KR101356129B1 - Manufacuring method of template polymer and conducting polymer composite including conductive polymer droplet in template polymer, and template polymer and conducting polymer composite made by the same - Google Patents

Abstract

The present invention relates to a method for producing a composite composition comprising droplets of a conductive polymer in a mold polymer matrix, and to a composite composition comprising droplets of conductive polymers in a mold polymer matrix produced thereby.
According to the present invention, a method for preparing a composite composition including droplets of a conductive polymer in a template polymer matrix may be performed by controlling the size and amount of nanoparticles functionalized with the copolymer to be mixed, thereby controlling droplets of the conductive polymer in the template polymer matrix. It is possible to control the size of the droplets, thereby minimizing and optimizing the addition amount of the nanoparticles functionalized with the copolymer in preparing the composite composition including droplets of the conductive polymer in the template polymer matrix.

Description

TECHNICAL FIELD OF THE INVENTION A method for producing a composite composition comprising droplets of a conductive polymer in a mold polymer matrix, and a composite composition comprising droplets of conductive polymers in a mold polymer matrix prepared by the same POLYMER, AND TEMPLATE POLYMER AND CONDUCTING POLYMER COMPOSITE MADE BY THE SAME}

The present invention relates to a method for producing a composite composition comprising droplets of a conductive polymer in a template polymer matrix, and to a composite composition comprising droplets of conductive polymers in a template polymer matrix produced thereby.

π-conjugated polymers are expected to be possible for future-oriented applications such as the electronics industry. They are attracting attention due to their electrical properties, mechanical flexibility, and relatively easy manufacturing methods. In particular, it is known that control of the electrical conductivity of polymers is possible if a well-aligned polymer with less conjugation interference defects can be produced. However, existing electroconductive polymers have only a conductive property and have a disadvantage of being insoluble and not easy to process.

In addition to the purpose of improving the mechanical, thermal, and electrical properties of these electrically conductive polymers, many studies have been conducted to impart new functions that cannot be obtained with a single material. Research is being done.

By introducing nanoparticles as a surfactant which can improve the dispersibility between the electrically conductive polymer and the polymer resin, the conductive polymers form a continuous conductive network in the template polymer matrix, thereby hopping electrons. Attempts have been made to improve conductivity by acting as a passageway for the tunneling effect.

In the composite material of the electrically conductive polymer and the polymer resin, the state of the microstructure plays an important role in improving performance and expressing new functions. For example, the mechanical, thermal, and electrical properties obtained vary greatly depending on whether one component constituting the material forms or is dispersed in a continuous phase inside the material.

The second phase partially introduced into the composite material forms a continuous phase, and the state of the percolation structure (the structure in which the second phase in the form of particles continuously contacts and flows electricity) that determines the electrical characteristics and the second phase. It is known that the critical volume indicating the onset of percolation structure formation by the phase is highly dependent on the shape and size of the second phase. The minimum amount of conductive filler particles required to form a continuous conductive network is the electrical threshold.

In the composite material between the conductive polymer and the polymer, the higher the content of the surfactant added to improve the dispersibility, the more difficult the manufacturing process due to the increase in viscosity, the lower the physical properties and the higher the cost, so that the technical aspects and economic Considering the aspects, it is desirable to lower the electrical critical point of the surfactant added as much as possible.

Factors affecting the electrical critical point include particle type, size and shape, melt viscosity of polymer, process conditions, dispersibility of particles in polymer, and interfacial energy between polymer and particles. In order to improve the dispersibility and interfacial adhesion of the conductive polymer particles in the polymer matrix, studies to lower the electrical critical point have been actively conducted.

It is an object of the present invention to provide a method for producing a composite composition comprising droplets of a conductive polymer in a template polymer matrix.

The present invention also aims to provide a composite composition comprising droplets of a conductive polymer in a template polymer matrix produced by the process of the present invention.

The present invention for the above purpose,

Preparing nanoparticles functionalized with a copolymer; Preparing a template polymer;

Preparing a conductive polymer; And

Mixing the nanoparticles functionalized with the copolymer, the template polymer, and the conductive polymer; And

It provides a method for producing a composite composition comprising a droplet of a conductive polymer in a mold polymer matrix comprising the step of annealing the nanoparticles functionalized with the copolymer, the template polymer, and the conductive polymer mixture.

In the method for producing a composite composition comprising droplets of a conductive polymer in the template polymer matrix of the present invention, conductive polymer droplets formed in the template polymer matrix by the size of the nanoparticles functionalized with the copolymer It characterized in that to adjust the size of.

In the method for producing a composite composition comprising a droplet of a conductive polymer in the template polymer matrix of the present invention, the size of the nanoparticles functionalized with the copolymer is characterized in that 2 nm to 15 nm.

According to the present invention, a method for preparing a composite composition including droplets of a conductive polymer in a mold polymer matrix is performed by controlling the size and amount of nanoparticles functionalized with a copolymer, thereby reducing droplets of the conductive polymer in the mold polymer matrix. It is possible to control the size of, that is, in the method for producing a composite composition comprising a droplet (droplet) of the conductive polymer in the template polymer matrix of the present invention, the nanoparticles functionalized with the copolymer, the template polymer, and the As the addition ratio of the nanoparticles functionalized with the copolymer in the step of mixing the conductive polymer is characterized in that the droplet size of the conductive polymer is reduced.

In a composite composition comprising droplets of a conductive polymer in the template polymer matrix of the present invention, the nanoparticles functionalized with the copolymer are mixed at 0.1 to 1% based on the volume of the composite composition. do. When the nanoparticles functionalized with the copolymer are mixed to 0.1 volume% or less, a portion that does not surround the conductive polymer may occur. When the mixture is mixed to 1 volume% or more, the effect of increasing the mixing amount does not occur.

In a composite composition comprising droplets of a conductive polymer in the template polymer matrix of the present invention, the template polymer is polystyrene, nylon, polyethylene, polyisoprene, sbs rubber, polydicyclopentadiene, polytetrafluoroethylene, Poly (phenylene sulfide), silicone, aramid, cellulose, rayon, poly (methyl methacrylate), poly (vinylidene chloride), poly (vinylidene fluoride), carbon fiber, polyisobutylene, polychloroprene, poly Butadiene, polypropylene, poly (vinyl chloride), poly (vinyl acetate), polyvinylpyrrolidone, polycyanoacrylate, polyacrylonitrile, poly (aryleneethynylene), poly (phenyleneethynylene) , Polyaniline, polyphenylene, ethylene vinyl alcohol, fluoroplastics, ionomers, polyacrylates, polybutadiene, polybutyl , Polyethylene, polyethylene chlorate, polymethylpentene, polypropylene, polystyrene, polyvinylchloride, polyvinylidene chloride, polyamide, polyamide-imide, polyaryletherketone, polycarbonate, polyketone, polyester , Polyetheretherketone, polyetherimide, polyethersulfone, polyimide, polyphenylene oxide, polyphenylene sulfide, polyphthalamide, polysulfone, polyethylene terephthalate, epoxy resin, polyurethane, and combinations thereof It includes one selected from the group consisting of.

In the composite composition comprising a droplet of the conductive polymer in the mold polymer matrix of the present invention, the mold polymer is characterized in that it comprises polystyrene.

In the composite composition comprising a droplet of the conductive polymer in the template polymer matrix of the present invention, the conductive polymer is polytriphenylamine, polyacetylene (PA), polythiophene (PT), poly ( Poly (3-alkyl) thiophene (P3AT), polypyrrole (PPY), polyisothianapthelene (PITN), polyethylene dioxythiophene (PEDOT), polyparaphenylene vinyl Ethylene (polyparaphenylene vinylene: PPV), poly (2,5-dialkoxy) paraphenylene vinylene [poly (2,5-dialkoxy) paraphenylene vinylene], polyparaphenylene (PPP), polyparaphenylene sulfide (polyparaphenylene sulphide: PPS), polyheptadiyne (PHT), poly (3-hexyl) thiophene [poly (3-hexyl) thiophene: P3HT], and polyaniline [polyaniline: PANI]. It is characterized by more than one species.

A composite composition comprising droplets of a conductive polymer in a template polymer matrix of the present invention, wherein the conductive polymer comprises polytriphenylamine.

In a composite composition comprising droplets of a conductive polymer in a template polymer matrix of the present invention, the nanoparticles functionalized with the copolymer may be formed of gold, silver, copper, palladium, or platinum having a diameter of 1 to several hundred nm. It is characterized in that the metal nanoparticles.

In the composite composition including a droplet of the conductive polymer in the mold polymer matrix of the present invention, the volume ratio of the mold polymer and the conductive polymer when mixed is characterized in that 1: 1: 0.05 to 0.3.

The present invention also provides a composite composition comprising droplets of a conductive polymer in a template polymer matrix produced by the process of the present invention.

In the composite composition comprising a droplet of the conductive polymer in the template polymer matrix of the present invention, the peripheral portion of the droplet of the conductive polymer is characterized in that the nanoparticles functionalized with the copolymer is surrounded. Nanoparticles functionalized with the copolymer have the effect of improving the conductivity of the entire composite composition surrounding the periphery of the conductive polymer droplets.

According to the present invention, a method for preparing a composite composition including droplets of a conductive polymer in a mold polymer matrix is performed by controlling the size and amount of nanoparticles functionalized with a copolymer, thereby reducing droplets of the conductive polymer in the mold polymer matrix. It is possible to control the size of the, has the effect of minimizing and optimizing the addition amount of the nano-particles functionalized with the copolymer in the preparation of the composite composition comprising droplets of the conductive polymer in the template polymer matrix.

1 shows two Au-PSN ₃ -b-PS TEM images of 5 nm and 20 nm in diameter synthesized according to an embodiment of the present invention.
FIG. 2 illustrates a case in which the diameter prepared in Example 1 of the present invention does not include Au-PSN ₃ -b-PS prepared in Comparative Example 1 when the diameter includes 5 nm of Au-PSN ₃ -b-PS. SEM images of the conductive film are shown.
Figure 3 shows the results of measuring the size of the conductive polymer droplet dispersed in the polystyrene matrix of the template polymer prepared according to an embodiment of the present invention.
Figure 4 measures the size of the conductive polymer droplet (droplet) dispersed in the polystyrene matrix of the template polymer prepared according to an embodiment of the present invention, and shows the result.
5 is a droplet size and a comparative example according to the addition ratio of gold nanoparticles Au-PSN ₃ -b-PS functionalized with a copolymer of 5 nm and 20 nm in Examples 2 and 3 of the present invention; The relationship between the droplet size and the addition ratio of the PTPA-b-PS copolymer is shown.
FIG. 6 shows SEM images at the same addition ratios of gold nanoparticles Au-PSN ₃ -b-PS functionalized with a copolymer of 5 nm and 20 nm in Examples 2 and ₃ .

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples.

< Manufacturing example  1> Gold Nanoparticles Functionalized with Copolymers Au - PSN ₃ -b- PS Produce

0.5 mmol of 11-bromo-1-undecane-thiol, 0.5 mmol of HAuCl ₄ , 0.5 mmol of tetraoctylammonium (TOAB) and NaBH ₄ 5 mmol was used to synthesize the gold nanoparticles functionalized with a bromine group by the burst method, and the gold nanoparticles functionalized with the bromine group were dissolved in a sodium azide solution to prepare azide functionalized gold nanoparticles.

Next, a polymer was prepared by a RAFT (Reversible Addition-Fragmentation Chain Transfer) reaction. Terminally carboxylated trithiocarbonate as a RAFT agent, and RAFT polymerized monomer to the RAFT agent, to prepare a polystyrene polymer, polystyrene-poly para azide styrene block copolymer, Mn of each styrene block is 1.9, aza Mn of the id-substituted styrene block was 0.5 kg / mol.

The azide (N ₃ ) functionalized gold nanoparticles prepared above and the alkyne-PSCl-b-PS alkyne-terminated copolymer prepared above were click-reacted as shown below.

Thereafter, the chloride group was substituted with an azide group to synthesize two types of Au-PSN ₃ -b-PS having a diameter of 5 nm and 20 nm. Two synthesized Au-PSN ₃ -b-PS TEM images of 5 nm and 20 nm in diameter are shown in FIG. 1.

< Manufacturing example  2> conductive polymer Poly Triphenylamine  Produce

In order to prepare poly triphenylamine as a conductive polymer, first, vinyl triphenylamine is prepared as follows, and the vinyl triphenylamine prepared as described above is subjected to polytriphenylamine by nitroxide mediated radical polymerization. Synthesized.

< Manufacturing example  3> Mold Polymer Polystyrene Manufacturing

Polystyrene was prepared by dispersion polymerization generally known in the art using styrene monomer as a template polymer.

< Example  1>

In the solvent THF, polytriphenylamine prepared in Preparation Example 2 as a conductive polymer, polystyrene prepared in Preparation Example 3 as a template polymer was mixed in a volume ratio of 95: 5, 5 nm prepared in Preparation Example 1, A composite composition was prepared by mixing gold nanoparticles Au-PSN ₃ -b-PS functionalized with a copolymer of 20 nm to 1.0 volume%. The composite composition was spin coated onto a silicon substrate and annealed at 170 ° C. for 8 hours.

< Comparative Example  1>

A composite composition was prepared in the same manner as in Example 1, except that the gold nanoparticles coated with the copolymer were not mixed.

< Experimental Example  1-1> SEM  Photo measurement

SEM image of the conductive film when the diameter prepared in Example 1 does not include Au-PSN ₃ -b-PS prepared in Comparative Example 1 when the diameter of 5 nm Au-PSN ₃ -b-PS Was measured and the result is shown in FIG. In FIG. 2, the size of the scale bar represents 1 μm.

In FIG. 2, the case in which the diameter prepared in Example 1 includes 5 nm of Au-PSN ₃ -b-PS is generated more than when (a) does not include Au-PSN ₃ -b-PS. It can be seen that the size of the conductive polymer droplets being reduced significantly.

< Example  2>

To prepare a composite composition comprising 0.1, 0.2, 0.5, 1.0% by volume of the gold nanoparticles Au-PSN ₃ -b-PS functionalized with a copolymer having a diameter of 5 nm prepared in Preparation Example 1 to the total composite composition After annealing at 200 ° C. for 48 hours, the size of the conductive polymer droplet dispersed in the polystyrene matrix as a template polymer was measured, and the results are shown in FIG. 3.

In FIG. 3, as the ratio of Au-PSN ₃ -b-PS gold nanoparticles functionalized with a copolymer having a diameter of 5 nm is increased from 0.1% to 1.0% by volume, the conductive polymer dispersed in the polystyrene matrix which is a template polymer It was confirmed that the size of the droplets (droplet) is reduced.

< Example  3>

To prepare a composite composition comprising 0.1, 0.5, 1.0, 5.0% by volume of gold nanoparticles Au-PSN ₃ -b-PS functionalized with a copolymer having a diameter of 20 nm prepared in Preparation Example 1 to the total composite composition After annealing at 200 ° C. for 48 hours, the size of the conductive polymer droplets dispersed in the polystyrene matrix as the template polymer was measured, and the results are shown in FIG. 4.

In addition, the droplet size and PTPA-b- as a comparative example according to the addition ratio of gold nanoparticles Au-PSN ₃ -b-PS functionalized with a copolymer of 5 nm and 20 nm in Examples 2 and 3 above. The relationship of droplet size with the addition ratio of PS copolymer is shown in FIG.

In FIG. 5, as the addition ratio of the gold nanoparticles Au-PSN ₃ -b-PS functionalized with the copolymer decreases, the droplet size decreases, but the gold nanoparticles Au-PSN ₃ -b- functionalized with the copolymer decrease. It can be seen that the droplet size does not change when the addition ratio of PS is added more than 3% by volume. In addition, it can be seen that the size of the droplets generated in the case of Example 2 and Example 3 is significantly reduced compared to the comparative example.

In Example 2 and Example 3, SEM photographs were prepared in FIG. 6 at the same addition ratios of gold nanoparticles Au-PSN ₃ -b-PS functionalized with a copolymer of 5 nm and 20 nm. When the size of the gold nanoparticles functionalized with the copolymer is 5 nm, the addition of 1% by volume of the gold nanoparticles Au-PSN ₃ -b-PS functionalized with the copolymer sufficiently surrounds the vicinity of the droplets. When the size of the functionalized gold nanoparticles is 20nm, even if 1% by volume of the gold nanoparticles Au-PSN ₃ -b-PS functionalized with the copolymer it can be seen that it surrounds only a portion of the droplets (droplet) generated.

Claims (13)

Preparing nanoparticles coated with a block copolymer of AbB type;
Preparing a template polymer;
Preparing a conductive polymer; And
Mixing the nanoparticles coated with the block copolymer, the template polymer, and the conductive polymer; And
Annealing the nanoparticles coated with the block copolymer, the template polymer, and the conductive polymer mixture,
Nanoparticles coated with the block copolymer is gold, silver, copper, palladium, or platinum,
The template polymer is polystyrene, nylon, polyethylene, polyisoprene, sbs rubber, polydicyclopentadiene, polytetrafluoroethylene, poly (phenylene sulfide), silicone, aramid, cellulose, rayon, poly (methyl methacrylate). , Poly (vinylidene chloride), poly (vinylidene fluoride), carbon fiber, polyisobutylene, polychloroprene, polybutadiene, polypropylene, poly (vinyl chloride), poly (vinyl acetate), polyvinylpyrrolidone , Polycyanoacrylate, polyacrylonitrile, poly (aryleneethynylene), poly (phenyleneethynylene), polyaniline, polyphenylene, ethylene vinyl alcohol, fluoroplastics, ionomers, polyacrylates Latex, polybutadiene, polybutylene, polyethylene, polyethylene chlorate, polymethylpentene, polypropylene, polystyrene, polyvinyl chloride, Rivinylidene chloride, polyamide, polyamide-imide, polyaryletherketone, polycarbonate, polyketone, polyester, polyetheretherketone, polyetherimide, polyethersulfone, polyimide, polyphenylene jade Seeds, polyphenylene sulfides, polyphthalamides, polysulfones, polyethylene terephthalates, epoxy resins, polyurethanes, and combinations thereof,
The conductive polymer is polytriphenylamine, polyacetylene (PA), polythiophene (PT), poly (3-alkyl) thiophene [poly (3-alkyl) thiophene: P3AT], polypyrrole: PPY), polyisothianapthelene (PITN), polyethylene dioxythiophene (PEDOT), polyparaphenylene vinylene (PPV), poly (2,5-dialkoxy) paraphenylene vinylene [poly (2,5-dialkoxy) paraphenylene vinylene], polyparaphenylene [polyparaphenylene (PPP), polyparaphenylene sulphide (PPS), polyheptadiyne (PHT), poly (3-hexyl) Composite composition comprising droplets of conductive polymer in a template polymer matrix, characterized in that at least one selected from the group consisting of theophen [poly (3-hexyl) thiophene: P3HT], and polyaniline [polyaniline: PANI] Method of preparation.
The method of claim 1,
Conductive polymer droplets formed in the template polymer matrix by the size of the nanoparticles coated with the mixed block copolymer in the step of mixing the nanoparticles, the template polymer, and the conductive polymer coated with the block copolymer Method for producing a composite composition comprising a droplet of the conductive polymer in the mold polymer matrix, characterized in that the size of the control.
3. The method of claim 2,
The nanoparticles coated with the block copolymer has a size of 2 nm to 15 nm, the method of producing a composite composition comprising droplets of a conductive polymer in a template polymer matrix.
The method of claim 1,
In the step of mixing the nanoparticles coated with the block copolymer, the template polymer, and the conductive polymer, the droplet size of the conductive polymer decreases as the addition ratio of the nanoparticles coated with the block copolymer increases. A method for producing a composite composition comprising droplets of a conductive polymer in a template polymer matrix, characterized in that.
The method of claim 1,
Nanoparticles coated with the block copolymer is a method for producing a composite composition comprising droplets of a conductive polymer in a template polymer matrix, characterized in that mixed by 0.1 to 1% by volume based on the volume of the composite composition. .
delete The method of claim 1,
Wherein the template polymer comprises polystyrene and comprises droplets of conductive polymer in a template polymer matrix.
delete The method of claim 1,
The conductive polymer is a method for producing a composite composition comprising a droplet of the conductive polymer in a mold polymer matrix, characterized in that it comprises a polytriphenylamine.
delete The method of claim 1,
The volume ratio of mixing the template polymer and the conductive polymer is 1: 0.05 to 0.3 method of producing a composite composition comprising a droplet (droplet) of the conductive polymer in the mold polymer matrix, characterized in that.
A composite composition comprising droplets of a conductive polymer in a template polymer matrix prepared by any one of claims 1-5, 7, 9, and 11.
13. The method of claim 12,
Composite composition comprising a droplet of the conductive polymer in the polymer matrix matrix surrounding the droplet of the conductive polymer is surrounded by the nanoparticles coated with the block copolymer.

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