KR20040052636A - Polymers and novel metals composites by alcohol reduction - Google Patents

Abstract

PURPOSE: A method for preparing a mixture composition of a polymer and a noble metal by alcohol reduction is provided, to obtain a material (particle) whose optical, magnetic and catalytic properties can be controlled by the change of composition ratio and pH. CONSTITUTION: The method comprises the step of preparing a noble metal, its mixture compound or its composite(2) with a polymer(1) by alcohol reduction or polyol process. Preferably the reaction is carried out by using a single alcohol such as methanol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol and isopropylene glycol or a mixture of an alcohol and water as a solvent and reducing agent; a water-soluble polymer as a dispersant and reduction accelerator; and a sulfur-containing polymer to improve the physical and chemical binding force between a polymer and a noble metal or as a binding auxiliary. The surface of a polymer is treated to make it be charged state in a solvent, and a metal (complex) ion having the opposite charge is adhered to the surface of a polymer and grows at the surface.

Description

Preparation of Mixed Composition of Polymers and Precious Metals by Alcohol Reduction Method {Polymers and novel metals composites by alcohol reduction}

In general, the precious metal material is used in many fields industrially because of excellent optical, electrical, and catalytic performance. Compared to such excellent performance, it has been pointed out that it is expensive and difficult to recover after use. In order to overcome this drawback, the maximum effect should be made in a small amount. One such method is to reduce the size of the metal to increase the surface area. However, when the size is reduced, it is pointed out that recovery is impossible after use or during use. A method that can compensate for these disadvantages is to use polymers, inorganic materials, etc. as a support. In particular, it is true that the combination of polymer and metal has been studied in that size and shape control are advantageous.

Looking at the techniques for forming a conventional polymer-metal complex briefly as follows.

① Method using Copolymerization

(CW Chen, T. Serizawa and M. Akashi, Langmuir , 15, 1999, 7998-8006)

② -radiation synthesis

(Dazhen Wu, Xuewu Ge, Yuhong Huang, Zhicheng Zhang, Qiang Ye, Materials Letters , 57, 2003, 3549-3553)

(3) Charge electric charges to polystyrene and metal particles to bond them with electrical force (AG Dong, YJ Wang, Y. Tang, N, Ren, WL Yang and Z. Cao, Chem . Comm ., 2002, 350-351)

However, these technologies have a disadvantage in that the economy is relatively low due to the complexity of the manufacturing process, and more efficient and simple synthesis methods are required to solve these problems.

Industrial Applicability In the present invention, a coating or a mixture of nano-size noble metals is used as a support using an industrially widely used polymer as an alcohol reduction method for a business field requiring optical, electrical and catalytic performance of noble metal materials. This is to maximize the efficiency of using precious metals. In particular, it is applied to the reaction environment and polymer system where it is difficult to use metal directly, and it is not only used as UV paint, but also for special use and industrial use that requires the use of these properties by changing optical, magnetic and chemical properties of particles. It can be used as.

1 is a single precious metal (gold, silver, platinum, palladium, rhodium, iridium, ruthenium, osnium, etc.) particles or a mixture of two or more kinds of these precious metals, the compound is a film surface by the chemical or physical bonding force to the polymer surface Figure (a) being coated and figure (b) with particles adhering to the polymer surface.

※ Explanation of code for main part of drawing

1: high molecular weight used as a support body, 2: precious metals metal particles (gold, silver, platinum, palladium, rhodium, iridium, ruthenium, osmium, etc.) or two or more types of mixtures of these precious metals, compounds

Hereinafter, the present invention will be described in more detail. As described above, the present invention provides a simple method of combining a polymer and precious metals (Ag, Pt, Pd, Au, Rh, Ru, Ir, Os) particles by using alcohol reduction, thereby providing This is to increase the recovery rate, to overcome the constrained usage environment, and to apply to a wider field.

The alcohol reduction method used in the present invention is a method for obtaining nano-sized metal particles in colloidal phase by reducing metal salts using a liquid alcohol organic solvent having a hydroxyl group. In this case, the colloidal solution may be stabilized by adding a dispersant, and in particular, when PVP (polyvinylpyrrolidone) is used as the dispersant, the dispersant may serve as both a dispersant and a reducing accelerator. It is also known to obtain uniform metal particles by applying heat to promote reduction.

The alcohol reduction method is described in more detail as follows.

The alcohol reduction method refers to a method of reducing metal salts in liquid alcohols having a hydroxyl group. In this method, since a hydroxyl group plays a role of a reducing agent, there is no need to add a reducing agent, and in order to increase the dispersibility of the metal colloid, a dispersing agent is added and a reaction is used in the manufacture of metal colloids. The typical process of alcohol reduction is as follows. When H ₂ PtCl ₆ , HAuCl ₄ , RhCl ₃ , RuCl _3, etc. are dissolved in a 1: 1 mixture of ethanol and water, and the water-soluble polymer is added and refluxed and heated, nanoparticles such as platinum, gold, rhodium and rusium You get a dispersion. At this time, ethanol plays a role of solvent and reducing agent, and water-soluble polymer plays a role of dispersant and reduction accelerator at the same time. The polyol process refers to a process of reducing the reaction by raising the reaction temperature by using a high boiling alcohol (polyol) for the purpose of reducing metals which are not easily reduced at low temperatures as a kind of alcohol reduction method. At this time, as the high boiling alcohol (polyol), ethylene glycol, diethylene glycol, trimethylene glycol, isopropylene glycol and the like are used.

This method can be easily used as a method for preparing a polymer-metal mixed composition to obtain a polymer-metal mixed composition. In particular, when the polystyrene particles prepared in advance using a liquid polyol as a solvent or a dispersion medium are put together with a metal salt and heated, the desired metal can be adsorbed onto the polymer. These reactions are introduced by introducing sulfur compounds or twilight compounds for the purpose of smooth coupling between the polymer and the noble metal during the manufacturing process of the polymer, alcohol reduction method, or polyol process, or by treating the surface of the polymer so as to be in a cation or an anion state on the solvent, thereby exhibiting an opposite charge Metal complex ions or ions can be more smoothly carried out by using a technology that is adsorbed on the surface of the polymer to cause the growth on the surface of the polymer particles.

As a representative experiment of the present invention, the results of experiments with varying concentrations of polystyrene and silver were obtained as shown in Figure 1. The reaction temperature and time were the same, and the experiments were carried out only by changing the composition ratio. The results are shown in Figure 1.

The preparation of the polymers and metal salts used in the present invention may employ any suitable process, such as all manufacturing techniques through synthesis and reaction known in the art.

EXAMPLE

Example 1

Using ethylene glycol (or ethanol) as a solvent, polystyrene (200 nm to 500 nm) 100 ppm to 1000 ppm (based on the total solution) and the silver component-based additives were reacted by mixing 250 ppm to 5000 ppm (based on the total solution).

Example 2

Ethylene glycol (or ethanol) was used as a solvent, and 100 ppm to 1000 ppm (based on total solution) of PMMA (200 nm to 500 nm) and gold-based additives were mixed by 250 ppm to 5000 ppm (based on total solution).

Example 3

Using ethylene glycol (or ethanol) as a solvent, polystyrene (200 nm to 500 nm) 100 ppm to 1000 ppm (based on the total solution) and the platinum component-based additives were reacted by mixing 250 ppm to 5000 ppm (based on the total solution).

Example 4

Using ethylene glycol (or ethanol) as a solvent, PMMA (200 nm to 500 nm) 100 ppm to 1000 ppm (based on the total solution) and the palladium component-based additives were reacted by mixing 250 ppm to 5000 ppm (based on the total solution).

In spite of its excellent performance, precious metals have used many other metals which are inferior in performance but inexpensive due to their disadvantages of being expensive, impossible to recover after use, and having many limitations in use. By using the new reaction method to easily prepare a mixed composition of a polymer and a metal, it is possible to increase the use efficiency of the precious metal.

In addition, the optical, magnetic, and chemical properties of precious metal particles are added to the field of use of pure polymers, which will greatly contribute to the development of polymer applications such as the development of high speed printing toner.

Claims (2)

A technique using an alcohol reduction method or a polyol process to synthesize a single precious metal or two or more kinds of these precious metals, a mixture of a compound and a polymer, and synthesize a compound. Alcohol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, isopropylene glycol and the like as a solvent and a reducing agent in the alcohol reduction method and the polyol process of claim 1 The same single alcohol mixture or alcohol and water mixtures are used, water-soluble polymers are used as dispersing and reducing accelerators, sulfur-containing polymers are used to enhance the physical and chemical bonds between polymers and precious metals, or alcohol reduction and polyol processes In this case, the sulfur component is used as a binding aid, or the surface of the polymer is treated in a cation or an anion state in a solvent so that metal complex ions or ions having opposite charges are adsorbed on the surface of the polymer to cause growth on the surface of the polymer particle. Technology.