JPH0731177B2 - Detection agent for olefins and its detection method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a detection agent for olefins and a method for detecting olefins using the detection agent.

[Conventional technology]

In recent years, there has been a strong demand from the fruits and vegetables market participants for a safe and easy-to-use olefin detection agent.

Among the olefins, ethylene is particularly attracting attention as a plant hormone showing a wide range of physiological activities such as ripening, aging, coloration and fruit loss of fruits as well as promotion or inhibition of flowering and growth of plants.

Therefore, an attempt to effectively utilize these physiological activities possessed by ethylene by measuring the ethylene concentration, as seen in the study of the freshness-retaining agent in the distribution process of fruits and vegetables, makes effective use of products, and It is considered to be of great significance from the viewpoint of supply, and active research is underway.

Conventionally, as an olefin detection agent that can be easily handled, an example using a heavy metal oxidizing agent is known. However, since such an oxidant contains heavy metals, it may cause environmental pollution when discarded.

[Problems to be solved by the invention]

An object of the present invention is to provide a detection agent for olefins that is safe and easy to handle, and a method for detecting olefins using the detection agent.

[Means for solving problems]

The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, by supporting benzyltri-lower-alkylammonium polyhalide, which is a halogenating agent, on a support, a highly sensitive olefins detection agent can be obtained. I was able to. Then, they have found that olefins can be detected safely and easily by using the detecting agent, and have completed the present invention.

That is, the present invention has the following formula: (In the formula, R _{1 to} R ₃ represent the same or different lower alkyl groups having 1 to 6 carbon atoms; X represents a halogen atom; and n is 3 to 5
The benzyl tri-lower alkylammonium polyhalide represented by the formula (1) is carried on a carrier, and the detection agent for olefins is characterized by the above.

Furthermore, the present invention relates to a method for detecting olefins, characterized in that the fading degree of the detection agent for olefins is measured by the reaction between the detection agent for olefins and the olefins.

In the above formula, examples of the lower alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group and hexyl group.

In the above formula, X represents one or two kinds of halogen atoms, n represents an integer of 3 to 5, and X _n is, for example, Br ₃ , ClBr ₂ , Cl ₂ I or Cl _4. I, etc. can be mentioned.

The olefin detection agent of the present invention is, for example, a highly safe benzyltri-lower alkylammonium polyhalide represented by the above formula, benzyltri-loweralkylammonium tribromide, benzyltri-loweralkylammonium dibromochloride, benzyltri-loweralkylammonium monoiodo. It can be produced by supporting at least one of dichloride, benzyltri-lower alkylammonium monoiodotetrachloride and the like on a suitable carrier.

As such a carrier, silica gel, alumina, perlite (white igneous particles made of air bubbles of inorganic silicate glass produced by crushing and heating and expanding igneous rock such as pearlite. The chemical components are: SiO ₂ and Al ₂ O ₃ as the main components), florisil (as the chemical component, magnesium silicate as the main component), solid oxides such as zeolite, and those containing such oxides. be able to.

The method for supporting the benzyltri-lower alkylammonium polyhalide on the carrier is not particularly limited, and for example, in a solution prepared by dissolving benzyltri-loweralkylammonium polyhalide in a suitable solvent, the carrier is added,
A method of stirring and then distilling off the solvent and drying can be applied.

The mixing ratio of the carrier and benzyltri-lower alkylammonium polyhalide is not particularly limited, and for example, 1 to 50% by weight of benzyltri-loweralkylammonium polyhalide can be supported on the carrier, and preferably 5 to 30%. It is advisable to support a weight percent of benzyltri-lower alkylammonium polyhalide.

By thus supporting benzyltri-lower-alkylammonium polyhalide on a carrier, the olefin detection agent of the present invention can be obtained.

The particle size and shape of the olefins detection agent of the present invention are not particularly limited (for example, it can be used in the form of powder, granules, or lumps), but the benzyltri-lower-alkylammonium polyhalide has a yellow or orange fading state. The convenience of use can be improved by packing a transparent column, a tablet, a breathable transparent synthetic resin bag, or the like that can be easily measured.

The olefins detection method of the present invention can be carried out, for example, by placing a fixed amount of an olefins detection agent in a transparent container and contacting the detection agent with the olefins for a predetermined time.

The olefins used in the present invention include ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-
Pentene, 2-pentene, 2-methyl-1-butene, 3
-Methyl-1-butene, 2-methyl-2-butene, 1-
Hexene, 2,3-dimethyl-2-butene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like can be mentioned.

The container of the olefin detection agent used in the present invention,
A bag made of a transparent synthetic resin (for example, polyethylene) having air permeability and a transparent column (for example, glass, polyethylene, etc.) can be used.

In the reaction of the olefin detection agent and the olefin contained in the bag as described above according to the present invention, the olefin detection agent and the olefin are placed in another transparent container (for example, glass, polyethylene, etc.). Put it in and let it react for a certain time. The amount of the olefins can be known by knowing the time until the fading state from the yellow or orange color of the detection agent to the white state through pale yellow and the fading state can be known (note that the amount of the olefins is known in advance. The fading state which was facilitated by the same operation using the olefins of
Consider the relationship between the time until the fading state and the amount of olefins).

In the reaction between the olefin detection agent and the olefins put in the column as described above in the present invention, in particular, the column can be allowed to react for a certain period of time without being placed in another container. At this time, the amount of the olefins can be known by knowing the volume showing the fading state of the detecting agent and the time until the fading state (the same as the case of using a known amount of olefins in advance. The relationship between the volume showing the fading state prepared by the above procedure, the time to reach the fading state, and the amount of olefins should be examined). Then, in order to easily know the volume showing this fading state, it is preferable to mark marks such as scales at appropriate intervals on the surface of the column in the fading direction of the olefins.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to Examples. It should be noted that these examples do not limit the scope of the present invention.

Example 1 Production of olefin detection agent 4.5 g of silica gel C-200 (manufactured by Wako Pure Chemical Industries, Ltd.), which is a solid acid carrier, was added to a solution prepared by dissolving 0.5 g of benzyltrimethylammonium monoiodotetrachloride in 20 ml of methylene chloride. Was added in small portions. After the addition was completed, the mixture was stirred at room temperature for 10 minutes, and then the solvent was distilled off under reduced pressure. Then, it was further dried under reduced pressure at 80 ° C. for 1 hour to obtain 5 g of an olefin detection agent (yellow).

Example 2 Detection of olefins 10 mg of the olefin detection agent obtained in Example 1 was sealed in a breathable transparent bag (polyethylene, thickness: 0.01 mm, size: 2 × 2 cm), It was placed in a 65 ml Erlenmeyer flask and sealed. A pure ethylene gas having a predetermined concentration was injected into four of the five Erlenmeyer flasks thus prepared, and the time required until the yellow color of the olefin detection agent turned white was measured. The results are shown in Table 1.

Using a mixed gas (ethylene concentration of 3000 ppm) containing 2 ml of carbon dioxide gas of 300,000 ppm in ethylene concentration of 3,000 ppm, the fading time was measured in the same manner as above, and as a result, the olefin detection agent became white within 10 minutes. It was

Example 3 Detection of olefins Five glass columns (internal diameter: 6 mm, length: 10 cm) packed with 0.5 g of the olefin detection agent obtained in Example 1 were prepared. Ethylene pure gas having a predetermined concentration was circulated in these columns at a flow rate of 5 ml / min for 10 hours, and the length of the portion where the olefin detection agents in the columns became white was determined. The results are shown in Table 2.

Using a mixed gas consisting of 100 ppm ethylene gas and 1,000 ppm carbon dioxide gas, the length of the white portion was measured in the same manner as above, and the result was 2.4 mm.

〔The invention's effect〕

The olefin detection agent of the present invention is easy to handle,
It is also highly safe, and the amount of olefins can be detected easily and with high sensitivity by knowing the fading state of this drug.

Claims (2)

[Claims] 1. The following formula: (In the formula, R _{1 to} R ₃ represent the same or different lower alkyl groups having 1 to 6 carbon atoms; X represents a halogen atom; and n is 3 to 5
The benzyl tri-lower alkylammonium polyhalide represented by the formula (1) is supported on a carrier. 2. A method for detecting olefins, which comprises measuring the fading degree of the olefins detecting agent according to claim 1 by reacting the olefins with the olefins.