AU2018101611B4

AU2018101611B4 - Ethephon Formulation

Info

Publication number: AU2018101611B4
Application number: AU2018101611A
Authority: AU
Inventors: Peter Vaughan
Original assignee: Adama Australia Pty Ltd
Current assignee: Adama Australia Pty Ltd
Priority date: 2018-10-26
Filing date: 2018-10-26
Publication date: 2022-06-09
Anticipated expiration: 2026-10-26
Also published as: BR112021007695A2; AR116842A1; AU2019366155B2; AU2018101611A4; AU2019366155A1; WO2020082106A1

Abstract

The invention is concerned with highly loaded ethephon formulations, especially suited for use in cotton crops. Ethephon can initiate fruiting, promote early boll opening, enhance defoliation and assist in scheduled harvesting. 5 The invention includes a novel method of making a formulation having a concentration ofethephon ofat least900g/L 10 15

Description

Ethephon Formulation

Technical Field

The invention relates to novel ethephon formulations. In particular, the invention is

concerned with highly loaded ethephon formulations.

Background Art Ethephon (2-chloroethylphosphonic acid) is a well-known plant growth regulator,

which decomposes in plant tissue to ethylene. It is regarded as being of low toxicity and is used to promote ripeness in such crops as coffee, cotton, pineapple, rice,

tobacco, tomatoes and wheat.

Ethephon is particularly used in cotton crops, because it can initiate fruiting, promote

early boll opening, enhance defoliation and assist in scheduled harvesting. For convenience below, ethephon will be discussed with reference to cotton. However, it

is to be understood that the ethephon formulations of the invention are not limited to cotton crops.

Ethephon has high solubility in water and consequently foliar applications of ethephon

are typically made using soluble liquid formulations. The concentration of ethephon in

a formulation depends on the purity of the technical grade supplied by the manufacturer. The starting material of ethephon used for current formulating is in a

liquid concentrate form, containing water and other excipients, such as dyes.

High concentration formulations are generally desirable: a highly loaded formulation can deliver the required quantity of active ingredient to a user in a smaller volume,

saving packaging, freight costs, storage volume and energy costs and reducing waste.

Ethephon is generally used at a high rate, for example up to 2.1 kg ai/ha in cotton.

Therefore it would be beneficial to provide formulations of ethephon which are more highly loaded than those currently available.

It has been discovered that it is possible to provide ethephon formulations that are more highly loaded yet stable, by using as starting material a solid form of ethephon,

rather than the liquid concentrate used for formulations until now.

Summary of the Invention

Accordingly, the invention provides a method of preparing an ethephon formulation having an active ingredient concentration of more than 900g/L, the method including

the steps of:

(a) melting solid ethephon to a molten state;

(b) mixing the molten ethephon with water; and

(c) allowing or causing the water and ethephon mixture to cool to ambient temperature while blending the mixture.

The invention also provides a soluble concentrate ethephon formulation having a concentration of more than 900g/L. The formulation may be produced using the

method of the invention.

Preferably, the concentration of ethephon in the formulation is about 1000 g/L.

It has been found that the specific gravity of ethephon (1.4 at 20 degrees Celsius) is

sufficient to enable a higher maximum concentration of more than 900 g/L ai in the formulation of the invention, even when the solid ethephon has a purity of only 900

g/kg or even as low as 710 to 720 g/kg.

It will be appreciated that the method of the invention is more efficient than the

current method for ethephon formulations. In the current method, the supplier of the active ingredient produces a liquid technical concentrate, by combining solid ethephon with water. The liquid technical concentrate is then supplied to the formulator, who

further dilutes it to a required concentration, using water, and includes other additives as desired. In the method of the invention, however, the supplier provides solid ethephon to the formulator, who then melts and dilutes it, as described above.

The formulation of the invention may include ethephon and water only, or may include any other desirable or convenient ingredient. To maintain the high loading of active

ingredient in the formulation, there may be no other ingredient, apart from water.

Testing has shown that the highly loaded formulations of the invention are stable, with

an expected shelf life of at least two years. Testing also indicates that the formulations of the invention are stable in cold conditions.

Trial results on cotton crops have shown that formulations of the invention are as

effective as prior art ethephon formulations in relation to defoliation and opening of bolls

In order that the invention in its various aspects may be more readily understood and put into practice, one or more preferred embodiments thereof will now be described.

Detailed Description of Preferred Embodiments

Example 1: Soluble Concentrate Formulation (S) containing 1000 g/L Ethephon

Solid ethephon TGAC 90% Min, supplied by Jiangsu Anpon, of Jiangsu Province, China,

was heated at 80 degrees Celsius until molten. (The melting point of ethephon is 74-75

degrees Celsius.)

304.9 g/L of potable water (town supply) was charged into a plastic blending vessel

equipped with a propeller type stirrer. Mixing was commenced and 1109.9 g/L of the still-molten ethephon was added while continuing to mix.

The mixture was blended on slow speed (200-300 rpm) until it had cooled to ambient temperature.

The resultant SL formulation was analysed and contained 1109.9 g/L ethephon

(Technical 90.1%) as active ingredient with 304.90 g/L water. The formulation was a

clear, straw coloured liquid, with negligible odour. Its pH at 1% v/v dilution was 1-2 measured using CIPAC MT 75.3. It had a density at 20 degrees Celsius of 1.405 - 1.425 g/mL, measured with Density Meter Anton Paar DMA 48. Its persistent foam in standard water was maximum 60 ml foam after one minute, using CIPAC MT 47.2, at 10.0 mL/200 mL. It showed solution stability in standard water at 23 degrees Celsius, having nil sediment after 18 hours, according to CIPAC MT 41 at 5.00 mL/100 mL.

The formulation was suitable for packaging in a HDPE container with a screw cap

closure.

The formulation was subjected to accelerated storage conditions in that HDPE

container. It was determined to be stable to heat for 2 weeks at 54 degrees Celsius and

therefore is expected to be shelf stable for at least 2 years.

The formulation was subjected to cold storage condition for 7 days at 0 degrees

Celsius. The absence of any separation or crystal growth indicated that the formulation was cold storage stable.

Example 2: Field Tests

Three field trials were conducted to evaluate the efficacy of the ethephon formulation of Example 1, identified as AD-AU-1805. In the trials, AD-AU-1805 was compared with

the commercially registered formulation "Promote Plus 900", containing 900 g

ethephon/L. In addition, AD-AU-1805 was compared with Promote Plus 900 in tank mixtures with other defoliants commonly used with ethephon in cotton, including:

• "Escalate 500" containing 500 g/L thidiazuron

• "Escalate Ultramax" containing 240 g/L thidiazuron + 120 g/L diuron

• D-C Tron oil adjuvant

In the tables below, DAT means 'days after treatment'.

Field Test 1: Berrigan

The ethephon formulation of Example 1, identified as AD-AU-1805, was applied, alone

and in combination with other active ingredients, at various rates to a cotton crop at

Berrigan, New South Wales. Performance was compared to known ethephon formulations, alone and in combination with other active ingredients.

The formulations were trialled for Mean Percentage Defoliation, as set out in Table 1 below.

Table 1: Mean Percentage Defoliation

Treatment Rate 6 DAT 9 DAT 13 DAT g ai/ha Untreated 4.3 d 5.6 e 22.1 d PROMOTE PLUS 900 936 29.7 bc 47.8 a-d 54.3 bc PROMOTE PLUS 900 1440 35.1 abc 44.3 a-d 51.9 bc PROMOTE PLUS 900 2160 50.4 a 59.7 a 71.3 a AD-AU-1805 936 26.2 bc 40.9 bcd 50.5 bc AD-AU-1805 1440 19.9 cd 31.8 d 46.4 c AD-AU-1805 2160 43.9 ab 52.4 abc 58.4 abc ESCALATE 500 SC + D-C-TRON 50 22.5 cd 38.1 cd 56.1 abc ESCALATE 500 SC + PROMOTE 50+360 26.1 bc 40.4 bcd 51.6 bc PLUS 900 + D-C-TRON ESCALATE 500 SC + PROMOTE 50+720 25.8 bc 43.0 a-d 56.4 abc PLUS 900 + D-C-TRON ESCALATE 500 SC + AD-AU-1805 50+360 27.7 bc 42.2 a-d 51.8 bc + D-C-TRON ESCALATE 500 SC + AD-AU-1805 50+720 44.1 ab 54.2 abc 60.7 abc + D-C-TRON F probability 0.002 <0.001 0.003 LSD 5 % 18.6 18.6 16.8

Means within the same cell with a letter in common are not significantly different (P>0.05)

The ethephon formulation of Example 1, identified as AD-AU-1805, was applied, alone and in combination with other active ingredients, at various rates to the same cotton

crop at Berrigan, New South Wales. Performance was compared to known ethephon formulations, alone and in combination with other active ingredients.

The formulations were trialled for Mean Percentage Fresh Leaf Remaining on Plants as set out in Table 2 below.

Table 2: Mean Percentage Fresh Leaf Remaining on Plants

Treatment Rate 6 DAT 9 DAT 13 DAT g ai/ha Untreated 85.1 f 81.5 f 67.9 d PROMOTE PLUS 900 936 57.9 cde 40.3 a-e 35.6 bc PROMOTE PLUS 900 1440 54.3 a-e 40.5 a-e 34.5 bc PROMOTE PLUS 900 2160 36.2 a 20.8 a 14.6 a AD-AU-1805 936 56.5 b-e 42.0 b-e 35.8 bc AD-AU-1805 1440 69.2 ef 55.7 e 44.3 c AD-AU-1805 2160 48.0 a-d 35.6 a-d 30.1 abc ESCALATE 500 SC + D-C-TRON 50 63.9 de 49.1 de 34.2 bc ESCALATE 500 SC + PROMOTE 50+360 64.4 de 46.1 cde 35.4 bc PLUS 900 + D-C-TRON ESCALATE 500 SC + PROMOTE 50+720 65.4 de 43.5 b-e 30.3 abc PLUS 900 + D-C-TRON ESCALATE 500 SC + AD-AU-1805 50+360 62.7 cde 47.7 de 36.5 bc + D-C-TRON ESCALATE 500 SC + AD-AU-1805 50+720 44.6 abc 32.9 a-d 27.6 abc + D-C-TRON F probability <0.001 <0.001 0.004 LSD 5 ° 18.2 19.9 18.8

and in combination with other active ingredients, at various rates to the same cotton

The formulations were trialled for Mean Regrowth as set out in Table 3 below, using a (0-10 scale) at 13 DAT.

Table 3: Mean Regrowth

Rate Canopy level g ai/ha Lower Middle Upper Untreated 8.7 8.0 c 7.3 c PROMOTE PLUS 900 936 7.0 5.0 ab 3.0 ab PROMOTE PLUS 900 1440 6.7 4.7 a 3.0 ab PROMOTE PLUS 900 2160 7.0 5.0 ab 1.3 a AD-AU-1805 936 8.0 6.0 ab 4.7 b AD-AU-1805 1440 7.3 5.3 ab 2.3 ab AD-AU-1805 2160 7.7 6.3 b 2.0 a ESCALATE 500 SC + D-C-TRON 50 7.0 5.7 ab 2.7 ab ESCALATE 500 SC + PROMOTE 50+360 PLUS 900 + D-C-TRON 7.7 5.3 ab 2.3 ab ESCALATE 500 SC + PROMOTE 50+720 PLUS 900 + D-C-TRON 7.7 5.7 ab 2.3 ab ESCALATE 500 SC + AD-AU-1805 50+360 + D-C-TRON 7.0 4.7 a 2.3 ab ESCALATE 500 SC + AD-AU-1805 50+720 + D-C-TRON 7.3 5.3 ab 2.3 ab F probability 0.18 0.032 0.012 LSD 5 % ns 1.6 2.5

NS - not significant

Field Test 2: Narrabri

and in combination with other active ingredients, at various rates to a cotton crop at Narrabri, New South Wales. Performance was compared to known ethephon

formulations, alone and in combination with other active ingredients.

The formulations were trialled for Mean Percentage Defoliation, are as set out in Table 4 below.

Table 4: Mean Percentage Defoliation

Treatment Rate 4 DAT 7 DAT 11 DAT g ai/ha Untreated 7.0 16.1 f 19.5 g PROMOTE PLUS 900 936 16.1 24.9 ef 28.5 fg PROMOTE PLUS900 1440 15.6 38.2 bcd 47.8 bcd PROMOTE PLUS900 2160 15.9 46.3 ab 58.4 ab AD-AU-1805 936 8.8 32.7 cde 38.3 def AD-AU-1805 1440 10.0 44.4 ab 48.9 a-d AD-AU-1805 2160 14.6 35.4 b-e 47.4 bcd ESCALATE 500 SC + D-C-TRON 50 9.7 31.3 cde 39.5 c-f ESCALATE 500 SC + PROMOTE 50+360 9.0 28.6 cde 42.2 cde PLUS 900 + D-C-TRON ESCALATE 500 SC + PROMOTE 50+720 12.4 32.5 cde 42.7 cde PLUS 900 + D-C-TRON ESCALATE 500 SC + AD-AU-1805 50+360 12.6 26.3 ef 39.9 cde + D-C-TRON ESCALATE 500 SC + AD-AU-1805 50+720 7.6 39.0 bc 50.3 abc + D-C-TRON F probability 0.71 <0.001 0.003 LSD 5% ns 18.6 16.8

ns - not significant

crop at Narrabri, New South Wales. Performance was compared to known ethephon formulations, alone and in combination with other active ingredients.

The formulations were trialled for Mean Percentage Fresh Leaf Remaining on Plants as set out in Table 5 below.

Table 5: Mean Percentage Fresh Leaf Remaining on Plants

Treatment Rate 4 DAT 7 DAT 11 DAT g ai/ha Untreated 89.3 80.0 g 78.2 f PROMOTE PLUS 900 936 80.9 72.6 fg 68.9 ef PROMOTE PLUS 900 1440 74.7 56.5 b-e 48.0 bc PROMOTE PLUS 900 2160 74.7 49.2 ab 35.4 a AD-AU-1805 936 84.5 63.5 c-f 56.5 cd AD-AU-1805 1440 80.5 51.4 abc 47.0 bc AD-AU-1805 2160 78.7 58.3 b-e 48.4 bc ESCALATE 500 SC + D-C-TRON 50 86.1 65.1 def 55.1 cd ESCALATE 500 SC + PROMOTE 50+360 85.0 66.2 def 53.2 bcd PLUS 900 + D-C-TRON ESCALATE 500 SC + PROMOTE 50+720 83.8 62.7 c-f 53.4 bcd PLUS 900 + D-C-TRON ESCALATE 500 SC + AD-AU-1805 50+360 83.3 67.8 ef 57.2 cd + D-C-TRON ESCALATE 500 SC + AD-AU-1805 50+720 85.4 55.4 bcd 43.8 ab + D-C-TRON F probability 0.184 <0.001 <0.001 LSD 5 % ns 12.2 11.0

ns - not significant

and in combination with other active ingredients, at various rates to the same cotton crop at Narrabri, New South Wales. Performance was compared to known ethephon

formulations, alone and in combination with other active ingredients.

The formulations were trialled for Mean Percentage Desiccated Leaf as set out in Table 6 below.

Table 6: Mean Percentage Desiccated Leaf Remaining on Plants

Treatment Rate 4 DAT 7 DAT 11 DAT g ai/ha Untreated 3.7 a 3.9 2.3 a PROMOTE PLUS 900 936 3.1 a 2.4 2.6 a PROMOTE PLUS 900 1440 9.6 bc 5.3 4.2 a-d PROMOTE PLUS 900 2160 9.4 bc 4.5 6.2 e AD-AU-1805 936 6.7 abc 3.9 5.2 cde AD-AU-1805 1440 9.5 bc 4.3 4.1 a-d AD-AU-1805 2160 6.7 abc 6.3 4.2 a-d ESCALATE 500 SC + D-C-TRON 50 4.2 a 3.6 5.4 cde ESCALATE 500 SC + PROMOTE 50+360 6.0 ab 5.2 4.6 b-e PLUS 900 + D-C-TRON ESCALATE 500 SC + PROMOTE 50+720 3.8 a 4.8 3.8 abc PLUS900+ D-C-TRON ESCALATE 500 SC + AD-AU-1805 50+360 4.0 a 5.9 3.0 ab + D-C-TRON ESCALATE 500 SC + AD-AU-1805 50+720 6.9 abc 5.5 5.9 de + D-C-TRON F probability 0.013 0.60 0.004 LSD 5 % 4.2 ns 2.0

ns - not significant

Field Test 3: Gunnedah

and in combination with other active ingredients, at various rates to a cotton crop at Gunnedah, New South Wales. Performance was compared to known ethephon

formulations, alone and in combination with other active ingredients.

The formulations were trialled for Mean Percentage Defoliation as set out in Table 7

below.

Table 7: Mean Percentage Defoliation

Treatment Rate 3 DAT 7 DAT 10 DAT g ai/ha Untreated 47.9 d 72.9 c 97.6 PROMOTE PLUS 900 1440 84.1 ab 99.0 ab 95.6 PROMOTE PLUS 900 2160 78.9 abc 96.0 ab 99.5 AD-AU-1805 1440 78.5 abc 96.6 ab 100.0 AD-AU-1805 2160 87.0 a 99.5 a 99.5 ESCALATE ULTRAMAX + D-C- 85.4 ab 99.5 a 99.8 TRON 50 ESCALATE ULTRAMAX + 50+360 82.4 ab 99.8 a 99.0 PROMOTE PLUS 900 + D-C TRON ESCALATE ULTRAMAX+ 50+720 84.8 ab 99.1 ab 97.4 PROMOTE PLUS 900 + D-C TRON ESCALATE ULTRAMAX + AD-AU- 50+360 81.3 ab 98.2 ab 100.0 1805 + D-C-TRON ESCALATE ULTRAMAX + AD-AU- 50+720 80.5 ab 96.8 ab 99.4 1805 + D-C-TRON F probability <0.001 <0.001 0.086 LSD 5 % 12.0 6.8 ns ns - not significant Means within the same cell with a letter in common are not significantly different (P>0.05)

crop at Gunnedah, New South Wales. Performance was compared to known ethephon formulations, alone and in combination with other active ingredients.

The formulations were trialled for Mean Percentage Fresh Leaf Remaining on Plants as

set out in Table 8 below.

Table 8: Mean Percentage Fresh Leaf Remaining on Plants

Treatment Rate 3 DAT 7 DAT 10 DAT g ai/ha Untreated 36.6 f 22.9 b 2.2 b PROMOTE PLUS 900 1440 6.7 a-d 0.6 a 0.5 a PROMOTE PLUS 900 2160 11.9 cd 1.8 a 0.5 a AD-AU-1805 1440 8.8 bcd 0.2 a 0.0 a AD-AU-1805 2160 1.2 a 0.0 a 0.5 a ESCALATE ULTRAMAX + D-C- 50 6.1 abc 0.0 a 0.2 a TRON ESCALATE ULTRAMAX+ 50+360 11.0 bcd 0.0 a 0.1 a PROMOTE PLUS 900 + D-C TRON ESCALATE ULTRAMAX+ 50+720 4.4 ab 0.0 a 0.6 a PROMOTE PLUS 900 + D-C TRON ESCALATE ULTRAMAX + AD-AU- 50+360 4.8 ab 0.0 a 0.0 a 1805 + D-C-TRON ESCALATE ULTRAMAX + AD-AU- 50+720 8.8 bcd 2.6 a 0.0 a 1805 + D-C-TRON F probability <0.001 <0.001 0.008 LSD 5 % 10.2 5.6 1.6

ns - not significant

The formulations were trialled for Mean Percentage Boll Opening Post Treatment as set out in Table 9 below.

Table 9: Mean Percentage Boll Opening Post Treatment

Treatment Rate 3 DAT 7 DAT 10 DAT g ai/ha Untreated 34.3 44.2 d 68.1 PROMOTE PLUS 900 1440 37.7 76.7 abc 88.6 PROMOTE PLUS 900 2160 32.4 66.0 a-d 81.3 AD-AU-1805 1440 19.5 92.9 a 98.5 AD-AU-1805 2160 38.8 90.3 a 91.5 ESCALATE ULTRAMAX + D-C- 50 25.5 61.6 bcd 79.4 TRON ESCALATE ULTRAMAX + 50+360 24.3 57.3 bcd 69.3 PROMOTE PLUS 900 + D-C TRON ESCALATE ULTRAMAX + 50+720 29.8 66.4 a-d 86.1 PROMOTE PLUS 900 + D-C TRON ESCALATE ULTRAMAX + AD-AU- 50+360 33.7 68.2 a-d 80.5 1805 + D-C-TRON ESCALATE ULTRAMAX + AD-AU- 50+720 19.5 54.6 cd 71.6 1805 + D-C-TRON F probability 0.70 0.032 0.086 LSD 5 % ns 27.3 ns

ns - not significant

It will be appreciated from the data in Tables 1 to 9 that the efficacy of the

formulations of the invention is at least comparable to that of prior art formulations. However the formulations of the invention, being more concentrated, are more efficient. An increase in concentration from 900 g ai/L to 1000 g ai/L represents an 11%

reduction in the volume of material to be formulated, transported, stored and applied by the end user.

Claims

1. A method of preparing an ethephon formulation having an active ingredient concentration of more than 900 g/L, the method including the steps of:

(a) melting solid ethephon to a molten state;

(b) mixing the molten ethephon with water; and

2. The method of claim 1, wherein the formulation is a soluble concentrate.

3. The method of claim 1 or 2, wherein the active ingredient concentration of ethephon in the formulation is about 1000 g/L.

4. An ethephon formulation prepared by the method of any one of claims 1to 3.

5. The ethephon formulation of claim 4, when used as a plant growth regulator or a harvest aid.