JPS58171667A - Quick deciding method of organotin compound - Google Patents

Abstract

PURPOSE:To simply and quickly detect Sn in plastics or antipollution paints, by extracting and dissolving an organotin compound by adding a chlorine group solvent to a sample and adding a coloring reagent to this solution and observing generated coloration. CONSTITUTION:An organotin compound containing in plastics or antipollution paints is extracted by a chlorine group solvent such as CHCl3, CCl4, etc. It is good to use an ultrasonic washing machine for dissolving quickly high molecular compounds of coating, etc. Solid matters such as pigment in the solution are filtered and then, the same volume of a coloring reagent solution is added to a suitable quantity (about 2ml) of the filtrate and is mixed. Hereafter, a coloring state of the chlorine group solvent layer is observed. An aqueous solution of dithizone, alizarin S, oxine, etc. is used for the coloring reagent. If organic Sn exists, the color of the dithizone is changed from blue to yellow by using the dithizone dissolving in concentrated ammonia water and detection is made possible in about 10min from the sample treatment to the finish of detection with <=1ppm detecting sensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a rapid determination method that can easily detect organic compounds.

The di-n-octyltin compound, which has been used as an FK agent for thermal processing of polyvinyl chloride (PVC), is a low-toxic compound that has been approved by the American Food and Drug Administration and the West German Federal Bureau of Health. but.

Recently, antifouling room materials such as Jiyochi anti-adhesion paint.

Several organotin compounds have been approved and used to provide anti-fouling properties to self-borinosing ship bottom coatings and the like.

Therefore, although these are low-toxicity paints, it is necessary to bury the paint in tubes on site, and in particular, it is required to confirm the absence of tin compounds at the time of obstetric disposal. There is still no known detection method that can easily and quickly detect the presence or absence of organic tin compounds in the field.

In view of these circumstances, the present inventor has conducted intensive research to develop a determination method that can quickly and easily detect organic tin compounds that are coated in antifouling paints, etc. Compound?
! Simply extract the organic tin compound using a chlorinated bath agent such as chloroform, add aqueous ammonia in which dithizone is dissolved as a coloring reagent, and stir thoroughly. The inventors discovered that chloroporumnose changed from blue to yellow and that the presence or absence of organic tin compounds could be determined extremely quickly with just a simple pretreatment.Based on this knowledge, the present invention was made. .

That is, the present invention adds a chlorinated solvent to a composition containing an organic substance to extract and dissolve an organotin compound, and then adds a coloring reagent to the composition to form an organotin compound depending on the color development of the chlorinated solvent. This paper proposes a rapid determination method for organotin compounds, which is characterized by detecting the presence or absence of the presence or absence of an organic tin compound.

The present invention will be explained in detail below.

Compositions containing organic substances that can be used as sealing plates for which the method of the present invention can be applied include violet and plastics.

and organic wastes, among others antifouling paints using organic tin compounds as antifouling agents, whose general composition is as follows.

Ma) IJ x+organotin compound g+cg, 0+containing solvent+coloring pigment Here, matrix is a general term for polymers and polymer compounds that serve as supports for antifouling agents in coatings, and most of the organic tin compounds are among these. Dispersed in colloidal form. Therefore, a strong solvent is required to extract and photograph organotin compounds from antifouling paints.

The solvent used in the present invention is a chlorine bath agent.

An example of this is chloroform.

Examples include carbon tetrachloride and tetrachloroethylene.

An example in which the method of the present invention is applied to rapid determination of organic tin ions in an antifouling paint will be described below.

That is, O1 to 0.2f of the antifouling paint was collected.

Chloroform, which is a chlorinated solvent, is cooled for 10 minutes and mixed and dissolved for 2 to 3 minutes using an ultrasonic cleaning machine. - Solids such as Cu and 0 are separated and removed from the solution thus obtained using a syringe-type Millipore filter. Then, collect the above solution or this P solution into a test tube, and add ldj amount of coloring reagent k ti 7JFI.
After stirring L.

Separated chloroform) - Color status ff.

The presence or absence of the 9M bleaching compound is detected by observing the yellow coloration.

The coloring reagent used in the method of the present invention is as follows.

For example, dithizone, rIR dyes such as chrome azurol S, alizarin S, and oxine can be used. The case where dithizone is used as a coloring reagent will be explained below.

Dithizone reacts with organic tin ions to produce a unique color (yellow).
It forms a complex salt with .

In the present invention, organic tin compounds are well known from the Isshiki situation, but since dithizone is insoluble in water, dithizone is dissolved in ammonia water and used in baths prepared to various concentrations as shown below. The liquid is used as an oshiki test lee.

Preparation Example 1 Dithizone f Conc of the above distribution was dissolved in 100% of NHs water to obtain a coloring reagent. Dithizone concentration approximately 5×10”
mol / t 0 Adjustment example 2゜The above amount of dithizone Conc NH,'7jC10'
Dissolve in O- to make a coloring reagent. Dithizone once approx. 5 x 1
0-5 mol/10 Preparation Example 3 The above weight of dithizone is dissolved in 7% NH and water.

This is a saturated bath solution since dithizo/ is not completely dissolved, and the supernatant is used as a coloring reagent. Dithizone concentration approximately 5X
10 mol/t0 Adjustment Example 4゜Take the coloring reagent from Adjustment 3 and add it to 100 Wt1. with 7 NH and water. It was diluted to make two coloring reagents.

Dithizone concentration: Approximately 5 x 10'' mob / L0 Preparation Example 5゜ Take 1kl of the coloring reagent from Preparation Example 4 and add it to 7% NH
, diluted with water to 10'0- to prepare a coloring reagent.

Antizone concentration: approximately 5 x 10j7mot/10 As explained in detail, there are two effects per method of the present invention.

(1) Since the yellow color has an extremely high contrast with the blue color of the blank, it is very easy to distinguish whether the organic tin compound is present or not. .

(2) Sample processing is extremely simple, making it suitable for simple on-site analysis.

(8) The process from sampling to color development to checking and confirming the presence or absence of organic tin compounds can be done in just 10 minutes, making it extremely efficient.

((1) The detection sensitivity is 1 ppm or less, which is sufficient for on-site paint management, and can detect all organic tin compounds.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Tributyltin acetate, tributyltin chloride, tributyltin fluoride, bis-tributyltin oxide 1. , triphenyltin acetate, triphenyltin chloride, and bis=(tributyltin)-α
, ll for σ'-dibrome succinate, respectively
! A chloroform bath solution with an I degree of 1000 ppm was prepared, about 2- of it was taken into a test tube, and the above Preparation Examples 1 to 3 were added to the solution.
The same amount of the coloring reagent was added to the mixture, and the first color was developed, and the situation immediately after the second color was developed was compared with the blank. The results are shown in Table 1.

As is clear from Table 1.

The color development of the two shows a marked contrast and is extremely easy to distinguish.

(2) All of the seven organotin compounds tested showed the same coloration, and this method is applicable to all organotin compounds.

Table 1 Example 2 To confirm the practical concentration of dithizone, approximately 2000 ppm of tributyltin acetate/chloroform solution was placed in a test tube, and added to the above Preparation Example 4 or 5. Approximately the same amount of the coloring reagent was added to develop a gayo color.

The results are shown next.

As can be seen from the above, even if a very dilute dithizone solution is used, it is possible to detect an organic tin compound of 9tJ, but the reason why a 2-type color is observed is when the degree of dithizone in Preparation Example 4 is 5.
When using a coloring test with a concentration of X 10 mol/1 or more, the practical range is from that concentration to the saturation concentration.

Example 3 In order to confirm whether the detection sensitivity of organic tin compounds shows a practically sufficient level, 1.10.100 ppm each of tributyltin chloride and triphenyltin chloride was added.
/chloroform solution was prepared, each 2- was placed in a test tube, and the same amount of the coloring reagent of Preparation Example 1 was added to each test tube to develop color.

The results are shown in Table 2.

Table 2 As shown in Table 2.

(1) Both tributyltin chloride and triphenyltin chloride exhibited sufficiently deep yellow coloration even at low concentrations of ippm, and exhibited extremely high sensitivity.

(With regard to applicability in the case of a concentration ' of 211 ppm or less, extremely clear coloring was exhibited even at a concentration of +' 1 ppm, so it is considered that it can be applied even at a concentration lower than that.

Example 4゜ Using an antifouling paint containing a tin compound.

The practicality of the method of the present invention was confirmed as follows.

Ship bottom antifouling paint A whose resin is insoluble in seawater (Company A A/F
Paint) 0.2 tons of chloroform was shaken for 10 minutes, followed by FA using a cartridge-type Millipore filter (Nippon Millipore Riminotenodo's winter filter holder) to obtain transparent roloform. Solution sample A.

Add 1o-e of chloroform to ship bottom antifouling paint B (self-polishing type paint from Company B) 012.

Pale scarlet red sample C1 obtained by filtration in the same manner as sample A. Antifouling paint on the bottom of the ship (c<c crazy self-polishing type obstetrics) 0.22, chloropol, mu 10m7! A transparent sample C1 was obtained by adding and passing through the same process as sample A. Ship bottom antifouling paint D' (self-polishing type paint from Company D)
curing agent of 0. Sample D, which is a clear chloroform solution obtained by adding chloroform lod to IV and shaking, and ship bottom antifouling paint E that does not contain organotin compounds (Company D, A/
F paint) Add oo porum 1゜7 to O22 and evaporate in the same way as sample A to create each sample Ei.
Adjustment example 1 was applied to each sample. And the photocolor reagent of Preparation Example 2 was added to develop color.

The results are shown in Table 3.

The resin in each paint of Sample B and Sample C is a tributyltin methacrylic acid copolymer that dissolves in seawater while hydrolyzing, albeit very slightly, and at the same time, the tributyltin hydride generated at that time exhibits antifouling performance. .

As shown in Table 3, organic tin compounds in the antifouling paint could be detected in all samples.

As described above, the present invention provides a method for rapidly determining organotin compounds, which is industrially very useful.

Claims (1)

[Claims] A chlorinated solvent is added to a composition containing an organic substance to extract and dissolve an organotin compound, and a coloring reagent is added to the composition to detect the presence or absence of an organotin compound based on the color development of the chlorinated solvent. Jin, who does it! A rapid determination method for organotin compounds characterized by: