JPH01148143A - Adjuster of ethylene amount - Google Patents

Abstract

PURPOSE:To obtain the titled stable adjuster capable of properly controlling additional ripening, coloring, etc., readily adjusting an amount of C2H4, supportable on an inorganic compound, having excellent handleability, containing a specific benzyltrilower alkylammonium polyhalide. CONSTITUTION:A benzyltrilower alkylammonium polyhalide (e.g., benzyltrimethylammonium monoiododichloride) shown by the formula (R1-3 are 1-6C lower alkyl; n is 2 or 4) is dissolved in a solvent such as water or methylene chloride, incorporated with a carrier such as active carbon, zeolite, activated clay, active alumina or peat-moss, stirred, the solvent is distilled away, the resultant snbstance is dried and 5-30wt.% of the compound shown by the formula is supported on the carrier to give the titled adjuster.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an ethylene content regulator that allows easy regulation of ethylene content.

[Conventional technology]

Ethylene is attracting attention as a plant hormone that exhibits a wide range of physiological activities, including not only the ripening, aging, color development, and fruit drop of fruits, but also the promotion or suppression of flowering and growth of plants.

Attempts to effectively utilize these physiological activities of ethylene by suppressing ethylene concentration have led to the effective use of produce and the supply of higher quality substances, as seen in the study of freshness-preserving agents in the distribution process of fruits and vegetables. It is considered to be of great significance from the perspective of, and active research is underway.

Various oxidizing agents or reducing agents have been studied as ethylene content regulators, and there are many examples in which oxidizing agents are used. For example, an example using potassium permanganate (Japanese Unexamined Patent Publication No. 58-220648), an example using potassium bromate, Journal of the Japanese Society of Agricultural Chemistry, 1127 (1983
)] and examples using bromine.

[Problem that the invention seeks to solve]

The purpose of the present invention is to be stable, easy to adjust the amount of ethylene,
Another object of the present invention is to provide an ethylene amount regulator that can use an organic polymer compound as well as an inorganic compound as a carrier.

[Means for solving problems]

As a result of intensive research to solve the above-mentioned problems, the present inventors focused on the fact that quaternary ammonium polyhalide, which is a halogenating agent, is excellent in the following points 1 to 2, and developed the present invention.・Since it is an organic compound, it can be easily supported on polymeric compounds such as polyethylene and ethylene-vinyl acetate copolymer used for packaging fruits and vegetables. It can also be supported.

■ It is a very stable crystal and is easy to handle. ■ It easily reacts with ethylene even at low temperatures, and the color of the halogenating agent disappears after the reaction, making it easy to confirm the completion of the reaction.

(2) After reaction with ethylene, it becomes a quaternary ammonium halogen salt, which is preferable from the viewpoint of safety.

In the formula, R, -R, are the same or different carbon numbers 1 to 6
represents a lower alkyl group; n represents 2 or 4). 1llW
This relates to ff agents.

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.

The ethylene content regulator of the present invention can be obtained by supporting benzyl tri-lower alkylammonium monoiodo dichloride or benzyl tri-lower alkylammonium monoiodotetrachloride, which is a benzyl tri-lower alkylammonium polyhalide represented by the above formula, on a suitable carrier. can be manufactured.

Such carriers are not particularly limited, and carriers of inorganic or organic compounds, such as activated carbon, zeolite, perlite, activated clay, activated alumina, calcium carbonate, vermiculite, peat moss, and various organic polymer compounds, can be used. can.

Furthermore, the container itself, such as a polyethylene bag, can be used as a carrier.

The method of supporting benzyltrimethylammonium monoiodotetrachloride on the support is not particularly limited. For example, benzyltrimethylammonium monoiodo dichloride or benzyltrimethylammonium monoiodotetrachloride is dissolved in a suitable solvent, and the benzyltrimethylammonium monoiodotetrachloride is supported on the support. A method can be applied in which a compound is added, stirred, and then the solvent is distilled off and dried.

The mixing ratio of the support and the benzyl tri-lower alkylammonium polyhalide is not particularly limited, and for example, when activated carbon is used as the support, the mixing ratio is 5 to 30% of the amount of activated carbon.
% by weight of benzyl tri-lower alkyl ammonium polyhalide can be supported.

By supporting the benzyl tri-lower alkylammonium polyhalide on the carrier in this manner, the ethylene amount regulator of the present invention can be obtained. For convenience in use, the ethylene amount regulator of the present invention can also be filled with benzyl tri-lower alkyl ammonium polyhalide supported on a carrier into an air-permeable bag made of paper, cloth, or the like.

The ethylene amount regulator of the present invention can control the ethylene amount by reacting benzyl tri-lower alkyl ammonium polyhalide, which is an active ingredient, with ethylene to produce monoiodoethane.

〔Example〕

Examples of the present invention will be shown below. Note that these Examples do not limit the scope of the present invention.

Example 1 18°6 g of benzyltrimethylammonium chloride (
0.1mof) dissolved in 100mf of water, -
A solution of 16.3 g (0.1 m o j!) of iodine chloride in methylene chloride at 200 mA! was added dropwise to the solution at room temperature with vigorous stirring. Thereafter, after stirring for 30 minutes, the methylene chloride layer was separated, magnesium sulfate was added thereto, and after drying, the solvent was distilled off. The obtained crude crystals were recrystallized from a mixed solvent of methylene chloride/ether (10:1). The yield was 26.2 g (75% yield), and the melting point of the crystals was 125-126°C.

(a) Ethylene Words. 2g of the above benzyltrimethylammonium monoiodo dichloride
100mj of methylene chloride! Activated carbon was added little by little to the solution dissolved in .

After the addition was completed, the mixture was stirred at room temperature for 30 minutes, and then the solvent was distilled off under reduced pressure. Thereafter, the mixture was further maintained at 80° C. for 5 hours under reduced pressure to obtain an ethylene content regulator.

(b) Ethylene 9. 0.5 g of the ethylene amount regulator of the example (100 mg as benzyltrimethylammonium monoiodo dichloride) was placed in a 6 U flask with a capacity of 65 mf, and the flask was tightly stoppered. Next, 10 mf of 1100 pp of ethylene was injected into the container, and the ethylene concentration in the head space in the container was measured after the time shown in Table 1 had elapsed. As comparative examples, KBrO, -H, 5O4-activated carbon system (prepared according to Journal of the Japanese Society of Agricultural Chemistry, p. 1127, 1983)] (Comparative Example 1) and activated carbon (Comparative Example 2) were used. The results are shown in Table 1.

(Hereinafter, blank spaces) Table 1 This freshness retention effect was observed using Otori grapes (variety: Kyoho).

After putting 2 bunches of grapes (70 grapes) and each regulator used in (b) into a polyethylene bag with a thickness of 0.03 mm,
Vinyl tape was applied to the opening of the bag, and the bag was packaged in a semi-sealed layer. When the grapes were stored at room temperature (20-25"C), the number of grapes shed after the number of days shown in Table 2 was observed.The results are shown in Table 2.The numbers in the table are Shows the number of grains shed.

Table 2 Example 2 Benzyltrimethylammonium chloride 18°6g (
A solution prepared by dissolving iodine trichloride (0.1 moj) in 100 mf of water was added dropwise to 23.4 g of iodine trichloride (0.1 moj) in 200 ml of methylene chloride solution at room temperature with vigorous stirring. (It did not dissolve in the methylene chloride solution.) After stirring for 30 minutes, the precipitated pale yellow crystals were filtered and separated.Meanwhile, the methylene chloride layer of the obtained filtrate was separated, Magnesium sulfate was added to this, and after drying, the solvent was distilled off.The obtained crude crystals were combined with the crystals that had been collected by filtration, and then reconstituted with a mixed solvent of methylene chloride/ether (10:1). The yield was 34.4 g (yield 82%), and the melting point of the crystals was 104.5-105.5°C.

(a) Ethylene ζ Negative 1 Activated carbon was added little by little to a solution in which 2 g of the above benzyltrimethylammonium monoiodotetrachloride was dissolved in 100 ml of methylene chloride. After addition, 3
After stirring for 0 minutes at room temperature, the solvent was distilled off under reduced pressure. Thereafter, the mixture was further maintained at 80° C. for 5 hours under reduced pressure to obtain an ethylene content regulator.

(b) 0.5 g of the ethylene amount regulator of the example (100 mg as benzyltrimethylammonium monoiodotetrachloride) was placed in a 65 ml flask containing 9° ethylene, and the flask was tightly stoppered. Next, in this container, 10mj of 1100pp ethylene! After the injection, the ethylene concentration in the headspace in the container was measured after the time shown in Table 3 had elapsed.

As comparative examples, KBrO3-H2SO4-activated carbon system [Journal of the Japanese Society of Agricultural Chemistry, p. 1127, 1983]] (Comparative Example 1) and activated carbon (Comparative Example 2) were used.
) was used. The results are shown in Table 3.

Table 3 This freshness retention effect was observed using Otori grapes (variety: Kyoho).

After putting 2 bunches of grapes (70 grapes) and each regulator used in (b) into a polyethylene bag with a thickness of 0.03 mm,
Vinyl tape was applied to the opening of the bag, and the bag was packaged in a semi-sealed state. When the grapes were stored at room temperature (20-25"C), the number of grapes shed was observed after the number of days shown in Table 4 had passed.The results are shown in Table 4.The numbers in the table are Shows the number of grains shed.

Table 4 [Effects of the Invention] The ethylene amount regulator of the present invention can appropriately control ripening, color development, etc. of fruits etc. by appropriately selecting the amount used. Furthermore, the ethylene amount regulator of the present invention is stable and does not discolor when reacting with ethylene, so it is easy to handle.

Patent Deseto Ube Industries Co., Ltd.

Claims (1)

[Claims] The following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ I (In the formula, R_1 to R_3 are the same or different carbon numbers 1
- represents a lower alkyl group of 6; n represents 2 or 4)
An ethylene amount regulator comprising a benzyl tri-lower alkyl ammonium polyhalide represented by: