十二醇聚氧乙烯醚的表面性能及在水悬浮剂中的应用

doi:10.7503/cjcu20140331

摘要/Abstract

摘要：

探讨了十二醇聚氧乙烯醚(AEO)的EO链长对其临界胶束浓度(cmc)、表面张力(γ_cmc)、胶束生成自由能(ΔG_m)、分子面积(A_cmc)和亲水亲油平衡(HLB)值等表面性能的影响; 同时研究了不同EO链长的AEO对质量分数25%代森锰锌水悬浮剂(SC)的流变性能[黏度、储能模量(G')、流动点时的应变(γ_flow)、触变性]和物理贮存性能(热贮前悬浮率、热贮后悬浮率和倾倒性)的影响. 结果发现, AEO的cmc, γ_cmc, ΔG_m, A_cmc和HLB值随着EO链长的增加而增大; AEO能够明显改善代森锰锌SC的黏度, 以AEO-9所制备的SC黏度最小, 且AEO的EO链长越长, 所对应的SC结构恢复越慢, 恢复慢的样品其倾倒残留率过高; G'和γ_flow能反映SC内部结构变化, 可作为评价农药SC物理稳定性流变学指标.

关键词: 十二醇聚氧乙烯醚, 表面性能, 悬浮剂, 流变性能

Abstract:

The paper studies the critical micelle concentration(cmc), the equilibrium surface tension(γ_cmc), the standard free energy of micellization(ΔG_m), the area per molecular at cmc(A_cmc) and hydrophile lipophile balance(HLB), which are affected by the function of the oxyethylene group(EO) number in the alcohol ethoxylate(AEO). It also studies the influence of AEO with different EO number as dispersants on the rheological properties(viscosity, storage modulus G', γ_flow and thixotropy) and the physical stability(the suspension rate before and after the hot storage, residual pourability ratio) of Mancozeb(25%) suspension concentrate(SC). As the value of the oxyethylene group number increase from 4 to 20, the values of cmc, γ_cmc, ΔG_m, A_cmc and HLB are rising. The adding of AEO can reduce the viscosity of Mancozeb(25%) SC, and the SC with AEO-9 has the lowest viscosity. With the increase of the EO chains in AEO, the thixotropy recovery of SC which has higher residual pourability ratio decreases gradually. Through strain sweep, we find the values of G' and γ_flow reflect the structural variation of the SC, and then G' and γ_flowcan be used as suitable SC stability indicators.

Key words: Alcohol ethoxylate, Surface property, Suspension concentrate, Rheology

中图分类号:

O648

TrendMD:

秦娇龙, 庞文文, 杨小东, 张腾, 任天瑞. 十二醇聚氧乙烯醚的表面性能及在水悬浮剂中的应用. 高等学校化学学报, 2014, 35(10): 2182.

QIN Jiaolong, PANG Wenwen, YANG Xiaodong, ZHANG Teng, REN Tianrui. Studies on the Surface Properties of Alcohol Ethoxylate and the Application in Suspension Concentrate^†. Chem. J. Chinese Universities, 2014, 35(10): 2182.

图/表 17

Fig.1 Surface tension γ plotted as a function of concentration of AEOs

Table 1 Surface and micellar properties of AEO surfactants obtained in aqueous solution*

No.	γ_cmc/(mN·m^-1)	10⁵cmc/(mol·L^-1)	A_cmc/(nm²·molecule^-1)	ΔG_m/(kJ·mol^-1)	HLB
AEO-4	25.80	3.79	0.601	-25.14	9.96
AEO-7	26.80	4.63	0.941	-24.74	12.55
AEO-9	29.10	6.52	0.956	-23.89	13.49
AEO-15	37.50	7.86	0.960	-23.43	15.16
AEO-20	41.90	8.44	1.266	-23.25	15.69

Fig.2 Effects of EO number on cmc and γcmc at 25 ℃

Fig.3 Effects of EO number on Acmc and ΔGm at 25 ℃

Fig.4 Flow curves for AEO-SCs at 25 ℃ ● SC; ○ SC-AEO-4; ■ SC-AEO-7; ▼ SC-AEO-9;□ SC-AEO-15; Δ SC-AEO-20.

Fig.5 Viscosity curves for different AEO-SCs at constant shear rate(10 s-1) ● SC; ▽ SC-AEO-4; ◆ SC-AEO-7; □ SC-AEO-9;■ SC-AEO-15; ◇ SC-AEO-20.

Fig.6 Viscosity curves for different AEO-SCs at constant shear rate(100 s-1) ● SC; ○ SC-AEO-4; ■ SC-AEO-7; ▼ SC-AEO-9;□ SC-AEO-15; Δ SC-AEO-20.

Fig.7 FESEM images of SC(A) and SC-AEO-9(B)

Table 2 Rheological parameters of SC-AEOs

Sample	Bingham model				Herschel-Bulkley model
Sample	τ₀/Pa	η_P/(Pa·s)	R²	n	K/(Pa·sⁿ)	τ₀/Pa	R²
SC	18.22	0.0227	0.9458	1.1489	0.009358	18.47	0.9468
SC-AEO-4	8.967	0.01184	0.9945	0.8802	0.02433	8.828	0.9970
SC-AEO-7	1.2806	0.0302	0.9458	0.6507	0.2238	0.3696	0.9999
SC-AEO-9	0.8827	0.02191	0.9487	0.6551	0.1575	0.2436	0.9999
SC-AEO-15	2.8473	0.02439	0.9692	0.7128	0.1317	2.176	0.9982
SC-AEO-20	1.3026	0.02536	0.9498	0.6385	0.2040	0.4668	0.9999

Table 3 Stability analysis of SC-AEOs

Ssmple	W₁(%)	W₂(%)	S_t	τ₀/Pa	τ_flow/Pa	γ_flow(%)
SC	30.00	25.00	813.5	18.47	18.47	2.492
SC-AEO-4	94.55	91.05	745.6	8.828	2.228	29.09
SC-AEO-7	95.92	94.57	12.24	0.3696	0.2967	10.59
SC-AEO-9	94.42	96.12	11.12	0.2436	0.2286	13.46
SC-AEO-15	94.89	94.47	89.23	2.176	0.7787	27.70
SC-AEO-20	95.01	95.81	18.41	0.4668	0.6075	23.31

Fig.8 Dependence of the elastic modulus(G') on strain amplitude(γ) ● SC; ○ SC-AEO-4; ■ SC-AEO-7; ▼ SC-AEO-9;□ SC-AEO-15; Δ SC-AEO-20.

Fig.9 Strain sweep experiment of SC-AEOs ●○ SC; ▼▽ SC-AEO-4; ▲Δ SC-AEO-4;◆◇ SC-AEO-7; ■□ SC-AEO-9.G': solid circle; G″: hollow circle.

Table 4 Rheological data of three interval thixotropy and residual pourability test

Sample	Structure recovery ratio(%)				R(%)
Sample	5 s		7 s	10 s	15 s
SC	113.9	111.4	112.2	111.7	≥20
SC-AEO-4	76.69	83.84	91.68	99.07	10
SC-AEO-7	54.92	60.06	64.37	68.78	7
SC-AEO-9	44.26	49.70	54.05	58.41	≤5
SC-AEO-15	27.91	31.41	35.06	38.75	≤3
SC-AEO-20	40.63	45.17	48.97	52.93	≤3

Fig.10 Three interval thixotropy curves of SC-AEOs ● SC; ○ SC-AEO-4; ■ SC-AEO-7; ◇ SC-AEO-9;◆ SC-AEO-15; Δ SC-AEO-20.

Fig.11 Conformation of AEO-4(A), AEO-9(B) and AEO-20(C)

Fig.12 Effect of AEOs with different EO chains on dispersion ability of particles (A) Short or no AEO: flocculation; (B) proper EO chains: dispersion; (C) too long EO chains: bridging.

Fig.13 Illustration of the effect of AEOs (A) Without dispersant or AEO with short EO chain as dispersant; (B) AEO with long EO chain as dispersant.

参考文献 44

[1]	Luckham P. F., Powder Technology, 1989, 58(2), 75—91
[2]	Luckham P. F., Pesticide Science, 1989, 25(1), 25—34
[3]	GuoW. L., Liquid Pharmaco Kinetical Preparations, Chemical Industry Press, Beijing, 2004, 196—224
	(郭武棣. 液体制剂, 北京:化学工业出版社, 2004, 196—224)
[4]	Faers M. A., Kneebone G. R., Pesticide Science,1999, 55(3), 312—325
[5]	Winzeler H. B., Vogel R., Dudler A., Advances in Pesticide Science,1979, 3, 798—809
[6]	Xu Y. K., World Pesticides, 1980, 6, 1—6
	(徐义宽. 世界农药, 1980, 6, 1—6)
[7]	Zhou Y., Tang A. S., Agrochemicals,1995, 34(5), 6—9
	(周瑛, 唐霭淑. 农药, 1995, 34(5), 6—9)
[8]	Shen D. L., Tan C. X., Agrochemicals,1998, 37(11), 11—13
	(沈德隆, 谭成侠. 农药, 1998, 37(11), 11—13)
[9]	Shen J., The Research of Rheology and Physical Storage Stability in Pesticide Suspension Concentrate , the Chinese Academy of Agricultural Sciences, Beijing, 2008
	(沈娟. 农药悬浮剂流变学特性及贮存物理稳定性研究, 北京: 中国农业科学院, 2008)
[10]	Wu Q. M., Ruan J. M., Huang B. Y., Acta Chimica Sinica,2006, 64(15), 1543—1547
	(伍秋美, 阮建明, 黄伯云. 化学学报, 2006, 64(15), 1543—1547)
[11]	Maranzano B. J., Wagner N. J., Journal of Rheology,2001, 45(5), 1205—1222
[12]	Duro R., Alvarez C., Martínez-Pacheco R., European Journal of Pharmaceutics and Biopharmaceutics,1998, 45(2), 181—188
[13]	Nasu A., Otsubo Y., Colloids and Surfaces A: Physicochemical and Engineering Aspects,2008, 326(1), 92—97
[14]	Lv Y., Liu H., Sang Y., Journal of Materials Science,2010, 45(3), 706—712
[15]	Feng J. Y., Analytical Chemistry, 1999, 27(3), 289—291
	(冯建跃. 分析化学, 1999, 27(3), 289—291)
[16]	Ma C., Liu F., Mu W.,Modern Agrochemicals, 2006, 4, 15—17
	(马超, 刘峰, 慕卫. 现代农药, 2006, 4, 15—17)
[17]	Liu Y., Study on the Environmental Friendly Pesticide Formulation Based on the Green Surfactants, Zhejiang University, Hangzhou, 2012
	(刘迎. 基于绿色表面活性剂的农药环境友好型制剂的研究, 杭州: 浙江大学, 2012)
[18]	Wang Z.D., Hu L. M.,Speciality Petrochemicals, 1996, (6), 58—62
	(王正东, 胡黎明. 精细石油化工, 1996, (6), 58—62)
[19]	Li Z. X., Chen W. H., China Surfactant Detergent & Cosmetics,1990, 6, 25—29
	(李智新, 陈文海. 日用化学工业, 1990, 6, 25—29)
[20]	Martin J.S., Nonionic Surfactants: Physical Chemistry, CRC Press, New York, 1987, 500
[21]	Wei Y. C., Zhang H. Y., Wu W. K., Chinese Journal of Experimental Traditional Medical Formulae,2011, 2, 53—56
	(韦迎春, 张海燕, 邬伟魁. 中国实验方剂学杂志, 2011, 2, 53—56)
[22]	Zhang D. X., Zhang G. S., Chen B., Agrochemicals Research & Application,2010, 1, 18—20
	(张大侠, 张贵森, 陈波. 农药研究与应用, 2010, 1, 18—20)
[23]	Xian Y., Wang L. P., Pesticide Science and Administration,2003, 24(7), 20—21
	(鲜艳, 王列平. 农药科学与管理, 2003, 24(7), 20—21)
[24]	Dai Y. J., Zhang Z. D., Pesticide Science and Administration,2006, 3, 12—14
	(戴永军, 张兆栋. 农药科学与管理, 2006, 3, 12—14
[25]	Rosen M. J., CohenA. W., Dahanayake M., J. Phys. Chem., 1982, 86(4), 541—545
[26]	Adkins S., Chen X., Nguyen Q. P., J. Colloid Interf. Sci., 2010, 346(2), 455—463
[27]	Carey M. C., Small D. M., J. Colloid Interf. Sci., 1969, 31(3), 382—396
[28]	Yang Y. W., Deng N. J., Yu G., Zhou Z. K., Attwood D., Booth C., Langmuir,1995, 11(12), 4703—4711
[29]	Gao C. Y., Feng Y. P., Lin L., Fine Chemical Intermediates,2009, 39(4), 11—13
	(高长义, 冯银鹏, 林丽. 精细化工中间体, 2009, 39(4), 11—13)
[30]	Zhang G. S., Li L. G., World Pesticides,2010, 32(4), 40—47
	(张国生, 李琳光. 世界农药, 2010, 32(4), 40—47)
[31]	Kausalya R. N., Foster A., Styring M. G., J. Colloid Interf. Sci., 1990, 136(2), 588—592
[32]	Corkill J. M., Goodman J. F., Ottewill R. H., Transactions of the Faraday Society,1961, 57, 1627—1636
[33]	Kratzat K., Finkelmann H., Langmuir,1996, 12(7), 1765—1770
[34]	Schick M. J., Beyer E. A., Journal of the American Oil Chemists’ Society,1963, 40(2), 66—68
[35]	Geng L., Study on the Correlations Between Critical Micelle Concentration and Molecular Energies, Jiangnan University, Wuxi, 2012
	(耿林. 表面活性剂的临界胶束浓度与分子能量项和分子结构的关系研究, 无锡: 江南大学, 2012)
[36]	Raghavan S. R., Khan S. A., Journal of Rheology,1995, 39(6), 1311—1325
[37]	Ran Q., Somasundaran P., Miao C., J. Colloid Interf. Sci., 2009, 336(2), 624—633
[38]	Lü S. Y., Shao Z. Q., Zhang Z. L., Wang F. J., Wang W. J., Chem. J. Chinese Universities,2012, 33(2), 409—415
	(吕少一, 邵自强, 张振玲, 王飞俊, 王文俊. 高等学校化学学报, 2012, 33(2), 409—415)
[39]	Xie Y., Lü Z. Y., Sun Z. Y., An L. J., Li X. H., Wu Z. H., Chem. J. Chinese Universities,2013, 34(6), 1521—1526
	(谢宇, 吕中元, 孙昭艳, 安立佳, 李秀宏, 吴忠华. 高等学校化学学报, 2013, 34(6), 1521—1526)
[40]	Bo X.L., Huang Q. L., Wang G. P.,Agrochemicals, 2006, 4, 231—236
	(卜小莉, 黄啟良, 王国平. 农药, 2006, 4, 231—236)
[41]	Hu S. H., Li H., Hu W., Journal of Hubei University of Technology,2012, 27(2), 57—60
	(胡圣飞, 李慧, 胡伟. 湖北工业大学学报, 2012, 27(2), 57—60)
[42]	BoX. L., Huang Q. L., Wang G. P., Pesticide Science and Administration,2006, 27(4), 24—28
	(卜小莉, 黄啟良, 王国平. 农药科学与管理, 2006, 27(4), 24—28)
[43]	Mezger T.G., The Rheology Handbook: for Users of Rotational and Oscillatory Rheometers, Vincentz Network GmbH & Co. KG, 2006
[44]	Hao R. G., Hu Z. L., Liu S. J., China Writing Instruments,2009, 4, 9—13
	(郝瑞光, 胡卓林, 刘守君. 中国制笔, 2009, 4, 9—13)