Introduction

Tristyrylphenol ethoxylates (TSPEOn) are important nonionic surfactants which are widely used in pesticide formulations to enhance the penetration and spread of the active ingredient. As the nonionic surfactant, TSPEOn was second only to alkylphenol ethoxylates (APEOn) in China (1). A typical TSPEOn surfactant formulation is comprised of tristyrene with an average of 16 ethoxylate (EO) units, usually within the range of 1 to 33 ethoxylate units as depicted in Figure 1 (2, 3). Studies have shown that TSPEOn had moderate acute toxicity, subchronic toxicity, thyroid, and liver toxicity in mammals (4, 5). Furthermore, its degradation intermediates, styrenated phenols were demonstrated to have acute toxicity or estrogenic activity in Pseudokirchneriella subcapitata and Oryzias latipes (6–8). Considering the toxicity and the large production volumes, the United States Environmental Protection Agency has set a TSPEOn limit of no more than 15% in pesticide formulations in (4). However, concern about its residue and environmental behavior continue to this day, such information is currently lacking.

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FIGURE 1

Previous studies had shown that relatively high concentrations of TSPEOn were detected in the agricultural ecosystem, such as cherries, peaches, and kiwifruit (1). Additionally, the dissipation behavior of TSPEOn was reported in lettuce under greenhouse and field conditions with half-lives of 2.18–5.36 and 1.82–5.52 days, respectively. TSPEOn were relatively persistent in the field. It can be concluded that the cultivation system and plant type jointly affect the absorption and degradation of TSPEOn (9, 10). Cowpea [Vigna unguiculata (L.) Walp.] is an ideal food for diabetic due to its phospholipid can promote insulin secretion and participate in glucose metabolism, which is widely cultivated in the tropical and subtropical region of Asia. However, cowpea is susceptible to a variety of diseases and insect infestations, such as aphids, thrips, cowpea weevil, and liriomyza (11–15). Pesticide application is a probable major source of TSPEO residues during cowpea cultivation (11, 16–18). Further research is needed to study the potential different dissipation behavior of TSPEOn by cowpea growing in terms of public health and food safety.

In this study, a cowpea field experiment was carried out in Guangdong province, the main region of cowpea production in China, which was treated with TSPEOn at different doses. Different 24 tristyrylphenol ethoxylate homologs were all analyzed in cowpea from the field experiments to shed light on the dissipation rates and distribution profiles of different TSPEO homologs in cowpea. The acute and chronic dietary exposure risks of TSPEOn in cowpea for different subgroups (age and gender) based on supervised field trial data and relevant toxicological parameters were also assessed. The results obtained in this study have important implications in understanding the residue fate of TSPEOn.

Materials and methods

Reagents and chemicals

The standard of Technical TSPEO16 (a mixture of TSPEOn with an average of 16 EO units) was purchased from Jiangsu Zhongshan Chemical Co., Ltd., (Nanjing, China) and purified by using preparative liquid chromatography (LC) as described in our earlier study (19). Ultrapure water (18.2 MΩ⋅cm) was prepared by Milli-Q purification system (Millipore, Bedford, MA, USA). Octadecyl (C18) and primary secondary amine (PSA) sorbents were purchased from Bonna-Agela Technologies, Ltd., (Tianjin, China). Multiwalled carbon nanotubes (MWCNTs) were obtained from Nanjing XFNANO Materials Technologies (Nanjing, China). Acetonitrile (≥ 99.95%) was liquid chromatography-mass spectrometry (LC-MS) grade (Thermo Fisher Scientific, Waltham, MA, USA). Anhydrous magnesium sulfate and sodium chloride were analytical grade (Sinopharm Chemical Reagent Company, Beijing, China).

Field trails and sampling

Field trials of cowpea were designed under open conditions according to the Guideline for testing pesticide residues in crops (NY/T 788-) and the Standard operating procedures on pesticide registration residue field trials (20). For the field dissipation experiments, the emulsifier 601 (Technical TSPEO16) was diluted with water (500-fold dilution) and sprayed on the cowpea and bare soil at a dose of 2,250 g/ha during the vegetative period. A separate plot with the no-TSPEOn application was used as a control. Cowpea planting density and fertilization management in the experimental field were designed, according to the conditions of local planting. The area of each plot was 15 m2. Representative 2 kg cowpea and soil samples were collected randomly from each plot at 2 h, 1 d, 3 d, 5 d, 7 d, 10 d, 14 d, and 21 d after spraying. Both the cowpea and soil samples were stored in plastic bags with proper labels before being transferred to the laboratory.

For the terminal residue experiments, the emulsifier 601 was applied at dosage of 225 g/ha and 450 g/ha, respectively. Two and three applications were made with an interval of 5 d. Representative 2 kg cowpea and soil samples were collected separately from each plot at 5, 7, 10, 14, and 21 d after the last application. The mature cowpea samples were collected from the top, middle, and bottom of the shelf from each plot. All cowpea samples were cut into small pieces, homogenized and stored at −20°C until analysis. All soil samples were collected from 0 to 15 cm of the layer, dried at room temperature, ground to a powder using an electric grinder and sifted through a 2-mm sieve. All samples were packed in seal aluminum foil bags, and then stored at –20°C until analysis.

Instrument condition

Tristyrylphenol ethoxylates (TSPEOn) analysis was performed by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) according to our previous study (1). Shimadzu Triple Quadrupole LCMS- system (Shimadzu, Kyoto, Japan) equipped with a Xbridge C18 (2.1 × 50 mm, 5 μm, Waters, Milford, MA, USA) precolumn and a Nova-Pak Silica (2.1 × 150 mm, 4 μm, Waters, Milford, MA, USA) column were used to separate the different homolog TSPEOn. The flow was kept at 0.30 mL/min. The mobile phases were 2 mM ammonium acetate water (A) and acetonitrile (B), and the gradient elution program was as follows: mobile phase B was ramped from 95 to 88% over 5 min, varied from 88 to 80% over 5.5 min, held at 80% for 2.0 min, and then increased to 95% over 0.5 min, thereby maintaining initial chromatographic condition within 7 min. The column temperature was maintained at 40°C. The injection volume was 2 μL.

Mass spectrometry (MS/MS) analysis was accomplished using a tandem quadrupole mass spectrometer (LCMS-, Shimadzu, Kyoto, Japan) in time programmed multiple-reaction monitoring mode in positive mode. The source parameters were optimized and performed as follows: the ion source temperature (TEM) was 450°C. The base ions were the ammonium adduct ions [(M + NH4)+ or (M + 2NH4)2+]. All the MS parameters were listed in Supplementary Table 1 in supporting information. The LabSolutions software was used to acquire and analyze the data (version 5.82, Shimadzu).

Sample preparation

The 10 g homogenized samples (cowpea and soil) were weighed into a 50-mL polypropylene centrifuge tube with a screw cap. To this, 10 mL ultrapure water (only to soil) and 10 mL acetonitrile were subsequently added. The sample tubes were vigorously vortexed for 1 min, and then ultrasound for 10 min. After that, 1 g sodium chloride and 4 g anhydrous magnesium sulfate were added, and the tube was vortexed for another 1 min and then centrifuged at 6,000 rpm for 5 min. 1 mL supernatant was transferred into a 10-mL centrifuge tube containing different purifying agents (150 mg anhydrous magnesium sulfate, and 5 mg MWCNTs for cowpea extraction and 5 mg MWCNTs, 25 mg PSA, and 25 mg C18 for soil extraction). After vertexing for 1 min, the tube was centrifuged at 10,000 rpm for 5 min. Finally, the resulting supernatant was filtered into an autosampler vial through a 0.22-μm membrane (Bonna-Agela Technologies Inc., Tianjin, China) for HPLC-MS/MS analysis.

Method validation

The method validation results for TSPEOn in cowpea are shown in Supplementary Table 2. Recovery experiments were performed to evaluate the accuracy and precision of the method. Five replicates of spiked blank samples at three spiking levels were prepared. The recoveries of all the TSPEO homologs (n = 6–29) in cowpea ranged from 79.7 to 120%, with RSDs of 0.70–20.1%. The linearities of all the TSPEO homologs (n = 6–29) were evaluated by analyzing matrix-matched standard solutions, and the correlation coefficients (R2) were higher than 0.990. The limits of detection (LODs) and the limits of quantification (LOQs) were determined based on the signal-to-noise ratios of 3 and the lowest spiked concentration of each analyte, respectively. The LODs and LOQs for the homologs of TSPEOn were 0.001–0.14 and 0.06–5.13 μg/kg, respectively. The method validation results for TSPEOn in soil were listed in our previous research (19). The recoveries and RSDs ranged from 64.2 to 113% and 1.30 to 17.3%, respectively.

Data processing and statistical analysis

The dissipation kinetics of all 24 TSPEO homologs in cowpea and soil were estimated according to the pseudo first-order dynamics equation:

where C0 (μg/kg) and Ct (μg/kg) indicate the concentrations of TSPEO homologs and ΣTSPEOn at time 0 (d) and time t (d), k is the dissipation rate constant. The half-life (T1/2) was calculated from k by using the equation:

The acute dietary intake risk (aHI) was estimated based on the following equations (10, 21).

where NESTI is the national estimated short-term intake. HR is the highest residue concentration (μg/kg), which is obtained on the highest residue level of the terminal residue experiments. LP is the large portion consumption of cowpea (dark-colored vegetables instead) for the consumers (97.5th percentile of eaters, g/day person), and bw is the mean body weight, which is shown in Supplementary Table 3 (11). In this study, the population was divided into eight groups according to age and gender: child (≤ 11 years), youngster (12–18 years), adult (18–60 years), and elder (> 60 years) for both male and female. The consumption data of dark-colored vegetables was used instead in the dietary risk assessment, when the cowpea consumption data were unavailable. ARfD is the acute reference dose (1.67 mg/kg/d), which was determined using the lowest observed adverse effect level of 500 mg/kg/d and an uncertainty factor of 300 (4, 22).

The chronic dietary intake risk (hazard quotient, HQ) was estimated based on the following equations (10, 21).

where NEDI is the national estimated daily intake. STMR is the median residue in the terminal residue experiments (μg/kg). F is the mean daily consumption of cowpea (dark-colored vegetables instead, g/day person), as shown in Supplementary Table 3 (11), ADI is the acceptable daily intake (0.5 mg/kg/d) calculated using the no observed adverse effect level of 50 mg/kg/d and an uncertainty factor of 100 (4, 22).

Results and discussion

Dissipation of homolog tristyrylphenol ethoxylates (n = 6–29) in cowpea system

The dissipation kinetics curves of different homolog TSPEOn (n = 6–29) and ΣTSPEOn in cowpea were shown in Figure 2. The initial concentrations of TSPEOn (n = 6–29) and ΣTSPEOn deposited on cowpea samples were 23.9–2,316 μg/kg (Figures 2A–X) and 16,506 μg/kg (Figure 2Y) at 2 h after TSPEOn treatment, respectively. After 21 d, 96.1–99.8% of the initial residues of TSPEOn (n = 6–29) were dissipated. The dissipation half-lives of homolog TSPEOn (n = 6–29) and ΣTSPEOn were found to be slightly varied from 2.42 to 4.20 d, which were comparable to those in lettuce (1.82–4.34 d) and cucumber (1.80–4.30 d) in the previous studies (9, 10), indicating that all the homolog TSPEOn (n = 6–29) could be dissipated fast in these vegetables.

FIGURE 2

Similar results were observed in the soil as shown in Figure 3. The dissipation trends of all TSPEOn (n = 6–29) and ΣTSPEOn followed pseudo first-order kinetics. After 21 d, the dissipation rates of homolog TSPEOn (n = 6–29) and ΣTSPEOn can reach 85.3–93.9% in soil, which were slightly lower than those in cowpea. The variety of dissipation rates of homolog TSPEOn (n = 6–29) in cowpea and soil might be related to several factors, including log Kow, climatic conditions, photo-degradation, microorganism biodegradation, preferential absorption, and character of soil (23–30). According to the length of ethoxylate chain, the TSPEOn has been divided into two groups, namely short-chain TSPEOn (n ≤ 16) and long-chain TSPEOn (n > 16) in this study. From Figures 2, 3, it was found that the dissipation half-lives of short-chain TSPEOn (n ≤ 16) were a little bit higher than those of long-chain TSPEOn (n > 16) in cowpea and soil. A regression analysis between the dissipation half-lives and the different homolog TSPEOn (n = 6–29) in cowpea and soil was conducted in Figures 4A,B. It was found that the dissipation half-lives of the homolog TSPEOn (n = 6–29) were significantly decreased with the increasing EO unites in TSPEOn structure in cowpea and soil, indicating that the length of EO chain would be an essential factor influencing the dissipation half-lives of TSPEOn in the cowpea ecosystem.

FIGURE 3 FIGURE 4

Distribution of tristyrylphenol ethoxylates in cowpea ecosystem

The terminal residues of ΣTSPEOn in cowpea are shown in Supplementary Figure 1. The terminal concentrations of ΣTSPEOn were detected and ranged from 40.0 to 1,374 μg/kg in cowpea, which increased with the incremental application frequency and dosage. The typical distributions of homolog TSPEOn (n = 6–29) at 450 g/ha after two applications in cowpea in terminal residue experiments were characterized in Figure 5, and the distributions of other terminal residue experiments were shown in Supplementary Figures 2–4. It was found that a significant bimodal profile was observed in the homolog TSPEOn (n = 6–29) distribution in cowpea. One concentration peak-value was occurred at TSPEO12 (3.04–58.3 μg/kg), and the other was observed at TSPEO22 (6.22–88.4 μg/kg).

FIGURE 5

As shown in Figure 6, a typical normal distribution profile was presented in the commercial TSPEO mixture, but bimodal profiles were observed for TSPEOn in cowpea and soil samples. Compared with the commercial TSPEO mixture, the contributions of TSPEO homologs with short EO unites (n = 6–13) increased from 21.8 to 33.3% in cowpea and soil. All these results implied that the biotransformation would be taken place among the homologs TSPEOn (n = 6–29) in the cowpea ecosystem. However, it has been reported that the long-chain nonylphenol ethoxylate (NPEOn) can biodegraded into more lipophilic shortened EO chain NPEOn by attacking and shortening the hydrophilic part of the molecule of NPEOn under anaerobic conditions (31–34). Short-chain NPEOn presented more toxicity and persistence than long-chain nonylphenol ethoxylate (NPEOn).

FIGURE 6

Risk assessment of tristyrylphenol ethoxylates in cowpea

Assessments of acute and chronic dietary intake risk for cowpea consumption are shown in Table 1. For the acute dietary intake risk, the HRs of ΣTSPEOn in cowpea samples were 1,374, 957, 560, 200, and 301 μg/kg at the interval to harvest of 5, 7, 10, 14, and 21 d, respectively. Accordingly, the aHI values for child (≤ 11 years), youngster (12–18 years), adult (18–60 years), and elder (> 60 years) were 0.04–0.30%, 0.03–0.19%, 0.02–0.15%, 0.02–0.15% for males, and 0.05–0.32%, 0.03–0.18%, 0.02–0.16%, 0.02–0.16% for females, respectively. These results indicate that there is little or no acute risk to humans.

TABLE 1

For the chronic dietary intake risk, the STMRs of ΣTSPEOn in cowpea were 770, 639, 320, 144, and 103 μg/kg at the interval to harvest of 5, 7, 10, 14, and 21 d, respectively. Therefore, the HQs for child (≤ 11 years), youngster (12–18 years), adult (18–60 years), and elder (> 60 years) were 0.05–0.40%, 0.04–0.28%, 0.03–0.24%, and 0.03–0.24% for male, 0.05–0.40%, 0.04–0.27%, 0.03–0.25%, 0.03–0.25% for female, respectively, significantly lower than the acceptable risk level (100%). These results suggest that the risk of chronic dietary intake of ΣTSPEOn based on the terminal residues of different interval to harvest is acceptably low. The assessment results were coincided with the study of cucumber (10). Nevertheless, it should be noted that children are the most susceptible population to acute dietary intake risk and chronic dietary intake risk, and the impact on the health of children should be monitored in future.

Conclusion

In the present study, the dissipation and terminal residues of TSPEO homologs in a cowpea ecosystem were studied. The dissipation rates of all the homolog TSPEOn (n = 6–29) in cowpea were higher than in soil. The long-chain TSPEOn presented a higher dissipation rate than that of short-chain TSPEOn in the cowpea ecosystem. The fact that the typical bimodal profiles of TSPEO homologs and the noticeable increase of short TSPEOn (n = 6–13) indicated that the long-chain TSPEOn would be degraded to short-chain TSPEOn in the cowpea ecosystem. The risks of acute and chronic dietary intake of ΣTSPEOn in cowpea for general consumers in China were distinctly lower than the acceptable levels (100%). But children were the most susceptible population to acute and chronic dietary intake risks, which should be paid more attention to. This study provides proper guidance and feasibility suggestions for the TSPEOn application in pesticide formulations.

Data availability statement

The raw data supporting the conclusions of this article will be made available by the authors, without undue reservation.

Author contributions

ML: investigation, sample processing, and writing – original draft. QW: formal analysis. XL: investigation. NY: sample processing. MJ: writing – review and editing. LZ: methodology and data curation. JW: supervision. FJ: writing – review and editing and funding acquisition. All authors contributed to the article and approved the submitted version.

Funding

This work was funded by the National Key Research and Development Program of China (YFC), the Agricultural Science and Technology Innovation Program and the Young Talents Program under Chinese Academy of Agricultural Sciences.

Conflict of interest

The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

Publisher’s note

All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors and the reviewers. Any product that may be evaluated in this article, or claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.

Supplementary material

The Supplementary Material for this article can be found online at: https://www.frontiersin.org/articles/10./fnut../full#supplementary-material

References

EPB1 - Pesticide formulations containing alkoxylated tristyrylphenol hemi-sulfate ester neutralized alkoxylated amine surfactants - Google Patents

Pesticide formulations containing alkoxylated tristyrylphenol hemi-sulfate ester neutralized alkoxylated amine surfactants Download PDF

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EPB1

EPB1 EPA EPA EPB1 EP B1 EP B1 EP B1 EP A EP A EP A EP A EP A EP A EP B1 EP B1 EP B1

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formula

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Estep Carolyn Moore

Shui-Chui Victor Chow

Michael James Hopkinson

Tammy Tyler Shannon

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• diesters Chemical class 0.000 description 1
• MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
• dilution Substances 0.000 description 1
• dilution Methods 0.000 description 1
• dispersion Substances 0.000 description 1
• effects Effects 0.000 description 1
• flowable concentrates for seed treatment Substances 0.000 description 1
• fungicidal effect Effects 0.000 description 1
• ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
• hydrocarbyl group Chemical group 0.000 description 1
• insecticidal effect Effects 0.000 description 1
• ionic surfactant Substances 0.000 description 1
• irritation Effects 0.000 description 1
• longterm Effects 0.000 description 1
• mining Methods 0.000 description 1
• modification Effects 0.000 description 1
• modification Methods 0.000 description 1
• phosphoric acid esters Chemical class 0.000 description 1
• raw material Substances 0.000 description 1
• regulatory effect Effects 0.000 description 1
• saponification reaction Methods 0.000 description 1
• saturated elastomer Polymers 0.000 description 1
• saturated fatty acids Chemical class 0.000 description 1
• saturated fatty acids Nutrition 0.000 description 1
• scission Effects 0.000 description 1
• severe injury Effects 0.000 description 1
• shampoo Substances 0.000 description 1
• HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
• soap Substances 0.000 description 1
• soil Substances 0.000 description 1
• supplementation Effects 0.000 description 1
• supplementing effect Effects 0.000 description 1
• suspension Substances 0.000 description 1
• temporal effect Effects 0.000 description 1
• toxicity Effects 0.000 description 1
• toxicity Toxicity 0.000 description 1
• transesterification reaction Methods 0.000 description 1
• unsaturated fatty acids Chemical class 0.000 description 1
• unsaturated fatty acids Nutrition 0.000 description 1
• water dispersible powder for slurry treatment Substances 0.000 description 1

Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
  • C08G65/—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
  • C08G65/—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
  • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C305/00—Esters of sulfuric acids
  • C07C305/02—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton
  • C07C305/04—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated
  • C07C305/10—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated being further substituted by singly-bound oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
  • C08G65/—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
  • C08G65/—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides

Definitions

• the present invention relates to a surfactant system for general use in agricultural compositions, including, but not limited to herbicidal, fungicidal and insecticidal formulations comprised of two components: an alkoxylated tristyrylphenol hemi-sulfate ester neutralized to the desired pH with an appropriate amount of an alkoxylated alkyl amine.
• Alkylphenol ethoxylates and their anionic derivatives are surfactants that are well known to industry and have historically been relied upon heavily by agricultural chemical producers.
• formulations containing APEs do not always provide the most desirable combination of design specifications, e.g. product efficacy, working parameters and cost.
• Traditional non-APE surfactant systems have not been readily adaptable substitutes for APE surfactants.
• calcium dodecylbenzene sulfonic acid used in conjunction with alkoxylated amines have not been as robust as the APE's and their derivatives due to unacceptable performance in one or more key performance areas, such as emulsion stability, acute toxicity, temporal and thermal stability, chemical and physical stability; solution, suspension or dilution dynamics; shear stress tolerance; viscosity; or lack of compatibility with mixing partners.
• Phosphate esters of alcohol ethoxylates which are non-APE surfactants found in many industrial uses, have long term stability problems due to hydrolytically driven transesterification and saponification reactions involving the mono-ester, di-ester, and free acid components of the surfactant mixture.
• Sulfated surfactants in flowable formulations are typically prone to hydrolytic decomposition, particularly when the formulations are stored in hot, summer warehouse conditions.
• ethoxylated tristyrylphenol hemi-sulfate esters which have been neutralized with ethoxylated amines are suitable as alternative ionic surfactants for general use in agricultural products.
• ethoxylated tristyrylphenol hemi-sulfate esters fall into the general classification of APE's, the tristyrylphenol group is structurally very different from known or conventional APE surfactants.
• the surfactants of the instant invention may be in the form of a surfactant compound, or composition containing one or more of the surfactant compounds or salts.
• compositions containing the instant surfactant compounds do not contain or are substantially free of known or conventional APEs.
• the surfactants of the instant invention are obtained from combining the appropriate ethoxylated tristyrylphenol hemi-sulfate ester with the appropriate ethoxylated amine.
• the steric configuration of the tristyrylphenol group protects the surfactant from hydrolytic cleavage typically observed in other known anionic sulfate ester surfactant systems.
• One aspect of the invention concerns the compounds of Formula (1) : (H-B) + A - (1), wherein A - is the conjugate base of the acid H-A, wherein H-A is an ethoxylated tristyrylphenol hemi-sulfate ester; and the (H-B) + is the conjugate acid of the base B, wherein B is an ethoxylated amine.
• An aspect of the invention are the compounds having the formula (H-B) + A - , where A - is the anion of the formula: wherein n is a number from 1 to 50 inclusive, and wherein (H-B) + is the cation of the formula: wherein R 2 is selected from the group consisting of C 1 -C 24 alkyl and C 2 -C 24 alkenyl-CH 2 -, and x + y is a number from 4 to 9 inclusive.
• a preferred embodiment of the invention are the compounds of formula (1), wherein A - is: wherein n is from about 4 to 25 (preferably 4 to 16, especially 8); and wherein (H-B) + is the cation of the formula: wherein R 2 is selected from the group consisting of n-octadecyl, n-hexadecyl and cis-9-octadecenyl, and x + y is a number from 4 to 9.
• a feature of the invention is where x + y is 5.
• the invention also concerns the process for the preparation of a compound of the formula (H-B) + A - in which (H-B) + and A - have the meanings given above, characterised by neutralizing an ethoxylated tristyrylphenol hemi-sulfate ester of formula (2a) infra (also referred to as HA) with an ethoxylated amine of formula (3a) infra (also herein referred to as B).
• HA ethoxylated tristyrylphenol hemi-sulfate ester of formula (2a) infra
• ethoxylated amine of formula (3a) infra also herein referred to as B.
• the ammoniumsulfate compounds or the product from the process of combining an aromatic acid HA with an ethoxylated amine B are both features of the instantly disclosed invention.
• the scope of the invention disclosed herein should not be construed to be limited by any particular chemical theory relating to the complexation, equilibration, reaction or acid-base chemistry of the components used to make the surfactants or other ingredients used to make other ultimately useful formulations such as, pesticide formulations.
• another aspect of the invention is the surfactant composition comprising one or more aromatic acids and one or more ethoxylated amines wherein the constituent components may or may not have interacted chemically so as to result in a change in form of the components.
• the invention encompasses the static composition of the appropriate components admixed together as well as the chemically integrated surfactant composition comprising at least one aromatic acid and at least one ethoxylated amine.
• Static composition denotes the composition composed of components wherein the components have not substantially changed by virtue of their combination with other composition components.
• “Chemically integrated composition” means a composition that results from the natural equilibration, complexation, dissociation or other chemical transformation if any that may occur after combination of the components and prior to ultimate use of the surfactant in a pesticide formulation. Therefore, the "chemically integrated composition” of the instant invention by definition encompasses the situation where there is a “static composition” as well as any resultant composition occurring at any point in time between initial creation and ultimate use in the field of products containing the surfactant. In other words, the disclosed invention is not limited to a static composition of chemically unaltered constituent components.
• Another aspect of the invention is the surfactant composition produced as a whole from the combination of the aromatic acid HA and the ethoxylated amine base B to the extent it is composed of products other than ammoniumsulfate compounds.
• Such a composition may contain chemically unaltered starting materials as well as other reaction products or by-products from reaction, equilibration, dissociation or complexation of the components in the composition.
• the invention also includes the process for obtaining a surfactant which is useful as a substitute for known or conventional APE's.
• the process of obtaining or making any of the surfactants is herein disclosed as part of the invention.
• the invention also includes the method of using the surfactant compounds of formula (1) and compositions thereof as substitutes for known or conventional APEs.
• the ethoxylated amines B and the aromatic acids HA used to make the surfactants of the invention are preferably those compounds that are readily available and inexpensive.
• cost of materials is only one factor in selecting specific ethoxylated amines B and aromatic acids HA used as starting materials. After performing a routine cost-benefit analysis and in view of other design parameters it may become apparent that more expensive and less readily available starting materials may be preferred.
• aromatic acids used in the instant invention may generally be defined by formula (2a): wherein n is a number from 1 to 50 inclusive.
• the ethoxylated amines useful for making the surfactants of the instant invention are one or more of the compounds defined by formula (3a): wherein R 2 is selected from the group consisting of C 1 -C 24 alkyl and C 2 -C 24 alkenyl-CH 2 , and x + y is anumber from 4 to 9 inclusive.
• R 2 is selected from the group consisting of C 1 -C 24 alkyl and C 2 -C 24 alkenyl-CH 2
• x + y is anumber from 4 to 9 inclusive.
• a preferred feature of the invention is where the ethoxylated amines are one or more of the ethoxylated amines of formula (3a): wherein R 2 is C 1 -C 24 alkyl and the average of x + y is a number from 4 to 9.
• R 2 is selected from the group consisting of n-octadecyl, n-hexadecyl and cis-9-octadecenyl
• x + y is a number from 4 to 9.
• a feature of the invention is where the average value of x + y is 5.
• a preferred embodiment of the invention is a pesticide formulation which contains the presently disclosed surfactants.
• the invention is not limited to pesticide formulations.
• Other useful formulations that may contain the instantly disclosed surfactants include shampoo formulations, detergent formulations generally and soap formulations used in the mining industry.
• the surfactants presently disclosed are considered to have of general applicability as alternatives to conventional APE's, and therefore would be expected to be useful in many other known formulations.
• the invention encompasses any formulation obtained by otherwise substituting the instantly disclosed surfactants as alternatives to known APEs surfactants as well as other surfactants.
• the instantly disclosed invention also encompasses any formulation obtained by supplementing compositions containing known or conventional APEs with the instantly claimed surfactants.
• any formulation that makes use of a surfactant additive would be subject to modification by substitution or supplementation with one or more of the surfactants of the instant invention.
• surfactants the compounds and compositions are referred to as "surfactants" in the instant application, it is expected that they will also have other nonsurfactant properties that may be useful independently of any inherent surfactant properties. Depending on the application of the instant invention, it may result in increased bioefficacy and/or reduced toxicity and irritation.
• compositions comprising the formulation of the surfactants disclosed above in formulations that contain one or more herbicides and one or more safeners (antidotes).
• herbicides When applying herbicides, the cultivated plants may also suffer severe damage owing to factors that include the concentration of the herbicide and the mode of application, the cultivated plant itself, the nature of the soil, and the climatic conditions such as exposure.
• a preferred embodiment of the invention is for example the formulation of the s-metolachlor and benoxacor, or s-metolachlor, atrazine and benoxacor each in combination with the surfactants of the instant invention.
• the surfactants are prepared by mixing at least one aromatic acid of formula (2a) with at least one ethoxylated amine of formula (3a) while controlling pH.
• the desired pH is maintained by precisely regulating the ratio of the acid and base components in the composition.
• the appropriate acid-base ratio and desired pH can be achieved according to the following procedure: 1) A known weight of the aromatic acid is dissolved in a 50/50 solution of isopropanol and water. 2) A tared amount of ethoxylated amine is slowly added to the aromatic acid with constant stirring using a magnetic stirrer while pH is monitored by use of a pH meter fitted with a silver chloride electrode. 3) When the desired pH is attained, the amount of required ethoxylated amine is measured.
• the ratio of aromatic acid : ethoxylated amine (acid : base) is determined and the surfactant is prepared by mixing the appropriate amounts of the two components with stirring.
• the preferred acid: base ratio is approximately 35:65 (weight ratio).
• the acidity or basicity of the constituent components may vary depending on the supplier of the materials or the particular batch, therefore the pH is the controlling factor in preparing the compounds, compositions and formulations of the instant invention.
• the pK a and pK b for the aromatic acid and the ethoxylated amine respectively may be varied to some extent by manipulating the type and degree of substitution for the compounds defined by formula (2a) and (3a).
• a preferred pH range for the surfactant is a pH from 3 to 9, a more preferred pH range is from 3 to 8.5, and an ultimately preferred pH range is from 5 to 8. It is less desirable to adjust pH after the aromatic acid and amine base components are mixed by the further addition of other acids or bases typically used to raise or lower pH because even minor amounts of additional salts can make a large difference in the observed properties of the product surfactant. It is also less desirable to have additional process steps or to have the added cost associated with purchasing, handling, storage and disposal of additional chemicals.
• the emulsion stability of the ethoxylated aromatic acid is typically greatest when the "average number of ethylene oxide units" (EO) on the aromatic acid is 4 to 25 (i.e. 4 to 25EO) and when the EO on the tallow amine is 4 to 9EO.
• EO average number of ethylene oxide units
• Average is defined as the arithmetic mean of a set of real numbers (in this case the number of ethylene oxide units in the ethoxylated aromatic acids or ethoxylated amines used to make the surfactant).
• Another feature of the invention is where there is a continuous and symmetrical bell curve population distribution around the EO. It also may be desirable that there be low dispersion preferably within one standard deviation ( ⁇ ) of the mean (average EO).
• the tristyrylphenol ethoxylates and the amine ethoxylates can be prepared using chemistry procedures well known in the art.
• the tristyrylphenol ethoxylate can be prepared by treating tristyrylphenol with a base (e.g. sodium hydroxide) followed by addition of the desired equivalents of ethylene oxide.
• Tristyrylphenol is either commercially available, may be prepared by known procedures or otherwise may be prepared using conventional chemistry knowledge. Examples of some commercial suppliers and product names for the ethoxylated amines (i.e. amine ethoxylates).
• the nonionic co-surfactants are those compounds known in the art for formulating surfactant systems.
• the nonionic co-surfactants include polyglycol ethers, polyglycol ether derivatives of aliphatic alcohols, cycloaliphatic alcohols, phenols, or saturated or unsaturated fatty acids. Said derivatives for example may contain 3 to 120 glycol ether groups and 8 to 30 carbon atoms in the hydrocarbon moiety.
• Preferred co-surfactants include for example tristyrylphenol ethoxylates (2 to 50EO, more preferably 16 to 35EO).
• the nonionic co-surfactants include ethyleneoxide-propyleneoxide (EO-PO) block copolymers and EO-PO block copolymer derivatives of aliphatic alcohols, cycloaliphatic alcohols or phenols (e.g butoxy EO-PO block copolymers).
• EO-PO ethyleneoxide-propyleneoxide
• EO-PO block copolymer derivatives of aliphatic alcohols, cycloaliphatic alcohols or phenols e.g butoxy EO-PO block copolymers.
• One preferred aspect of the invention includes the combination of the surfactant compositions herein with liquid pesticide compositions so as to obtain an emulsifiable concentrate formulation which can be directly mixed with water or other aqueous solutions to give an aqueous pesticide formulation without special mixing procedures.
• One preferred feature of the invention includes combining the surfactant system previously described with a nonionic co-surfactant and a liquid active ingredient to obtain an emulsifiable concentrate formulation which can be readily diluted with water or other liquid carriers requiring no special handling or mixing procedures.
• An example of such a formulation follows:
• An oil base suspension concentrate containing liquid metolachlor as active ingredient was prepared according to the following formulation: 80.0% by weight metolachlor, 3.0% by weight tristyrylphenol ethyoxylate (8EO) hemi-sulfate ester neutralized with tallow amine (5EO), 3.0% by weight tristyrylphenol ethoxylate (20EO), 14.0% by weight aromatic hydrocarbon solvent.
• the above ingredients were formulated as follows: The tristyrylphenol ethoxylate (8EO) hemi-sulfate ester neutralized with tallowamine (5EO) and the tristyrylphenol ethoxylate (20EO) are charged to a vessel containing the aromatic hydrocarbon solvent and blended. The technical metolachlor is then added and blended until uniform.
• surfactant system of the instant invention would be equally acceptable for, but not limited to, both aqueous and oil based formulations.
• Another preferred aspect of the invention includes the combination of the surfactant system of the instant invention with a solid active ingredient.
• An example of such a formulation is as follows:
• An aqueous suspension concentrate containing solid atrazine as active ingredient was prepared according to the following formulation: 43.5% by weight atrazine, 2.0% by weight tridecyl alcohol ethoxylate (6EO) 1.0 % by weight EO-PO block copolymer 2.0% by weight tristyrylphenol ethyoxylate (8EO) hemi-sulfate ester neutralized with tallow amine (8EO), 5.0% by weight ethylene glycol, and water to make up 100%.
• the above ingredients were formulated as follows: The atrazine technical is added gradually to a vessel containing the tridecyl alcohol ethoxylate (6EO), the EO-PO block copolymer, the tristyrylphenol ethoxylate (8EO) hemi-sulfate ester neutralized with tallow amine (8E0), the ethylene glycol and most of the water. The slurry is mixed until uniform and then milled to the appropriate particle size. The remaining water is added to meet assay specifications.
• 6EO tridecyl alcohol ethoxylate
• EO-PO block copolymer the tristyrylphenol ethoxylate (8EO) hemi-sulfate ester neutralized with tallow amine (8E0)
• E0 tallow amine
• Another preferred aspect of the invention includes the combination of the surfactant system of this invention with a combination of solid and liquid active ingredients.
• An example of such a formulation is as follows:
• aqueous suspension concentrate containing solid atrazine and liquid metolachlor as the two active ingredients was prepared according to the following formulation: 26.1% by weight s-metolachlor 33.7% by weight atrazine 1.31 % by weight benoxacor 0.4% by weight EO-PO block copolymer 0.67 % by weight tridecylalcohol (6EO) 3.15% by weight tristyrylphenol ethyoxylate (8EO) hemi-sulfate ester neutralized with tallow amine (5EO) 1.5% by weight tristyrylphenol ethoxylate (35EO), 0.7 % by weight antifoaming agent 0.03% by weight thickening agent, such as xanthan gum 0.03% by weight biostatic agent 1.6% by weight ethylene glycol, and water to make up 100%.
• 26.1% by weight s-metolachlor 33.7% by weight atrazine 1.31 % by weight benoxacor 0.4% by weight EO-PO block copolymer 0.67
• the above ingredients were formulated as follows: The atrazine technical is slowly added to a vessel containing the EO-PO block copolymer, some of the tridecyl alcohol (6EO), the biostatic agent, the antifoaming agent, most of the water, and most of the ethylene glycol. The contents of the vessel are mixed until uniform and then milled to the appropriate particle size. The thickening agent is added as a slurry with the remaining tridecyl alcohol and mixed until a uniform, stable final viscosity is reached. The assay is adjusted by the addition of water.
• the s-metolachlor and benoxacor are charged to a second, heated vessel and stirred until the benoxacor dissolves and the solution becomes uniform.
• the solution is cooled.
• the tristyrylphenol ethyoxylate (8EO) hemi-sulfate ester neutralized with tallow amine (5EO), tristyrylphenol ethoxylate (35EO), the remainder of the ethylene glycol, and a small amount of water are added and stirred until uniform.
• the contents of both vessels are then mixed together simultaneously and the final composition is trimmed for assay.
• nonionic surfactant components may be used in conjunction with the surfactant composition previously described.
• Preferred co-surfactants are polyglycol ethers of aliphatic alcohols.
• the nonionic surfactants may include, but are not limited to, castor oil ethoxylates, tristyrylphenol ethoxylates, ethylene oxide/propylene oxide block copolymers, and/or ethylene oxide/propylene oxide block copolymers of aliphatic alcohols.
• the crop protection compositions which are part of the instantly disclosed invention may be formulated in a form suitable for the intended application.
• Types of formulations include for example a flowable (FL) flowable concentrate for seed treatment (FS), wettable powder (WP), wettable dispersible granules (WDG), oil miscible flowable concentrate (OF), suspension concentrate (SC), emulsifiable concentrate (EC), liquid (L), water in oil emulsions (EW), granules (GR) water dispersible powder for slurry treatment (WS) and dry flowable (DF).
• FL flowable
• FS flowable
• WP wettable powder
• WDG wettable dispersible granules
• OF oil miscible flowable concentrate
• SC suspension concentrate
• EC emulsifiable concentrate
• L liquid
• EW water in oil emulsions
• GR granules
• WS dry flowable
• this invention provides new compounds useful as surfactants that are alternatives to known or conventional surfactant systems.
• the surfactants compounds of the instant invention are useful for formulating agrochemical compositions. Variations may be made in proportions, procedures and materials without departing from the scope of the invention as defined by the following claims.

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• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
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Description

• The present invention relates to a surfactant system for general use in agricultural compositions, including, but not limited to herbicidal, fungicidal and insecticidal formulations comprised of two components: an alkoxylated tristyrylphenol hemi-sulfate ester neutralized to the desired pH with an appropriate amount of an alkoxylated alkyl amine.
BACKGROUND OF THE INVENTION
• Alkylphenol ethoxylates (APE's) and their anionic derivatives are surfactants that are well known to industry and have historically been relied upon heavily by agricultural chemical producers. However, formulations containing APEs do not always provide the most desirable combination of design specifications, e.g. product efficacy, working parameters and cost. Traditional non-APE surfactant systems have not been readily adaptable substitutes for APE surfactants. For example, calcium dodecylbenzene sulfonic acid used in conjunction with alkoxylated amines have not been as robust as the APE's and their derivatives due to unacceptable performance in one or more key performance areas, such as emulsion stability, acute toxicity, temporal and thermal stability, chemical and physical stability; solution, suspension or dilution dynamics; shear stress tolerance; viscosity; or lack of compatibility with mixing partners.
• Phosphate esters of alcohol ethoxylates, which are non-APE surfactants found in many industrial uses, have long term stability problems due to hydrolytically driven transesterification and saponification reactions involving the mono-ester, di-ester, and free acid components of the surfactant mixture. Sulfated surfactants in flowable formulations are typically prone to hydrolytic decomposition, particularly when the formulations are stored in hot, summer warehouse conditions. Thus, there has been a need for an alternative surfactant system which could be easily made from readily available and cost effective raw materials and would be robust to chemical and physical conditions which might be encountered by the formulated product in its life span.
SUMMARY OF THE INVENTION
• Surprisingly, it has now been discovered that certain aromatic acids such as ethoxylated tristyrylphenol hemi-sulfate esters which have been neutralized with ethoxylated amines are suitable as alternative ionic surfactants for general use in agricultural products. Even though ethoxylated tristyrylphenol hemi-sulfate esters fall into the general classification of APE's, the tristyrylphenol group is structurally very different from known or conventional APE surfactants. The surfactants of the instant invention may be in the form of a surfactant compound, or composition containing one or more of the surfactant compounds or salts. In one embodiment of the invention, the compositions containing the instant surfactant compounds do not contain or are substantially free of known or conventional APEs. The surfactants of the instant invention are obtained from combining the appropriate ethoxylated tristyrylphenol hemi-sulfate ester with the appropriate ethoxylated amine.
• The steric configuration of the tristyrylphenol group protects the surfactant from hydrolytic cleavage typically observed in other known anionic sulfate ester surfactant systems.
DETAILED DESCRIPTION OF THE INVENTION
• One aspect of the invention concerns the compounds of Formula (1): (H-B)+A-   (1), wherein A- is the conjugate base of the acid H-A, wherein H-A is an ethoxylated tristyrylphenol hemi-sulfate ester; and the (H-B)+ is the conjugate acid of the base B, wherein B is an ethoxylated amine. An aspect of the invention are the compounds having the formula (H-B)+A-, where A- is the anion of the formula: wherein n is a number from 1 to 50 inclusive, and wherein (H-B)+ is the cation of the formula: wherein R2 is selected from the group consisting of C1-C24 alkyl and C2-C24 alkenyl-CH2-, and x + y is a number from 4 to 9 inclusive.
  A preferred embodiment of the invention are the compounds of formula (1), wherein A- is: wherein n is from about 4 to 25 (preferably 4 to 16, especially 8); and wherein (H-B)+ is the cation of the formula: wherein R2 is selected from the group consisting of n-octadecyl, n-hexadecyl and cis-9-octadecenyl, and x + y is a number from 4 to 9. A feature of the invention is where x + y is 5.
• The invention also concerns the process for the preparation of a compound of the formula (H-B)+ A- in which (H-B)+ and A- have the meanings given above, characterised by neutralizing an ethoxylated tristyrylphenol hemi-sulfate ester of formula (2a) infra (also referred to as HA) with an ethoxylated amine of formula (3a) infra (also herein referred to as B). The ammoniumsulfate compounds or the product from the process of combining an aromatic acid HA with an ethoxylated amine B (to the extent there is a difference) are both features of the instantly disclosed invention. The scope of the invention disclosed herein should not be construed to be limited by any particular chemical theory relating to the complexation, equilibration, reaction or acid-base chemistry of the components used to make the surfactants or other ingredients used to make other ultimately useful formulations such as, pesticide formulations. In this regard, another aspect of the invention is the surfactant composition comprising one or more aromatic acids and one or more ethoxylated amines wherein the constituent components may or may not have interacted chemically so as to result in a change in form of the components. The invention encompasses the static composition of the appropriate components admixed together as well as the chemically integrated surfactant composition comprising at least one aromatic acid and at least one ethoxylated amine. "Static composition" denotes the composition composed of components wherein the components have not substantially changed by virtue of their combination with other composition components. "Chemically integrated composition" means a composition that results from the natural equilibration, complexation, dissociation or other chemical transformation if any that may occur after combination of the components and prior to ultimate use of the surfactant in a pesticide formulation. Therefore, the "chemically integrated composition" of the instant invention by definition encompasses the situation where there is a "static composition" as well as any resultant composition occurring at any point in time between initial creation and ultimate use in the field of products containing the surfactant. In other words, the disclosed invention is not limited to a static composition of chemically unaltered constituent components.
• Another aspect of the invention is the surfactant composition produced as a whole from the combination of the aromatic acid HA and the ethoxylated amine base B to the extent it is composed of products other than ammoniumsulfate compounds. Such a composition may contain chemically unaltered starting materials as well as other reaction products or by-products from reaction, equilibration, dissociation or complexation of the components in the composition.
• The invention also includes the process for obtaining a surfactant which is useful as a substitute for known or conventional APE's. In addition to the surfactant product, the process of obtaining or making any of the surfactants is herein disclosed as part of the invention. The invention also includes the method of using the surfactant compounds of formula (1) and compositions thereof as substitutes for known or conventional APEs.
• The ethoxylated amines B and the aromatic acids HA used to make the surfactants of the invention are preferably those compounds that are readily available and inexpensive. However, cost of materials is only one factor in selecting specific ethoxylated amines B and aromatic acids HA used as starting materials. After performing a routine cost-benefit analysis and in view of other design parameters it may become apparent that more expensive and less readily available starting materials may be preferred.
• The aromatic acids used in the instant invention may generally be defined by formula (2a): wherein n is a number from 1 to 50 inclusive.
• The ethoxylated amines useful for making the surfactants of the instant invention are one or more of the compounds defined by formula (3a): wherein R2 is selected from the group consisting of C1-C24 alkyl and C2-C24 alkenyl-CH2, and x + y is anumber from 4 to 9 inclusive. A preferred feature of the invention is where the ethoxylated amines are one or more of the ethoxylated amines of formula (3a): wherein R2 is C1-C24 alkyl and the average of x + y is a number from 4 to 9. Additional preferred aspects of the invention are where R2 is selected from the group consisting of n-octadecyl, n-hexadecyl and cis-9-octadecenyl, and x + y is a number from 4 to 9. A feature of the invention is where the average value of x + y is 5.
• Another aspect of the invention is the composition comprising the formulation of the surfactants disclosed above in formulations that contain one or more other active ingredients. A preferred embodiment of the invention is a pesticide formulation which contains the presently disclosed surfactants. However, the invention is not limited to pesticide formulations. Other useful formulations that may contain the instantly disclosed surfactants include shampoo formulations, detergent formulations generally and soap formulations used in the mining industry. The surfactants presently disclosed are considered to have of general applicability as alternatives to conventional APE's, and therefore would be expected to be useful in many other known formulations. The invention encompasses any formulation obtained by otherwise substituting the instantly disclosed surfactants as alternatives to known APEs surfactants as well as other surfactants. The instantly disclosed invention also encompasses any formulation obtained by supplementing compositions containing known or conventional APEs with the instantly claimed surfactants. Generally, any formulation that makes use of a surfactant additive would be subject to modification by substitution or supplementation with one or more of the surfactants of the instant invention. Although the compounds and compositions are referred to as "surfactants" in the instant application, it is expected that they will also have other nonsurfactant properties that may be useful independently of any inherent surfactant properties. Depending on the application of the instant invention, it may result in increased bioefficacy and/or reduced toxicity and irritation.
• Another aspect of the invention is the composition comprising the formulation of the surfactants disclosed above in formulations that contain one or more herbicides and one or more safeners (antidotes). When applying herbicides, the cultivated plants may also suffer severe damage owing to factors that include the concentration of the herbicide and the mode of application, the cultivated plant itself, the nature of the soil, and the climatic conditions such as exposure. A preferred embodiment of the invention is for example the formulation of the s-metolachlor and benoxacor, or s-metolachlor, atrazine and benoxacor each in combination with the surfactants of the instant invention.
• The surfactants are prepared by mixing at least one aromatic acid of formula (2a) with at least one ethoxylated amine of formula (3a) while controlling pH. The desired pH is maintained by precisely regulating the ratio of the acid and base components in the composition. For example, the appropriate acid-base ratio and desired pH can be achieved according to the following procedure: 1) A known weight of the aromatic acid is dissolved in a 50/50 solution of isopropanol and water. 2) A tared amount of ethoxylated amine is slowly added to the aromatic acid with constant stirring using a magnetic stirrer while pH is monitored by use of a pH meter fitted with a silver chloride electrode. 3) When the desired pH is attained, the amount of required ethoxylated amine is measured. 4) The ratio of aromatic acid : ethoxylated amine (acid : base) is determined and the surfactant is prepared by mixing the appropriate amounts of the two components with stirring. For many of the pesticide formulations described herein the preferred acid: base ratio is approximately 35:65 (weight ratio). The acidity or basicity of the constituent components may vary depending on the supplier of the materials or the particular batch, therefore the pH is the controlling factor in preparing the compounds, compositions and formulations of the instant invention. The pKa and pKb for the aromatic acid and the ethoxylated amine respectively may be varied to some extent by manipulating the type and degree of substitution for the compounds defined by formula (2a) and (3a). Therefore, the selection of the particular acid or base used will also effect the acid : base ratio used to make the surfactants as well as the desired pH. A preferred pH range for the surfactant is a pH from 3 to 9, a more preferred pH range is from 3 to 8.5, and an ultimately preferred pH range is from 5 to 8. It is less desirable to adjust pH after the aromatic acid and amine base components are mixed by the further addition of other acids or bases typically used to raise or lower pH because even minor amounts of additional salts can make a large difference in the observed properties of the product surfactant. It is also less desirable to have additional process steps or to have the added cost associated with purchasing, handling, storage and disposal of additional chemicals.
• The emulsion stability of the ethoxylated aromatic acid, such as the ethoxylated tristyrylphenol hemi-sulfate ester of formula (2a)) neutralized with an ethoxylated tallow amine of formula (3a) is typically greatest when the "average number of ethylene oxide units" (EO) on the aromatic acid is 4 to 25 (i.e. 4 to 25EO) and when the EO on the tallow amine is 4 to 9EO. "Average" is defined as the arithmetic mean of a set of real numbers (in this case the number of ethylene oxide units in the ethoxylated aromatic acids or ethoxylated amines used to make the surfactant). Another feature of the invention is where there is a continuous and symmetrical bell curve population distribution around the EO. It also may be desirable that there be low dispersion preferably within one standard deviation (σ) of the mean (average EO).
• The tristyrylphenol ethoxylates and the amine ethoxylates can be prepared using chemistry procedures well known in the art. For example, the tristyrylphenol ethoxylate can be prepared by treating tristyrylphenol with a base (e.g. sodium hydroxide) followed by addition of the desired equivalents of ethylene oxide. Tristyrylphenol is either commercially available, may be prepared by known procedures or otherwise may be prepared using conventional chemistry knowledge. Examples of some commercial suppliers and product names for the ethoxylated amines (i.e. amine ethoxylates). Amine ethoxylate Supplier Product Name Average Number of EO Tallow amines Witco Witcamine TAM-X0
  (X = average number of EO) 2, 4, 4.5, 5, 6, 7, 8, 9, 10.5 and 15 Coco amines Witco Varonic K-2XX
  (XX = average number of EO) 02, 05, 10 and 15 Stephan Toximul TA-X
  (X = average number of EO) 2, 4, 4.5, 5, 6, 7, 8, 9, 10 and 15 Oleyl amine Witco Varonic Q-202 2
• Another preferred feature of the present invention is the combination of instant compounds of formula (1) with a nonionic co-surfactant. The nonionic co-surfactants are those compounds known in the art for formulating surfactant systems. The nonionic co-surfactants include polyglycol ethers, polyglycol ether derivatives of aliphatic alcohols, cycloaliphatic alcohols, phenols, or saturated or unsaturated fatty acids. Said derivatives for example may contain 3 to 120 glycol ether groups and 8 to 30 carbon atoms in the hydrocarbon moiety. Preferred co-surfactants include for example tristyrylphenol ethoxylates (2 to 50EO, more preferably 16 to 35EO). The nonionic co-surfactants include ethyleneoxide-propyleneoxide (EO-PO) block copolymers and EO-PO block copolymer derivatives of aliphatic alcohols, cycloaliphatic alcohols or phenols (e.g butoxy EO-PO block copolymers).
• One preferred aspect of the invention includes the combination of the surfactant compositions herein with liquid pesticide compositions so as to obtain an emulsifiable concentrate formulation which can be directly mixed with water or other aqueous solutions to give an aqueous pesticide formulation without special mixing procedures.
• The following examples illustrate further some of the specific features of the invention. Where not otherwise specified throughout this specification and claims, temperatures are given in degrees centigrade. Examples of components that may be used to formulate the compositions of the instant invention. Product Name Supplier Description Aromatic 150 Exxon Corporation aromatic hydrocarbon solvent Pegasol R-150 Mobil Chemical Company aromatic hydrocarbon solvent Cyclo Sol 150 Shell Chemical Company aromatic hydrocarbon solvent Pluronic P-65 BASF Corporation EO-PO block copolymer Toximul Stepan Company EO-PO block copolymer Antifoam A Dow Corning Corporation silicone antifoaming agent Y- Osi Specialties, Inc. silicone antifoaming agent Proxel GXL Zeneca Inc. biostatic Nipacide BIT20 Nipa Hardwicke, Inc. biostatic Renex 36 ICI Surfactants Tridecyl alcohol (6EO) Rhodasurf BC-610 Rhodia Inc. Tridecyl alcohol (6EO) Genopol X-060 Clariant Corporation formerly Hoechst Celanese Corporation Tridecyl alcohol (6EO) Witconol TD-60 Witco Corporation Tridecyl alcohol (6EO) Rhodopol 23 Rhodia Inc. Xanthan gum Kelzan Zeneca Inc. Xanthan gum Names and address of suppliers of materials. Supplier Address Witco Corporation Frantz Road, P.O. Box 646, Dublin, Ohio Stepan Company Northfield, Illinois Dow Corning Corporation Midland, MI Zeneca Inc. Wilmington, DE BASF, Corporation Mt. Olive, NJ Rhodia, Inc. Cranbury, NJ Nipa Hardwicke, Inc. Silverside Road, 104 Hagley Bldg., Wilmington, DE Osi Specialities, Inc. Greenwich, CT ICI Surfactants Wilmington, DE Clariant Corporation Charlotte, NC Shell Chemical Company Houston, TX Exxon Corporation Houston, TX Mobil Chemical Company Houston, TX
• One preferred feature of the invention includes combining the surfactant system previously described with a nonionic co-surfactant and a liquid active ingredient to obtain an emulsifiable concentrate formulation which can be readily diluted with water or other liquid carriers requiring no special handling or mixing procedures. An example of such a formulation follows:
Example 1
• An oil base suspension concentrate containing liquid metolachlor as active ingredient was prepared according to the following formulation: 80.0% by weight metolachlor, 3.0% by weight tristyrylphenol ethyoxylate (8EO) hemi-sulfate ester neutralized with tallow amine (5EO), 3.0% by weight tristyrylphenol ethoxylate (20EO), 14.0% by weight aromatic hydrocarbon solvent. The above ingredients were formulated as follows:
  The tristyrylphenol ethoxylate (8EO) hemi-sulfate ester neutralized with tallowamine (5EO) and the tristyrylphenol ethoxylate (20EO) are charged to a vessel containing the aromatic hydrocarbon solvent and blended. The technical metolachlor is then added and blended until uniform.
• It is understood that the surfactant system of the instant invention would be equally acceptable for, but not limited to, both aqueous and oil based formulations.
• Another preferred aspect of the invention includes the combination of the surfactant system of the instant invention with a solid active ingredient. An example of such a formulation is as follows:
Example 2
• An aqueous suspension concentrate containing solid atrazine as active ingredient was prepared according to the following formulation: 43.5% by weight atrazine, 2.0% by weight tridecyl alcohol ethoxylate (6EO) 1.0 % by weight EO-PO block copolymer 2.0% by weight tristyrylphenol ethyoxylate (8EO) hemi-sulfate ester neutralized with tallow amine (8EO), 5.0% by weight ethylene glycol, and water to make up 100%. The above ingredients were formulated as follows: The atrazine technical is added gradually to a vessel containing the tridecyl alcohol ethoxylate (6EO), the EO-PO block copolymer, the tristyrylphenol ethoxylate (8EO) hemi-sulfate ester neutralized with tallow amine (8E0), the ethylene glycol and most of the water. The slurry is mixed until uniform and then milled to the appropriate particle size. The remaining water is added to meet assay specifications.
• Another preferred aspect of the invention includes the combination of the surfactant system of this invention with a combination of solid and liquid active ingredients. An example of such a formulation is as follows:
Example 3
• An aqueous suspension concentrate containing solid atrazine and liquid metolachlor as the two active ingredients was prepared according to the following formulation: 26.1% by weight s-metolachlor 33.7% by weight atrazine 1.31 % by weight benoxacor 0.4% by weight EO-PO block copolymer 0.67 % by weight tridecylalcohol (6EO) 3.15% by weight tristyrylphenol ethyoxylate (8EO) hemi-sulfate ester neutralized with tallow amine (5EO) 1.5% by weight tristyrylphenol ethoxylate (35EO), 0.7 % by weight antifoaming agent 0.03% by weight thickening agent, such as xanthan gum 0.03% by weight biostatic agent 1.6% by weight ethylene glycol, and water to make up 100%. The above ingredients were formulated as follows: The atrazine technical is slowly added to a vessel containing the EO-PO block copolymer, some of the tridecyl alcohol (6EO), the biostatic agent, the antifoaming agent, most of the water, and most of the ethylene glycol. The contents of the vessel are mixed until uniform and then milled to the appropriate particle size. The thickening agent is added as a slurry with the remaining tridecyl alcohol and mixed until a uniform, stable final viscosity is reached. The assay is adjusted by the addition of water.
• The s-metolachlor and benoxacor are charged to a second, heated vessel and stirred until the benoxacor dissolves and the solution becomes uniform. The solution is cooled. The tristyrylphenol ethyoxylate (8EO) hemi-sulfate ester neutralized with tallow amine (5EO), tristyrylphenol ethoxylate (35EO), the remainder of the ethylene glycol, and a small amount of water are added and stirred until uniform. The contents of both vessels are then mixed together simultaneously and the final composition is trimmed for assay.
• It is again understood that such a formulation would be acceptable for, but not limited to, aqueous and oil based formulations.
• As indicated above, additionally, one or more nonionic surfactant components may be used in conjunction with the surfactant composition previously described. Preferred co-surfactants are polyglycol ethers of aliphatic alcohols. In particular, the nonionic surfactants may include, but are not limited to, castor oil ethoxylates, tristyrylphenol ethoxylates, ethylene oxide/propylene oxide block copolymers, and/or ethylene oxide/propylene oxide block copolymers of aliphatic alcohols.
• The crop protection compositions which are part of the instantly disclosed invention may be formulated in a form suitable for the intended application. Types of formulations include for example a flowable (FL) flowable concentrate for seed treatment (FS), wettable powder (WP), wettable dispersible granules (WDG), oil miscible flowable concentrate (OF), suspension concentrate (SC), emulsifiable concentrate (EC), liquid (L), water in oil emulsions (EW), granules (GR) water dispersible powder for slurry treatment (WS) and dry flowable (DF).
• Some additional preferred embodiments of the instant invention are contained in Tables 4 and 5 below.
• In summary, it is seen that this invention provides new compounds useful as surfactants that are alternatives to known or conventional surfactant systems. In particular, the surfactants compounds of the instant invention are useful for formulating agrochemical compositions. Variations may be made in proportions, procedures and materials without departing from the scope of the invention as defined by the following claims.

Claims (21)

1. A compound of the formula (H-B)+A-,
   wherein A- is: wherein n is a number from 1 to 50 inclusive,
   wherein (H-B)+ is the cation of the formula: wherein R2 is selected from the group consisting of C1-C24 alkyl and C2-C24 alkenyl-CH2-, and x + y is a number from 4 to 9 inclusive.
2. A compound according to claim 1, wherein n is 4 to 16.
3. A compound according to claim 2, wherein n is 8.
4. A compound according to claim 3, wherein R2 is selected from the group consisting of n-octadecyl, n-hexadecyl and cis-9-octadecenyl; and x + y is equal to 5.
5. A process for the preparation of a compound of the formula (H-B)+ A- in which (H-B)+ and A- have the meanings given in claim 1, characterised by neutralizing at least one aromatic acid of formula (2a): wherein n is a number from 1 to 50 inclusive,
   with at least one ethoxylated amine base of formula (3a): wherein R2 is selected from the group consisting of C1-C24 alkyl and C2-C24 alkenyl-CH2-, and x + y is a number from 4 to 9 inclusive, and wherein the product surfactant has a pH of 3 to 9.
6. A process according to claim 5, wherein R2 is C1-C24 alkyl.
7. A process according to claim 5, wherein the product surfactant has a pH of 3 to 8.5.
8. A process according to claim 5, wherein the product surfactant has a pH of 5 to 8.
9. A surfactant composition comprising a salt of: (a) at least one aromatic acid is a compound of the formula (2a): wherein n is a number from 1 to 50 inclusive; and (b) at least one ethoxylated amine base of the formula (3a): wherein R2 is selected from the group consisting of C1-C24 alkyl and C2-C24 alkenyl-CH2-, and x + y is a number from 4 to 9 inclusive, and wherein the surfactant composition has a pH of 3 to 9.
10. A surfactant composition according to claim 9, wherein R2 is C1-C24 alkyl.
11. A composition of claim 9, wherein the product surfactant has a pH of 3 to 8.5.
12. A composition of claim 9, wherein the product surfactant has a pH of 5 to 8.
13. A chemically integrated surfactant composition comprising at least one aromatic acid compound of formula (2a): wherein n is a number from 1 to 50 inclusive,
    and at least one ethoxylated amine base of the formula (3a): wherein R2 is selected from the group consisting of C1-C24 alkyl and C2-C24 alkenyl-CH2-, and x + y is a number from 4 to 9 inclusive, wherein the chemically integrated surfactant composition has a pH of 3 to 9,
    or the chemical interaction products thereof.
14. A chemically integrated surfactant composition according to claim 13, wherein R2 is C1-C24 alkyl.
15. A composition of claim 13, wherein the product surfactant has a pH of 3 to 8.5.
16. A composition of claim 13, wherein the product surfactant has a pH of 5 to 8.
17. A pesticide formulation comprising at least one pesticide and at least one aromatic acid neutralized with at least one ethoxylated amine wherein said aromatic acid is of the formula (2a): wherein n is a number from 1 to 50 inclusive,
    and the said ethoxylated amine is of the formula (3a): wherein R2 is selected from the group consisting of C1-C24 alkyl and C2-C24 alkenyl-CH2-, and x + y is a number from 4 to 9 inclusive.
18. A pesticide formulation according to claim 17, wherein R2 is C1-C24 alkyl.
19. A pesticide formulation of claim 17, wherein the pesticide is atrazine or glyphosate.
20. A method of protecting crops comprising the step of applying to the locus of the crops in need of protection an agriculturally effective amount of the formulation of claim 18.
21. Use of the compound of claim 1 as a surfactant.

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* Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title USB2 (en) -09-07 -06-08 Syngenta Crop Protection, Inc. Surfactant systems for agriculturally active compounds USA1 (en) * -01-19 -07-21 Coates John S. Alkoxylated amine and process therefor ARA1 (en) * -06-30 -05-23 Syngenta Participations Ag IMPROVED FORMULATIONS USB2 (en) * -11-22 -05-15 Basf Se Liquid water based agrochemical formulations KRB1 (en) * -05-16 -11-21 가부시끼가이샤 도꾸야마 Photoresist developer ESB1 (en) -02-13 -05-28 Consejo Superior De Investigaciones Cientificas SLOW RELEASE FORMULATIONS OF RESPECTFUL PESTICIDES WITH THE ENVIRONMENT. CAC (en) * -03-25 -06-14 Syngenta Participations Ag Surfactant compositions TWIB (en) * -05-08 -12-21 Croda Inc Surfactants in agrochemical formulations BRA2 (en) * -09-10 -04-12 Univ Texas composition for treating a formation having hydrocarbon, and methods for preparing a composition, and for treating a formation having hydrocarbon for recovering petroleum RUA (en) * -01-28 -03-10 Борд Оф Риджентс, Дзе Юниверсити Оф Техас Систем Alkoxylated styrylphenol sulfate as a new surfactant composition for use in the tertiary oil recovery method JPB2 (en) * -09-14 -03-02 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Composition comprising a pyripyropene insecticide and a base WOA2 (en) -09-14 -03-22 Basf Se Composition containing a pyripyropene insecticide and an adjuvant CNB (en) * -11-02 -05-29 浙江皇马科技股份有限公司 Preparation method of triphenylethylene phenol polyoxyethylene ether oleate USB2 (en) -03-12 -03-21 Basf Se Liquid concentrate formulation containing a pyripyropene insecticide I WOA1 (en) -03-12 -09-19 Basf Se Method for producing an aqueous suspension concentrate formulation of a pyripyropene insecticide KRB1 (en) -03-12 -12-13 바스프 에스이 Liquid concentrate formulation containing a pyripyropene insecticide ii WOA1 (en) -05-31 -12-05 Exxonmobil Chemical Patents Inc. Styrene removal in paraxylene recovery process WOA1 (en) * -08-08 -02-13 日华化学株式会社 Dyeing assistant for polyester fibre and method for dyeing polyester fibre using same, and method for manufacturing dyed material WOA1 (en) * -03-18 -09-24 Rhodia Operations Tri-substituted aromatic-containing additives and surfactants and methods for use CNB (en) * -07-17 -01-13 天津悦泰石化科技有限公司 For the surfactant and its production and use of urea for vehicle solution CNA (en) * -07-11 -05-05 Upl有限公司 A kind of solid agrochemical composition and its preparation process CNB (en) * -07-02 -11-08 中化化工科学技术研究总院有限公司 Pymetrozine-dinotefuran dry suspending agent and preparation method thereof

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Publication number Publication date ILA (en) -08-01 USB2 (en) -12-17 ZAB (en) -05-22 COA1 (en) -10-30 HUB1 (en) -10-28 MYA (en) -08-30 TWB (en) -02-11 ARA1 (en) -07-31 BRA (en) -09-04 IDA (en) -08-23 BRB1 (en) -10-19 JPA (en) -10-02 PLB1 (en) -08-29 RUC2 (en) -12-10 CZB6 (en) -11-18 CZA3 (en) -09-12 KRA (en) -11-24 EPA1 (en) -10-10 HUPA3 (en) -05-28 CRA (en) -11-18 HUPA2 (en) -04-29 DET2 (en) -07-28 CAC (en) -03-04 ATET1 (en) -03-15 PTE (en) -04-29 CAA1 (en) -06-22 AUA (en) -07-03 CNC (en) -08-03 GTA (en) -06-01 TRT2 (en) -05-21 NZA (en) -12-20 EGA (en) -02-26 WOA1 (en) -06-22 UAC2 (en) -09-15 JPB2 (en) -01-20 PLA1 (en) -05-06 CNA (en) -01-09 ILA0 (en) -04-21 KRB1 (en) -03-09 AUB2 (en) -07-25 EST3 (en) -07-16 USA1 (en) -05-16 DED1 (en) -03-31

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