoloration.

On the other hand, when PEO is used as the matrix polymer when the finger is in contact with the polymer film containing PDA-Im, finger fingerprints including pores appear clearly in both optical and fluorescence microscope images, whereas PMMA and Slight pores were observed with PVC and no pores with PS. This was estimated according to the degree of hydrophilicity of the matrix polymer. In other words, PS is a very hydrophobic polymer, and PMMA and PVC are also known as hydrophobic polymers.

Referring to FIG. 9, when PEO, PVP, PVA, and PVC are used as the matrix polymer, all of them show a blue film, and it can be seen that DA-Cs is polymerized by UV to form PDA-Cs. This may mean that DA-Cs can be self-assembled in the polymers. In addition, in all cases, flexibility was excellent, such as no bending or cracking when bending force was applied.

10 is a photograph showing the degree of water discoloration according to the relative humidity of the polymer film containing the PDA-Cs obtained according to the hydrochromic patch Preparation Examples 3-1 to 3-4. Specifically, it shows the degree of water discoloration in a state exposed for 5 minutes at a specific relative humidity.

Referring to FIG. 10, it can be seen that as the content of PEG having hydrophilicity and hygroscopicity is increased in the state of using PVP as the matrix polymer, the relative humidity value in which water discoloration occurs is reduced. Specifically, when 0.05 ml of PEG and 0.10 ml were added, water discoloration began to appear at 70% RH, and when 0.15 ml of PEG appeared to start at water discoloration at 60% RH. When 0.20 ml of Hg added, water discoloration began to appear at 50% RH.

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

Polymer matrix; And

Hydrochromic polymer patch having a polydiacetylene having a repeating unit represented by the formula (5) located in the polymer matrix:

[Formula 5]

In Chemical Formula 5,

a is an integer from 1 to 20, b is an integer from 1 to 20,

L 1 is
,
,
,
,
,
,
,
, or
E, E 1 , and E 2 are O or S irrespective of each other, c is an integer from 0 to 2,

L 2 is an alkylene having 1 to 10 carbon atoms or an arylene group having 5 to 12 carbon atoms, d is an integer of 0 to 1,

And, - IG is an ionic functional group, R - M +, or R + X

R − is a carboxylate anion, M + is an alkali metal cation,

R + is a quaternary ammonium group, X - is F -, Cl -, Br - , I -, PF 6 -, BF 4 -, Tf 2 N - (bis (trifluoromethane) sulfonimide), TfO - (trifluoromethanesulfonate), SCN - or CH 3 COO - it is.
The method of claim 1,

The polymer is a hydrochromic polymer patch of polyethylene oxide, polyvinyl alcohol or polyvinylpyrrolidone.
The method of claim 1,

The hydrochromic polymer patch containing about 1.5 to 3.5 parts by weight of the polymer relative to 1 part by weight of the polydiacetylene.
The method of claim 1,

Hydrochromic polymer patch further comprising a hydrophilic oligomer or plasticizer.
The method of claim 1,

The polydiacetylene having a repeating unit of Formula 5 is a polydiacetylene having a repeating unit represented by the following Formula 6 hydrochromic polymer patch:

[Formula 6]

In Formula 6, a, b, R -, and M + is of Formula 5 a, b, R - and the like, respectively, and M +.
The method of claim 5,

Wherein M + is cesium ion or rubinium ion.
The method of claim 5,

The polymer is a hydrochromic polymer patch of polyethylene oxide, polyvinyl alcohol or polyvinylpyrrolidone.
The method of claim 1,

The polydiacetylene having a repeating unit represented by Formula 5 is a polydiacetylene having a repeating unit represented by Formula 7 below:

[Formula 7]

Formula 7, a, b, L 1, c , e, R +, and X - is of Formula 5 a, b, L 1, c, e, R +, and X - and the like, respectively.
The method of claim 8,

R + is a hydrochromic polymer patch of N + -R 1 -heterocyclic quaternary ammonium represented by Formula 2a:

[Formula 2a]

In Chemical Formula 2a,

* Is a combination,

Ring B is a 5-membered or 6-membered heterocyclic compound having 1 to 3 N and 0 to 1 as O-membered hetero member, and a saturated or unsaturated heterocyclic compound,

R 1 is cyanoalkyl having 1 to 16 carbon atoms, haloalkyl having 1 to 16 carbon atoms, hydroxyalkyl having 1 to 16 carbon atoms, or aminoalkyl having 1 to 16 carbon atoms.
The method of claim 9,

Of formula 2a N + -R 1 - heterocyclic quaternary ammonium is the formula 2b or to N + -R 1 shown in Chemical Formula 2c - number of heterocyclic quaternary ammonium polymer discolored patches:

[Formula 2b]

[Formula 2c]

In Formula 2b, Ring C is a 5-membered or 6-membered unsaturated heterocyclic compound having N of 2 to 3 as a hetero member,

In Formula 2c, Ring D is a 5-membered or 6-membered unsaturated heterocyclic compound having N of 2 to 3 as a hetero member,

R 1 and R 1 ′ are each independently cyanoalkyl having 1 to 16 carbon atoms, haloalkyl having 1 to 16 carbon atoms, hydroxyalkyl having 1 to 16 carbon atoms, or aminoalkyl having 1 to 16 carbon atoms.
The method of claim 10,

The N + -R 1 -heterocyclic quaternary ammonium is N + -R 1 -azolium, N + -R 1 -azinium, or N + -R 1 R 2 -piperazini Hydrochromic polymer patch that is piperazinium.
The method of claim 11,

The N + -R 1 -azolium is N + -R 1 -diazolium or N + -R 1 -triazolium (hydroachromic polymer patch).
The method of claim 12,

The N + -R 1 - imidazolium diamond is to N + -R 1 represented by Formula 2-1-imidazolidin N + -R 1 represented by the following Formula 2-2 or imidazolium-pyrazolidine may imidazolium discoloration polymer patches.

In Formulas 2-1 and 2-2, R a is an alkylene group having 1 to 16 carbon atoms,

Y a is a cyan group, a halogen, a hydroxy group, or an amine group.
The method of claim 1,

The hydrochromic polymer patch may be blue.
The method of claim 1,

The hydrochromic polymer patch is a hydrochromic polymer patch.
Mixing the diacetylene monomer solution containing the diacetylene monomers represented by Formula 1 in the first solvent and the polymer solution containing the polymer in the second solvent;

Molding the mixed solution into a film;

Drying the film to form a polymer patch comprising the matrix of the polymer and the diacetylene monomers self-assembled therein; And

Method for producing a hydrochromic polymer patch comprising irradiating the polymer patch with ultraviolet or gamma rays to photopolymerize the diacetylene monomers to form a polydiacetylene.

[Formula 1]

In Chemical Formula 1,

a is an integer from 1 to 20, b is an integer from 1 to 20,

L 1 is
,
,
,
,
,
,
,
, or
E, E 1 , and E 2 are O or S irrespective of each other, c is an integer from 0 to 2,

L 2 is an alkylene having 1 to 10 carbon atoms or an arylene group having 5 to 12 carbon atoms, d is an integer of 0 to 1,

And, - IG is an ionic functional group, R - M +, or R + X

R − is a carboxylate anion, M + is an alkali metal cation,

R + is a quaternary ammonium group, X - is F -, Cl -, Br - , I -, PF 6 -, BF 4 -, Tf 2 N - (bis (trifluoromethane) sulfonimide), TfO - (trifluoromethanesulfonate), SCN - or CH 3 COO - it is.
The method of claim 16,

The first solvent and the second solvent is a hydrochromic polymer patch manufacturing method that is a volatile solvent mixed with each other.
The method of claim 17,

The first solvent and the second solvent is a non-polar solvent having a polar solvent, an amphiphilic solvent or a dipole moment irrespective of each other.
The method of claim 16,

The diacetylene monomer represented by Chemical Formula 1 is a diacetylene monomer represented by Chemical Formula 3:

[Formula 3]

Of Formula 3 a, b, R -, and M + is of the formula 1 a, b, R - and the like, respectively, and M +.
The method of claim 16,

The diacetylene monomer represented by Chemical Formula 1 is a diacetylene monomer represented by Chemical Formula 4:

[Formula 4]

Of Formula 4 a, b, L 1, c, e, R +, and X - is of the formula 1 a, b, L 1, c, e, R +, and X - and the like, respectively.