梳型碳氟高分子表面活性剂在硝磺草酮悬浮剂开发中的应用

张静静; 曾梦蝶; 宋凌云; 寇俊杰; 宋红健; 刘玉秀; 汪清民

doi:10.16801/j.issn.1008-7303.2022.0076

梳型碳氟高分子表面活性剂在硝磺草酮悬浮剂开发中的应用

doi: 10.16801/j.issn.1008-7303.2022.0076

张静静^{1, 2,},
曾梦蝶¹,
宋凌云¹,
寇俊杰¹,
宋红健^1, ,,
刘玉秀¹,
汪清民^1, ,

1.
南开大学化学学院，元素有机化学国家重点实验室，元素有机化学研究所，有机新物质创造前沿科学中心，天津 300071
2.
天津农学院基础科学学院，天津 300392

基金项目: 国家重点研发计划(2021YFD1700105)；国家自然科学基金(22107084).

详细信息

作者简介:
张静静，chemzhangjingjing@163.com

通讯作者:
宋红健，songhongjian@nankai.edu.cn

汪清民，wangqm@nankai.edu.cn

中图分类号: TQ450.6
计量
- 文章访问数: 186
- HTML全文浏览量: 45
- PDF下载量: 32
- 被引次数: 0
出版历程
- 收稿日期: 2022-06-10
- 录用日期: 2022-08-09
- 网络出版日期: 2022-08-15
- 刊出日期: 2022-10-10

Application of comb-type fluorocarbon polymer surfactant in the development of nitrosulfonone suspension concentrate

1.
State Key Laboratory of Elemento-Organic Chemistry, Research Institute of Elemento-Organic Chemistry, College of Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071, China
2.
College of Basic Science, Tianjin Agricultural University, Tianjin 300392, China

Funds: the National Key R&D Program of China (2021YFD1700105); the National Natural Science Foundation of China (22107084).

摘要

摘要: 为了探讨新型梳型含氟高分子表面活性剂在硝磺草酮悬浮剂开发中的应用，分别以该类表面活性剂 b1 和 b9 为分散剂，以商品化分散剂YUS-FS3000为对照，分别制备了25%硝磺草酮悬浮剂，并测定了其悬浮率、粒径、入水分散性和稳定性等理化性质，室内除草活性，以及分散剂 b1 的添加量对以上性能的影响。结果表明：以 b1 和 b9 为分散剂制备的硝磺草酮悬浮剂，在热贮、低温和冷冻3种条件下分别贮存14 d，其有效成分含量在25.52%~26.98%之间，3种条件下有效成分质量分数均为合格；同时，在3种贮存条件下的悬浮率均高于98.0%，且以 b1 为分散剂时，其分散性和稳定性优于以YUS-FS3000为分散剂；即使 b1 的添加量 (质量分数) 为2%时，在3种条件下分别贮存14 d，其有效成分含量在25.62%~26.01%之间，同时其悬浮率高于99.0%。3种25%硝磺草酮悬浮剂对稗草Echinochloa crusgalli的GR₅₀值 (使杂草生物量降低50%的除草剂剂量) 分别为有效成分29.03 (YUS-FS3000)、15.70 ( b1 ) 和10.19 ( b9 ) g/hm²。
- 梳型含氟高分子表面活性剂 /
- 分散剂 /
- 硝磺草酮 /
- 悬浮剂 /
- 稳定性 /
- 除草活性
Abstract: In order to explore the application of new comb-type fluorine-containing polymer surfactants in the development of nitrosulfonone suspension concentrate, 25% nitrosulfonone suspension concentrates with different dispersants were prepared by taking such surfactants b1 and b9 as dispersants and commercial dispersant YUS-FS3000 as control. The physicochemical properties such as suspensibility, nominal size, dispersibility in water, and stability, biological activity in a greenhouse, and the effect of the addition amount of dispersant b1 on the above properties were measured respectively. The results showed that the active ingredient content was 25.52%-26.98% under the three conditions of 54 ℃, 0 ℃, and −18 ℃ for 14 days, which was qualified under the three conditions. At the same time, the suspensibility was higher than 98.0% under three storage conditions, and the suspension concentrate prepared by b1 was better than that by YUS-FS3000 as dispersant. Even if the addition amount (mass fraction) of b1 was 2%, the active ingredient content was between 25.62% and 26.01% after being stored for 14 days under three conditions. At the same time, the suspensibility was higher than 99.0% under three storage conditions. The GR₅₀ (50% growth reduction) values of 25% mesotrione aqueous suspension concentrate prepared by these three dispersants on Echinochloa crusgalli (L.) Beauv were 29.03 (YUS-FS3000), 15.70 ( b1 ) and 10.19 ( b9 ) g (a.i.)/hm², respectively.
- comb-type fluoropolymer surfactants /
- dispersant /
- mesotrione /
- suspension concentrate /
- stability /
- herbicidal activity

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1 硝磺草酮的结构式

1. Structural formula of mesotrione

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图 1 1#、2# 和3# 在不同贮存温度下的粒径分布图

Figure 1. Particle size distribution of 1#, 2# and 3# at at different storage temperatures

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图 2 SEM表征的25%硝磺草酮悬浮剂颗粒在不同贮存温度下的形貌

Figure 2. The morphology of mesotrione 25% SC particles characterized by SEM at different storage temperatures

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图 3 由不同分散剂制备的25%硝磺草酮悬浮剂入水时的状态

Figure 3. The phenomenon of 25% mesotrione prepared by different dispersants entering water

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图 4 不同贮存温度条件下4#、5#、6# 和7# 粒径分布图

Figure 4. Particle size distribution of 4#, 5#, 6# and 7# at different temperatures

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表 1 Poly(PEGMEMA_m-FMA_n)^x表面活性剂的组成以及GPC数据^[20]

Table 1. Composition of surfactants and GPC data of Poly(PEGMEMA_m-FMA_n)^x ^[20]


样品 Sample	p	q	m/n^a	M_n^b × 10⁴/ Daltons	M_w^c × 10⁴/ Daltons	PDI^d	γ_min/ (mN/m)
b1	4	4	2/1	1.87	3.92	2.09	37.19 ± 0.50
b9	20	12	1/3	1.47	2.50	1.70	42.80 ± 0.26
注：^aPEGMEMA/FMA的摩尔进料比；^b数均分子质量；^c重均分子质量；^d多分散指数, M_w/M_n。Note: ^aMolar feed ratio of PEGMEMA/FMA;^bNumber-average molecular weight; ^cMass average molar mass; ^dPolydispersity, M_w/M_n.

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表 2 25%硝磺草酮悬浮剂的剂型配方 (分散剂种类不同)

Table 2. Formulation of 25% mesotrione SC (Different dispersants)

成分　　　　 Ingredient	1#	2#	3#
97% 硝磺草酮原药 97% mesotrione TC/g	36.0	36.0	36.0
分散剂 YUS-FS3000 Dispersant YUS-FS3000/g	YUS-FS3000 (5.6)	b1 (5.6)	b9 (5.6)
润湿剂 YUS-SXC Wetting agent YUS-SXC/g	1.4	1.4	1.4
硅酸镁铝 Magnesium aluminum silicate/g	1.4	1.4	1.4
1% 黄原胶 1% Xanthan gum/g	0.28	0.28	0.28
防腐剂 S-30 Preservatives S-30/g	0.28	0.28	0.28
乙二醇 Ethylene glycol/g	7.0	7.0	7.0
消泡剂1501 Antifoamer 1501/g	0.4	0.4	0.4
柠檬酸 Citric acid/g	0.7	0.7	0.7
去离子水 Deionized water/g	86.94	86.94	86.94
注：配方质量共140 g。Note: The mass of the formulation is 140 g.

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表 3 25%硝磺草酮悬浮剂的剂型配方 (分散剂添加量不同)

Table 3. Formulation of 25% mesotrione SC (Different amounts of dispersant)

成分　　　　 Ingredient	4#	5#	6#	7#
97% 硝磺草酮原药 97% mesotrione TC/g	25.8	25.8	25.8	25.8
分散剂 b1 Dispersant b1/g	2.0	6.0	8.0	10.0
润湿剂 YUS-SXC Wetting agent YUS-SXC/g	1.0	1.0	1.0	1.0
硅酸镁铝 Magnesium aluminum silicate/g	1.0	1.0	1.0	1.0
1% 黄原胶 1% Xanthan gum/g	0.2	0.2	0.2	0.2
防腐剂S-30 Preservatives S-30/g	0.2	0.2	0.2	0.2
乙二醇 Ethylene glycol/g	5.0	5.0	5.0	5.0
消泡剂1501 Antifoamer 1501/g	0.25	0.25	0.25	0.25
柠檬酸 Citric acid/g	0.5	0.5	0.5	0.5
去离子水 Deionized water/g	64.05	60.05	58.05	56.05
注：配方质量共100 g。Note: The mass of the formulation is 100 g.

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表 4 25%硝磺草酮悬浮剂的理化参数 (1)

Table 4. Physicochemical parameters of 25% mesotrione SC (1)

处理编号 Number	分散剂 Dispersant	贮存温度 Storage temperature/℃	粒径 Particle size/μm			有效成分质量分数 Active ingredient content/%	悬浮率 Suspensibility/%
处理编号 Number	分散剂 Dispersant	贮存温度 Storage temperature/℃	D₁₀	D₅₀	D₉₀	有效成分质量分数 Active ingredient content/%	悬浮率 Suspensibility/%
1#	YUS-FS3000	54	0.568	1.689	4.105	26.47 ± 0.09	98.4 ± 1.9
		0	0.642	1.821	4.235	26.22 ± 0.16	100 ± 0
		−18	0.661	1.858	4.172	26.25 ± 0.13	99.0 ± 1.4
2#	b1	54	0.514	1.917	4.794	26.73 ± 0.05	99.3 ± 0.4
		0	0.521	1.742	3.976	26.23 ± 0.13	99.9 ± 0.4
		−18	0.393	1.520	3.539	26.27 ± 0.11	100 ± 0
3#	b9	54	0.557	1.687	4.348	25.94 ± 0.04	98.8 ± 1.7
		0	0.597	1.615	4.206	25.52 ± 0.09	100 ± 0
		−18	0.558	1.886	5.069	25.54 ± 0.12	98.2 ± 0

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表 5 25%硝磺草酮悬浮剂的理化参数 (2)

Table 5. Physicochemical parameters of 25% mesotrione SC (2)

理化参数　　　 Physicochemical parameter	处理编号 Number
理化参数　　　 Physicochemical parameter	1# (YUS-FS3000)	2# (b1)	3# (b9)
pH 值 pH value	3.54	3.52	3.53
泡沫持久性 Persistent foam	0	0	0
分散性 Dispersity	良 Good	良 Good	良 Good
热贮稳定性 Stability at elevated temperature	合格 Qualified	合格 Qualified	合格 Qualified
冷冻稳定性 Stability at −18 ℃	合格 Qualified	合格 Qualified	合格 Qualified
低温稳定性 Stability at 0 ℃	合格 Qualified	合格 Qualified	合格 Qualified

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表 6 25%硝磺草酮悬浮剂1#~3# 对稗草的除草活性

Table 6. Herbicidal activity against Echinochloa crusgalli (L.) Beauv of 25% mesotrione SC (1#-3#)

处理编号 Number	分散剂类别 Dispersant	GR₅₀值 (有效成分) GR₅₀ value (a.i.)/(g/hm²)
1#	YUS-FS3000	29.03 ± 0.12
2#	b1	15.70 ± 0.05
3#	b9	10.19 ± 0.15

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表 7 25%硝磺草酮悬浮剂的理化参数 (3)

Table 7. Physicochemical parameters of 25% mesotrione SC (3)

处理编号 Number	分散剂质量分数 Dispersant amount/%	贮存温度 Storage temperature/℃	粒径 Particle size/μm			有效成分质量分数 Active ingredient content/%	悬浮率 Suspensibility/%
处理编号 Number	分散剂质量分数 Dispersant amount/%	贮存温度 Storage temperature/℃	D₁₀	D₅₀	D₉₀	有效成分质量分数 Active ingredient content/%	悬浮率 Suspensibility/%
4#	2	54	0.355	1.763	4.007	25.98 ± 0.21	99.9 ± 0.1
		0	0.526	1.477	3.726	26.01 ± 0.07	100 ± 0
		−18	0.396	1.607	4.010	25.62 ± 0.23	99.7 ± 0.4
2#	4	54	0.514	2.917	5.794	26.73 ± 0.05	99.3 ± 0.4
		0	0.521	1.742	3.976	26.23 ± 0.13	99.9 ± 0.5
		−18	0.393	1.520	3.539	26.27 ± 0.11	100 ± 0
5#	6	54	0.417	2.596	5.521	26.38 ± 0.22	99.5 ± 0.8
		0	0.405	1.421	3.349	26.07 ± 0.17	100 ± 0
		−18	0.409	1.398	3.598	25.84 ± 0.30	99.0 ± 1.2
6#	8	54	0.623	3.047	6.638	26.98 ± 0.12	98.5 ± 0.5
		0	0.438	1.305	3.112	26.25 ± 0.01	99.7 ± 0.5
		−18	0.409	1.342	3.540	26.13 ± 0.40	99.0 ± 1.4
7#	10	54	0.439	3.041	8.040	26.89 ± 0.22	99.2 ± 0.2
		0	0.421	1.312	3.354	26.78 ± 0.16	100 ± 0
		−18	0.406	1.265	2.905	26.22 ± 0.16	98.5 ± 0.2

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表 8 25%硝磺草酮悬浮剂的理化参数 (4)

Table 8. Physicochemical parameters of 25% mesotrione SC (4)

理化参数 Physicochemical parameter	处理编号 Number
理化参数 Physicochemical parameter	4#	2#	5#	6#	7#
pH 值 pH value	3.64	3.52	3.64	3.62	3.64
泡沫持久性 Persistent foam/mL	0	0	0	0	0
分散性 Dispersity	良 Good	良 Good	良 Good	良 Good	良 Good
热贮稳定性 Stability at elevated temperature	合格 Qualified	合格 Qualified	合格 Qualified	合格 Qualified	合格 Qualified
冷冻稳定性 Stability at −18 ℃	合格 Qualified	合格 Qualified	合格 Qualified	合格 Qualified	合格 Qualified
低温稳定性 Stability at 0 ℃	合格 Qualified	合格 Qualified	合格 Qualified	合格 Qualified	合格 Qualified

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表 9 分散剂b1不同添加量下25%硝磺草酮悬浮剂对稗草的除草活性

Table 9. Herbicidal activity against Echinochloa crusgalli (L.) Beauv of 25% mesotrione SC at different amounts of dispersant

处理编号 Number	b1 质量分数 Mass fraction of b1/%	GR₅₀值 (有效成分) GR₅₀ value (a.i.)/(g/hm²)
4#	2	13.28 ± 0.13
2#	4	15.70 ± 0.09
5#	6	8.17 ± 0.02
6#	8	36.34 ± 0.13
7#	10	39.46 ± 0.19

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参考文献(28)

[1]	SHANER D L, BRUNK G, NISSEN S, et al. Role of soil sorption and microbial degradation on dissipation of mesotrione in plant-available soil water[J]. J Environ Qual, 2012, 41(1): 170-178. doi: 10.2134/jeq2011.0187
[2]	孙约兵, 徐应明, 孙扬, 等. 新型除草剂硝磺草酮在玉米和土壤中的残留及降解行为[J]. 环境化学, 2013, 32(1): 144-149. doi: 10.7524/j.issn.0254-6108.2013.01.022 SUN Y B, XU Y M, SUN Y, et al. The residue and dissipation of mesotrione in maize and soil[J]. Environ Chem, 2013, 32(1): 144-149. doi: 10.7524/j.issn.0254-6108.2013.01.022
[3]	柏亚罗, 陈燕玲. 除草剂硝磺草酮的应用与开发进展[J]. 现代农药, 2016, 15(2): 42-47. doi: 10.3969/j.issn.1671-5284.2016.02.011 BAI Y L, CHEN Y L. Progress on application and development of mestrione as a herbicide[J]. Modern Agrochem, 2016, 15(2): 42-47. doi: 10.3969/j.issn.1671-5284.2016.02.011
[4]	张宏军, 季颖, 吴进龙, 等. 我国农药制剂最新登记情况分析[J]. 农药科学与管理, 2018, 39(6): 11-15. doi: 10.3969/j.issn.1002-5480.2018.06.005 ZHANG H J, JI Y, WU J L, et al. Recent status and management of pesticide formulations in China[J]. Pestic Sci Admin, 2018, 39(6): 11-15. doi: 10.3969/j.issn.1002-5480.2018.06.005
[5]	高德霖. 农药悬浮剂的物理稳定性问题[J]. 江苏化工, 1997, 25(5): 1-5. GAO D L. On physical stability of pesticide suspension concentrates[J]. Jiangsu Chem Ind[J]. 1997, 25(5): 1-5
[6]	Luckham P F. The physical stability of suspension concentrates with particular reference to pharmaceutical and pesticide formulations[J]. Pestic Sci. 1989, 25(1): 25-34.
[7]	HOROWITZ A I, PANZER M J. Poly(dimethylsiloxane)‐supported ionogels with a high ionic liquid loading[J]. Angew Chem Int Ed, 2014, 53(37): 9780-9783. doi: 10.1002/anie.201405691
[8]	PENG Y Y, LU F, TONG Q X. One-step synthesis, wettability and foaming properties of high-performance non-ionic hydro-fluorocarbon hybrid surfactants[J]. Appl Surf Sci, 2018, 433: 264-270. doi: 10.1016/j.apsusc.2017.10.012
[9]	ZHANG D, SHA M, PAN R M, et al. CF₃CF₂CF₂C(CF₃)₂-based fluorinated surfactants with high surface activity[J]. Chem Pap, 2019, 73(6): 1499-1508. doi: 10.1007/s11696-019-00701-4
[10]	MUNOZ G, DESROSIERS M, DUY S V, et al. Environmental occurrence of perfluoroalkyl acids and novel fluorotelomer surfactants in the freshwater fish Catostomus commersonii and sediments following firefighting foam deployment at the Lac-Mégantic railway accident[J]. Environ Sci Technol, 2017, 51(3): 1231-1240. doi: 10.1021/acs.est.6b05432
[11]	FANGA C, MEGHARAJ M, NAIDU R. Electrochemical detection of thioether-based fluorosurfactants in aqueous film-forming foam (AFFF)[J]. Electroanalysis, 2017, 29(4): 1095-1102. doi: 10.1002/elan.201600724
[12]	肖进新, 江洪. 碳氟表面活性剂[J]. 日用化学工业, 2001, 31(5): 24-27. doi: 10.3969/j.issn.1001-1803.2001.05.010 XIAO J X, JIANG H. Fluorinated surfactants[J]. China Surfactant Deterg & Cosmetics, 2001, 31(5): 24-27. doi: 10.3969/j.issn.1001-1803.2001.05.010
[13]	BLOCK J. Method and composition for removing calcium sulfate scale deposits from surfaces. US4144185[P], 1979-03-13.
[14]	EASTOE J, PAUL A, RANKIN A, et al. Fluorinated nonionic surfactants bearing either CF₃- or H-CF₂- terminal groups: adsorption at the surface of aqueous solutions[J]. Langmuir, 2001, 17(25): 7873-7878. doi: 10.1021/la010958n
[15]	刘国强, 张凌飞, 徐祖顺. 一种非离子碳氟表面活性剂的合成及表征[J]. 精细与专用化学品, 2011, 19(1): 24-27. doi: 10.3969/j.issn.1008-1100.2011.01.007 LIU G Q, ZHANG L F, XU Z S. Preparation and characterization of a kind of non-ionic fluorocarbon surfactants[J]. Fine Specialty Chem, 2011, 19(1): 24-27. doi: 10.3969/j.issn.1008-1100.2011.01.007
[16]	PARLATO M C, JEE J P, TESHITE M, et al. Synthesis, characterization, and applications of hemifluorinated dibranched amphiphiles[J]. J Org Chem, 2011, 76(16): 6584-6591. doi: 10.1021/jo200835y
[17]	WAGNER O, THIELE J, WEINHART M, et al. Biocompatible fluorinated polyglycerols for droplet microfluidics as an alternative to PEG-based copolymer surfactants[J]. Lab Chip, 2016, 16(1): 65-69. doi: 10.1039/C5LC00823A
[18]	ZHOU R, JIN Y, SHEN Y C, et al. Surface activity, salt and pH tolerance, and wettability of novel nonionic fluorinated surfactants with a short fluorocarbon chain[J]. J Dispers Sci Technol, 2020, 42(1): 152-159. doi: 10.1080/01932691.2020.1768862
[19]	WANG R G, SONG L Y, GUO Y Q, et al. Synthesis and structure-activity relationships of nonionic surfactants with short fluorocarbon chains[J]. J Mol Liq, 2021, 321: 114486. doi: 10.1016/j.molliq.2020.114486
[20]	SONG L Y, WANG R G, NIU K K, et al. Design, synthesis, characterization, and surface activities of comb-like polymeric fluorinated surfactants with short fluoroalkyl chains[J]. Colloids Surf A, 2021, 609: 125666. doi: 10.1016/j.colsurfa.2020.125666
[21]	杨琛, 李晓刚, 刘双清, 等. 10%嘧菌酯水稻悬浮种衣剂制备[J]. 农药, 2012, 51(5): 347-350. doi: 10.3969/j.issn.1006-0413.2012.05.010 YANG C, LI X G, LIU S Q, et al. Preparation of azoxystrobin 10% flowable concentrate for rice seed coating[J]. Agrochemicals, 2012, 51(5): 347-350. doi: 10.3969/j.issn.1006-0413.2012.05.010
[22]	硝磺草酮悬浮剂: GB 28138—2011[S]. 北京: 中国标准出版社, 2011. Mesotrione aqueous suspension concentrate: GB28138—2011[S]. Beijing: Standards Press of China, 2011.
[23]	农药悬浮率测定方法: GB/T 14825—2006[S]. 北京: 中国标准出版社, 2006. Determination method for suspensibility of pesticides: GB/T 14825—2006 [S]. Beijing: Standards Press of China, 2006
[24]	农药pH值测定方法: GB/T 1601—93[S]. 北京: 中国标准出版社, 1994. Determination method of pH value for pesticides: GB/T 1601—93[S]. Beijing: Standards Press of China, 1994
[25]	农药持久起泡性测定方法: GB/T 28137—2011[S]. 北京: 中国标准出版社, 2011. Testing method of persistent foaming for pesticides: GB/T 28137—2011 [S]. Beijing: Standards Press of China, 2011
[26]	农药热贮稳定性测定方法: GB/T 19136—2003[S]. 北京: 中国标准出版社, 2003. Testing method for the storage stability at elevated temperature of pesticides: GB/T 19136—2003 [S]. Beijing: Standards Press of China, 2003.
[27]	农药低温稳定性测定方法: GB/T 19137—2003[S]. 北京: 中国标准出版社, 2003. Testing method for the storage stability at low temperature of pesticides: GB/T 19137—2003 [S]. Beijing: Standards Press of China, 2003.
[28]	WANG Q M, LI H, LI Y H, et al. Synthesis and herbicidal activity of 2-cyano-3-(2-chlorothiazol-5-yl)methylaminoacrylates[J]. J Agric Food Chem, 2004, 52(7): 1918-1922. doi: 10.1021/jf035312a