TWI414652B - Material of photoluminescence fiber - Google Patents

Abstract

A material of photoluminescence fiber is formed by utilizing an electrospinning process. The material of photo-luminescence fiber includes a conjugated photoluminescence polymer and a polymer with hydrophilc group. A diameter of the material of the photoluminescence fiber is about 50 to 3000 nm.

Description

Luminous fiber material

The present invention relates to a photoluminescence fiber material, and more particularly to a luminescent fiber and a material thereof which can be prepared by an electrospinning process.

Luminous fiber is one of the currently attracting fiber materials, which can be applied to various industries, such as personal textiles, aviation and automotive interiors, home furnishings, medical testing, outdoor products, safety facilities, and the like. As for the method for producing the luminescent fiber, a melt spinning method, a solution spinning method, a surface coating method, or the like is conventionally used. However, the fiber size produced by the above conventional method does not conform to the recent development of nanotechnology, so there is research on the production of luminescent fibers by electrospinning. However, since the luminescent fiber material is mostly a brittle material, the problem of fiber rupture often occurs when electrospinning is used.

The invention provides a luminescent fiber material, which can continuously break without breaking and the required energy for stimulating luminescence decreases, thereby saving energy.

The invention provides a luminescent fiber material which is prepared by an electrospinning process, which comprises a conjugated luminescent polymer and a polymer material having a hydrophilic group.

In one embodiment of the present invention, the conjugated luminescent polymer is selected from the group consisting of poly-3-alkylthiophenes and derivatives thereof, polyfluorenes (PF) and derivatives thereof, and poly Poly-p-phenylene and its derivatives, polycarbazole poly(carbazoles), polyfluorene poly(indoles), polyquinoline and its derivatives, poly-p-diazonium poly(quinoxalines), One of polymers of polypyridine poly(pyridines), polyphenylene vinylene (PPV) and derivatives thereof.

In one embodiment of the invention, the polyfluorenes (PF) and derivatives thereof include poly(dialkyl fluorene), poly(fluorene) -co-thiophene)), poly(fluorene-co-bithiophene), poly(fluorene-co-benzothiadiazole), poly (fluorene-co-quinoxaline), poly(fluorene-co-fluorene-co-thienopyrazine) and its derivatives Things.

In one embodiment of the invention, the polystyrene derivative comprises poly 2-methoxy-5-(2'-ethylhexyloxy)-1-4-styrene (poly(2-methoxy-) 5-(2'-ethylhexyloxy)-1,4-phenylene vinylene), MEH-PPV), poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-(1-cyanide) Poly(2-methoxy-5-(2-ethyl hexyloxy)-1,4-(1-cyano vinylenephenylene) or poly 2,5-bis(3',7'-dimethyloctyloxy) -1,4-Benzene olefin (poly-2,5-biS(3',7'-dimethyl octyloxy)-1,4-phenylene vinylene).

In an embodiment of the invention, the above polymer material having a hydrophilic group includes a water-soluble resin.

In an embodiment of the invention, the above polymeric material having a hydrophilic group comprises a water soluble polymer.

In an embodiment of the invention, the hydrophilic group comprises a carboxyl group, a hydroxyl group, a guanamine group, an amine group or an ether group.

In one embodiment of the invention, the conjugated luminescent polymer is poly(2,3-dibutoxy-1,4-phenylene vinyl) (poly(2,3-dibutoxy-1,4-phenylene vinylene) ), DB-PPV) and a polymer material having a hydrophilic group are polyvinyl pyrrolidone (PVP).

In one embodiment of the present invention, the weight ratio of the conjugated luminescent polymer to the polymer material having a hydrophilic group is from 1/99 to 99/1.

In an embodiment of the invention, the luminescent fiber material further comprises a solvent or a co-solvent. Among them, the solvent includes tetrahydrofuran (THF), toluene, chloroform or dimethyl formamide (DMF). The co-solvent is selected from the group consisting of tetrahydrofuran, toluene, chloroform and dimethylformamide, at least two solvents of which are cosolvents. Wherein, when the cosolvent is composed of tetrahydrofuran and dimethylformamide, the volume ratio of tetrahydrofuran to dimethylformamide is from 100/0 to 50/50.

In an embodiment of the invention, the luminescent fiber material has a diameter between about 50 nm and 3000 nm.

The invention adopts a phase-separated conjugated luminescent polymer and a polymer material having a hydrophilic group as a luminescent fiber material, and is combined with an electrospinning technology, thereby preparing a continuous luminescent fiber material having a core-sheath structure, and The diameter of the material produced can be as low as nanometer. Therefore, compared with the conventional coating material, the wavelength range of the absorption wavelength light becomes large, and the maximum radiation wavelength has a red shift of 2 to 24 nm, so that the luminous efficiency is high and the required energy is also low.

The above described features and advantages of the present invention will be more apparent from the following description.

1 is a schematic illustration of a luminescent fiber material in accordance with an embodiment of the present invention.

Referring to Fig. 1, a luminescent fiber material 100 of the present invention is composed of a conjugated luminescent polymer 102 and a polymer material 104 having a hydrophilic group.

In an embodiment, the conjugated luminescent polymer 102 is, for example, selected from the group consisting of poly-3-alkylthiophenes and derivatives thereof, polyfluorenes (PF) and derivatives thereof, and polyparaphenylene. (poly-p-phenylene) and its derivatives, polycarbazole poly(carbazoles), polyfluorene poly(indoles), polyquinoline and its derivatives, poly-p-diaza poly(quinoXalines), polypyridine One of polymers of poly(pyridines), polyphenylene vinylene (PPV) and derivatives thereof.

The above polyfluorenes (PF) and derivatives thereof such as poly(dialkyl fluorene), poly(fluorene-co-thiophene), poly((poly(fluorene-co-thiophene))) Poly(fluorene-co-bithiophene), poly(fluorene-co-benzothiadiazole), poly(fluorene-co-benzoporphyrin) (poly(fluorene-co-quinoxaline)), poly(fluorene-co-fluorene-co-thienopyrazine) and its derivatives. Among them, a polystyrene derivative such as poly(2-methoxy-5-(2'-ethylhexyloxy)-1-4-styrene (poly(2-methoxy-5-(2'-ethylhexyloxy)-) 1,4-phenylene vinylene), MEH-PPV), poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-(1-cyanostyrene) (poly(2-methoxy) -5-(2-ethyl hexyloxy)-1,4-(1-cyano vinylenephenylene) or poly 2,5-bis(3',7'-dimethyloctyloxy)-1,4-benzene olefin (poly -2,5-bis(3',7'-dimethyl octyloxy)-1,4-phenylene vinylene).

The "polymer material 104 having a hydrophilic group" as described in the present embodiment is, for example, a water-soluble resin or a water-soluble polymer which is soluble or swellable in water to form a solution or dispersion. The above hydrophilic group is, for example, a hydroxyl group, a carboxyl group, a decylamino group, an amine group, an ether group or the like. The molecular weight of the polymer material 104 having a hydrophilic group can be controlled, and the strength and number of the hydrophilic groups can be adjusted and reacted to have activity of a novel functional group compound. Further, the polymer material 104 having a hydrophilic group may have functions such as adhesion, film formability, lubricity, gelation property, chelating property, dispersibility, flocculation property, abrasion resistance, and thickening property. Further, the polymer material 104 having a hydrophilic group of the present invention may be a transparent or opaque material. When the polymer material 104 having a hydrophilic group is transparent, it can be retained in the luminescent fiber material 100; conversely, if the above-mentioned polymer material 104 having a hydrophilic group is opaque, the luminescent fiber can be selected. After the material 100 is made, it is removed by a further step.

In one embodiment of the present invention, the weight ratio of the conjugated luminescent polymer 102 to the polymer material 104 having a hydrophilic group is from 1/99 to 99/1.

Further, the luminescent fiber material 100 of the present invention further includes a solvent or a cosolvent; for example, the solvent includes tetrahydrofuran (THF), toluene, chloroform or dimethylformamidine. Dimethyl formamide (DMF). The co-solvent may be a co-solvent selected from the group consisting of tetrahydrofuran, toluene, chloroform and dimethylformamide, at least two of which are solvents. Wherein, when the above cosolvent is composed of tetrahydrofuran and dimethylformamide, the volume ratio of tetrahydrofuran to dimethylformamide is from 100/0 to 50/50.

Fig. 2 is a schematic view showing the preparation of a luminescent fiber material of the present invention by an electrospinning technique.

Referring to Fig. 2, first, the conjugated luminescent polymer 202 is dissolved in a suitable solvent (e.g., toluene) to be injected into the center of the nozzle, and the polymer material 204 having a hydrophilic group is injected into the peripheral portion of the nozzle. Thereafter, after the high-voltage electricity is used to electrically discharge the blended luminescent fiber material 200 from the nozzle tip to form a liquid column, the charged liquid column is subjected to a process of stretching and whipping under the action of a lateral strong electric field. The solvent on the column is continuously volatilized, the diameter of the liquid column is greatly reduced from several hundred micrometers to several tens of nanometers, and then the luminescent fiber material having a diameter of about 50 nm to 3000 nm can be obtained on the grounded collecting plate.

Further, the luminescent fiber material of the present invention can control the diameter of the fiber and its luminescent property by the blending ratio of the polymer, the kind and ratio of the single solvent or the co-solvent, the solution concentration, the additive, the applied voltage, and the flow rate.

The optical characteristics of the luminescent fiber of the present invention will be described in detail below using an experimental example.

Experimental example

In the experimental example, poly(2,3-dibutoxy-1,4-phenylethylene) (DB-PPV) having a molecular weight of about 337,000 is used as a material of a conjugated luminescent polymer, and a polymer having a molecular weight of about 1,300,000 is used. Vinyl pyrrolidone (PVP) is a polymer material having a hydrophilic group and has a weight ratio of 1/3 to 1/10. Among them, toluene is used as a solvent in poly(2,3-dibutoxy-1,4-phenylethylene), and water (about 1.5 ml) and ethanol are added to polyvinylpyrrolidone (about 0.6 g). About 8.5 ml). The experimental conditions were that the distance from the end of the nozzle to the collecting plate was about 15 cm, the high voltage was 15 to 20 KeV, the flow rate of the conjugated luminescent polymer was about 2.5 to 5 ml/h, and the flow rate was about 2.5 to 5 ml/h. Wait until the luminescent fiber material containing DB-PPV/PVP is prepared by electrospinning technology (hereinafter referred to as "Experimental Example 1"), and then part of the luminescent fiber material is used to remove the PVP, leaving only DB-PPV (hereinafter referred to as For "Experimental Example 2").

3 and 4 are the absorption spectrum and emission spectrum of Experimental Example 1, Experimental Example 2, and DB-PPV solution and a conventional DB-PPV coating film, respectively. As is apparent from Fig. 3, the present invention has a larger light absorption range than the DB-PPV coated film, either in Experimental Example 1 containing DB-PPV/PVP or Experimental Example 2 in which PVP is removed. 4, the maximum absorption wavelength of the experimental example 1 of the present invention is 2 to 24 nm larger than the red shift of the DB-PPV coating film, indicating that the required energy for exciting the luminescence is lower than that of the conventional one. It can save energy.

In summary, the present invention is characterized in that the luminescent fiber material is prepared by an electrospinning technique, and includes a phase-separated conjugated luminescent polymer and a polymer material having a hydrophilic group, so that the obtained finished product exhibits a core sheath. structure. In addition, the luminescent coating material of the present invention has a larger light absorption range than the conventional luminescent coating film, and has a red shift of 2 to 24 nm than the luminescent coating film material, so that the energy required for exciting luminescence decreases. Can reduce energy consumption. Since the conjugated luminescent polymer of the present invention is made into a flexible luminescent fiber material, the obtained product can be widely used not only in textile and garment, aviation navigation, national defense industry, building decoration, transportation, night work, daily life. In the fields of life, entertainment and leisure, it can be applied to textiles such as solar film and smart materials.

Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.

100, 200. . . Luminous fiber material

102, 202. . . Conjugated luminescent polymer

104, 204. . . Polymer material having a hydrophilic group

1 is a schematic illustration of a luminescent fiber material in accordance with an embodiment of the present invention.

Figure 2 is a schematic illustration of the preparation of a luminescent fiber material of the present invention by electrospinning.

Fig. 3 is an absorption spectrum of Experimental Example 1, Experimental Example 2, and DB-PPV solution and a conventional DB-PPV coated film.

4 is an emission spectrum of Experimental Example 1, Experimental Example 2, and a DB-PPV solution and a conventional DB-PPV coated film.

100. . . Luminous fiber material

102. . . Conjugated luminescent polymer

104. . . Polymer material having a hydrophilic group

Claims (9)

A luminescent fiber material is prepared by an electrospinning process, the luminescent fiber material comprising a conjugated luminescent polymer and a polymer material having a hydrophilic group, wherein the conjugated luminescent polymer and the conjugated luminescent polymer The weight ratio of the polymer material of the group is from 1/99 to 99/1, and the conjugated luminescent polymer is selected from the group consisting of polyfluorenes (PF) and derivatives thereof, and the polyfluorenes (PF) and Its derivatives include poly(dialkyl fluorene), poly(fluorene-co-bithiophene), poly(茀-co-phenylthiadiazole) (poly(fluorene-co-benzothiadiazole)), poly(fluorene-co-fluorene-co-thienopyrazine) and its derivatives. The luminescent fiber material according to claim 1, wherein the polymer material having a hydrophilic group comprises a water-soluble resin. The luminescent fiber material according to claim 1, wherein the polymer material having a hydrophilic group comprises a water-soluble polymer. The luminescent fiber material of claim 1, wherein the hydrophilic group comprises a carboxyl group, a hydroxyl group, a guanamine group, an amine group or an ether group. The luminescent fiber material according to claim 1, wherein the conjugated luminescent polymer is poly(2,3-dibutoxy-1,4-phenylethylene) (poly(2,3-dibutoxy-) 1,4-phenylene vinylene), DB-PPV) and the polymer material having a hydrophilic group are polyvinyl pyrrolidone (PVP). The luminescent fiber material according to claim 1, further comprising a solvent or a co-solvent. The luminescent fiber material according to claim 6, wherein the solvent comprises tetrahydrofuran (THF), toluene, chloroform or dimethyl formamide (DMF). The luminescent fiber material according to claim 6, wherein the cosolvent is a cosolvent selected from the group consisting of tetrahydrofuran, toluene, chloroform and dimethylformamide. The luminescent fiber material according to claim 1, wherein the diameter is between 50 nm and 3000 nm.