JPS6140366A - Preparation of clathrate compound of dithiolate complex and cyclodextrin - Google Patents

Abstract

PURPOSE:To obtain the titled clathrate compound exhibiting low color fading with light and useful as a solid dye Q switch, etc., by contacting a dithiolate complex with cyclodextrin in the form of a solution. CONSTITUTION:A dithiolate complex [e.g. bis[4-(dimethylamino)dithiobenzyl] nickel(O)] is dissolved in a solvent (e.g. dichloroethane) which dissolves only dithiolate complex, and the solution is passed through a column packed with cyclodextrin, and thereafter, the cyclodextrin is taken out of the column and the solvent is distilled off from the mixture. As an alternative method, the above dithiolate complex solution is mixed with a dextrin solution (the solvent is the one dissolving only dextrin, e.g. water), and the solvent dissolving only dithiolate complex is removed from the mixture to obtain the objective compound. Each solution is preferably saturated solution.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for producing a dithiolate complex-cyclodextrin encapsulation compound used in a dye Q switch used in oscillating giant pulses from neodymium laser.

[Prior art]

Solid-state lasers have advantages such as good light directionality, monochromaticity, and high energy density per unit area, so they have recently been used in laser telescopes, laser radars, dye laser excitation light sources,
The scope of use is expanding to include light sources for spectroscopy, laser processing machines, etc. When a solid-state laser is normally oscillated by excitation with a xenon flash lamp, its output has an irregular waveform consisting of several to several hundred spikes. Laser oscillators used in laser distance meters, laser radars, and the like need to generate a large peak output with a fast rise and a narrow width. The giant pulse oscillation method was devised for this purpose, and by using this method, the start of laser oscillation is suppressed until the necessary time, and oscillation is performed with a large number of electrons pushed up to the excitation level. A narrow large peak power laser output can be produced. A pulse with increased peak output is called a giant pulse. This giant pulse method uses a Q switch to control laser oscillation. Q-switches include active Q-switches and passive Q-switches, the former including a rotating prism and a Kelssel-Bockel cell, and the latter including a dye Q-switch according to the present invention as well as an absorbing thin film.

Among solid-state lasers, neodymium lasers have a 704μ door and an oscillation wavelength in the near-infrared region, and together with ruby lasers, they occupy an important position among the solid-state lasers currently in practical use.

The dithiolate complex dye used in the dye Q switch of this neodymium laser contains a trace amount of radical generator (e.g. peroxide, tetrahydrofuran, dichloroethane, etc.)
Photobleaching or dark fading occurs even in the presence of It is difficult to completely remove the radical generator from the solvent, and the light from the flash lamp that leaks when it is attached to the laser causes photobleaching in the air, and the effective number of pulse oscillations is approximately 2.
About 900 times. Furthermore, even under dark conditions, the lifespan was estimated to be approximately 2.3 years at 60° C., which is the quality assurance temperature, based on an estimate from an accelerated deterioration test. Furthermore, it is difficult to remove peroxide (used as a polymerization initiator) from the polymer in plastic Q-switches in which dithiolate complex dyes are dispersed in the plastic. butyl methacrylate dispersion medium) has an estimated lifespan of 0,11 years at room temperature. Furthermore, when polyvinyl alcohol is used as a dispersion medium, the dithiolate complex completely decomposes during the production of the plastic Q switch.

Dithiolate complexes are also used as infrared absorbers for infrared cut films, agricultural films, and the like. When using these materials, light resistance was also a problem, and ultraviolet absorbers and the like had to be added. However, this method was not effective for dark fading because the cause of discoloration was due to peroxides contained in the polymer. Furthermore, some ultraviolet absorbers and antioxidants have the property of reducing dithiolate complexes and causing discoloration.

[Summary of the invention]

In order to overcome the above-mentioned drawbacks, the present inventors discovered the use of an inclusion compound of a dithiolate complex dye and a cyclodextrin, and completed the present invention.

That is, this invention provides a method for contacting a dithiolate complex with a cyclodextrin, at least a dithiolate complex in a solution state, and a cyclodextrin in a solution state. I can do the method. For example, contact can be advantageously carried out by packing cyclodextrin into a column as the same phase, pouring the dithiolate complex into a solution that dissolves only the dithiolate complex and flowing it through the column, and then taking out the cyclodextrin from the column and removing the solvent. Alternatively, both the dithiolate complex and cyclotextrin are dissolved in a solvent that dissolves only one of them, the resulting dithiolate complex solution and the cyclotextrin solution are mixed, and the solvent that dissolves only the dithiolate complex is removed while stirring. It may also be done by

The dithiolate complexes used in one embodiment of the present invention include bis[4-(dimethylamino)dithiobenzyl]nickel (O) (hereinafter abbreviated as BDN), bis-(dithiodiacetyl)-platinum, bis-( dithiodiacetyl)-
Nickel, bis(ri).

y'-dimethoxydithiobenzyl)-platinum, bis-(dithiobenzylco-platinum), and those with the following structural formulas: (Mikata Toatsu trade name, I RA-t s') (Mikata Toatsu Pressure product name, IRA-3j) (Mikata Toatsu product name, IRA-J6) (Mikata Toatsu product name, IRA-,?4) (Mikata Toatsu product name, xRA-2) (Mikata Toatsu product name, xRA-2) (Mikata Toatsu product name, IRA-za) (Mikata Toatsu product name, IRA-/su (Mikata Toatsu product name, IRA-76) (Mikata Toatsu product name, IRA-76) Trade name: IRA-,?υ Examples of the cyclodextrin used in an embodiment of the present invention include α-2β-2γ-cyclodextrin.
What was changed to HJ (Tris-0CR.

-α-cyclodextrin) can also be used. Although it is desirable to dissolve both the dithiolate complex and cyclodextrin to saturation in each solvent, this is not the case in order to increase the ratio of the clathrate to the unclathrated cyclodextrin.

Examples of the solvent that dissolves only the dithiolate complex in this invention include dichloroethane, dichloroform, and carbon disulfide.

Examples of the solvent that dissolves only cyclodextrin in this invention include water, glycerin, and the like.

The structure of the dithiolate complex-cyclodextrin clathrate compound according to this invention is still unclear, and the oil-soluble B
This is because DN is water-soluble. It is thought that this product is resistant to radical attack because a part of the dithiolate complex is protected by siphrobucchistri.

Next, add tsom to the toluene solution of curve aKBDN in Figure 1.
The photofading rate when irradiated with ultra-high pressure mercury lamp light with a light intensity of w/cd is shown. The reaction rate constant was 10, lOJ min-'. Curve b in Figure 1 also shows the photobleaching rate when an aqueous solution of the clathrate compound of 4CBDN and β-cyclodextrin is irradiated with ultra-high pressure mercury lamp light with a light intensity of isomw/cd. k = 6.7X/O-'9-'.

Thus, the clathrate was 15 times more stable.

Furthermore, even though the dimethyl sulfoxide solution of BDN was warmed to 70°C and ammonium persulfate was added, the color completely faded within 1 minute. Even after heating for 30 minutes, the absorption at /1100n decreased by only about 10%.

[Embodiments of the invention]

Example 1 The present invention will be explained below based on Examples and Reference Examples.
Packed into a TOCA column, 02 parts by weight of bis-(q,
lI/-dimethoxydithiobenzylone-platinum 100
Pour the solution dissolved in part by weight of dichloroethane. After completely draining the liquid under reduced pressure, γ-shikashi, lθTl,...
! The mixture was centrifuged at 0OOXG for 10 minutes and the supernatant was removed. The absorbance of this material at 1100 mm was O, Col. to this/! The absorbance after irradiation with light of 0rnW/at& for 30 minutes is 0. / ? Met. Also, mix 0 parts by weight of this solution and 5 parts by weight of 10% polyvinyl alcohol solution,
When placed in a 70wgφ aluminum petri dish and dried at 0°C, a 0.71m solid dye Q-switch film can be obtained. When this was subjected to an accelerated deterioration test, the shelf life was estimated to be 3.7 years at mold temperature.

Example 2 1OX part of β-cyclodextrin was added to 1cILφXt
Pack 0.1 parts by weight of BDN into a column with 1 ooi
Pour the solution dissolved in i parts of chloroform. After completely draining the liquid under reduced pressure, I-cyclodextrin was taken out and dried overnight using a vacuum pump. Things of the afternoon/
Dissolve in O'0θ irises of water, io℃,! ;0OOXσ
Centrifuge for 10 minutes and remove the supernatant. This one is ito
Onm absorbance was 0.37.

This product is placed in a quartz container (m), and a neodymium laser oscillation device having the configuration shown in Fig.
When I attached it to a Q-switch (G) and a semi-reflective (S), there was sufficient oscillation even after 10,000 oscillations.

Example 3 7 parts by weight of α-7 clodextrin are dissolved in 100 parts by weight of water. Dissolve 0.07 parts by weight of bis-(dithiodiaceterne-platinum) in roI parts of dichloroethane. Both are stirred vigorously with a Magnetex 4-ra while dichloroethane is evaporated by reducing the pressure. Black. A precipitate is formed, which is collected by filtration.

The collected precipitate is dried overnight using a vacuum pump. This product was dissolved in 100 parts by weight of water and centrifuged at 500°C and 500xG for 10 minutes to remove the supernatant. This one is too
The absorbance at nm is 0. / It was 2. To this/jO*W
The absorbance after irradiation with /ail light for 30 minutes is 0. /Met.

YO parts by weight of this solution and 5 parts by weight of a 10% polyvinyl alcohol solution were mixed and placed in a 70 mm aluminum petri dish, and dried at 0°C to form a solid dye Q switch film of θ,/2ym. When this was attached to a neodymium laser having the configuration shown in Figure 2, sufficient oscillation was observed. According to accelerated deterioration tests of this solid-state Q switch, the storage life was estimated to be 3.7 years at mold temperature.

Example 1: Dissolve 1 part of β-cyclodextrin in ioθ parts by weight of water. Dissolve 0.07 parts by weight of BDN in lθθ parts by weight of chloroform. While vigorously stirring with a magnetic 4-ra in both beakers, add 1 OOBL.
Dissolve in a certain amount of water, tot.

The mixture was centrifuged with 5oooxa for 10 minutes and the supernatant was removed.

This material had an absorbance of 0.36 at 1100 mm.

When this was attached to a neodymium laser having the configuration shown in Figure 2, sufficient oscillation was observed even after 10,000 oscillations.

Reference Example 1 0.0006 N parts of BDN is dissolved in 100 parts by weight of toluene. The absorbance of this product in tot and onmic was 0.37. When this was attached to the neodymium laser shown in Figure 2 and oscillated, the pulse output decreased to SO% after 2000 oscillations. When this material was irradiated with light of tsomW/d for 3θ minutes, the absorbance became θ, Oj-.

Reference Example θ,00.1 parts by weight of BDN and lO appropriate parts of n-butyl methacrylate were dissolved in 100 parts by weight of toluene,
This was applied to a 211 IN thick polymethyl methacrylate plate with a 4-blade to a final thickness of 100 μm and dried. The transmittance of this item at 11060n is 0
%Met. When this was subjected to an accelerated deterioration test, it was approximately 0 at room temperature.
．． It had a shelf life of /4 years.

〔Effect of the invention〕

According to this invention, a solid dye Q-switch with little photofading can be obtained by dissolving a dithiolate complex-cyclodextrin clathrate compound in water together with a water-soluble resin such as polyvinyl alcohol and drying.

Furthermore, a dithiolate complex-cyclodextrin inclusion compound can also be used for photoelectric conversion. Furthermore, it can be used as an infrared cut filter 4 in photometers for cameras, and also gives favorable results as a commercial sheet.

[Brief explanation of drawings]

Figure 1 shows BDN-β-cyclodextrin according to the present invention)
FIG. 2 is a diagram showing the photobleaching characteristics of IJn clathrate compounds and BDH, and a schematic diagram of the configuration of a neodymium laser oscillation device. In the figure, L...reflection mirror, Y...flash lamp, 3
・・・Neodymium-YAG crystal, ・・Q switch,!・
・Semi-reflective mirror. Ara 1 figure 041 space (te5 N) 兇2 figure

Claims (5)

[Claims] (1) A dithiolate complex-cyclodextrin clathrate compound, characterized in that the dithiolate complex and cyclodextrin are made into a dithiolate complex-cyclodextrin clathrate compound by contacting at least the dithiolate complex with cyclodextrin in a solution state. manufacturing method. (2) The contacting is carried out by packing the cyclodextrin into a column, dissolving the dithiolate complex in a solvent that dissolves only the dithiolate complex and flowing the solution through the column, and then taking out the cyclodextrin from the column and removing the solvent. A method for producing a dithiolate complex-cyclodextrin clathrate compound according to item 1. (3) The contact involves dissolving only one of the dithiolate complex and cyclodextrin in a solvent, and mixing the obtained dithiolate complex solution and cyclodextrin solution,
The method for producing a dithiolate complex-cyclodextrin clathrate compound according to claim 1, which is carried out by removing a solvent that dissolves only the dithiolate complex while stirring. (4) The dithiolate complex is bis[4-(dimethylamino)
A method for producing a dithiolate complex-cyclodextrin clathrate according to any one of claims 1, 2, and 3, which is dithiobenzyl]nickel (0). (5) The dithiolate complex-cyclodextrin clathrate compound according to claim 1 or 3, wherein the solvent that dissolves only the dithiolate complex is dichloroethane, and the solvent that dissolves only cyclodextrin is water. Production method.