阳离子纤维素-十二烷基苯磺酸钠的拟聚阴离子研究

doi:10.7503/cjcu20190057

摘要/Abstract

摘要：

采用浊度法、表面张力法、 zeta电位法和毛细管电泳法(CE)研究了典型的阳离子纤维素(JR400)与典型的阴离子表面活性剂十二烷基苯磺酸钠(SDBS)之间的缔合作用. 浊度法和zeta电位法实验结果表明, 在等电区附近产生的沉淀区随JR400浓度减小而变窄, 加入过量SDBS后沉淀消失, 而且发现阳离子纤维素同系物的分子量和取代度对结果的影响较小. 表面张力法实验结果显示, 该类复合体系的表面张力曲线表观上与典型“中性聚合物-阴离子表面活性剂”体系相似, 具有3个拐点(但第二拐点易被沉淀区覆盖)且SDBS与阳离子纤维素间形成缔合物. zeta电位法实验结果表明, 沉淀区前少量SDBS存在时该缔合物具有正电位, 因而维持聚阳离子特性; 沉淀区后过量SDBS存在时该缔合物具有负电位, CE分析进一步证明其为拟聚阴离子. 上述实验结果和结论对研究该类复合体系具有较大理论意义和实用价值.

关键词: 阳离子纤维素, 十二烷基苯磺酸钠, 缔合作用, 拟聚阴离子, 毛细管电泳

Abstract:

The complexation between typical cationic cellulose(JR400) and a typical anionic surfactant sodium dodecylbenzenesulfonate(SDBS) in aqueous solution was studied by nephelometry, tensiometry, zeta potential method and capillary electrophoresis(CE) in this paper. The turbidity and the zeta potential results show that precipitation zone(PZ) appears near to the isoelectric zone and shrinks with the declined concentration of JR400, and sediment disappears when SDBS in large excess, in addition to being less influenced by molecular weight and substitution degree of the cationic celluloses. The tensiometry results show that there are three critical concentration thresholds though the second critical concentration is commonly overlapped by PZ, which indicates the formation of complexes between SDBS and the polycations similar with “neutral polymer-anionic surfactant” systems. The zeta potential results show that the complexes formed ahead of PZ have the positive zeta potential so that keep the polycation properties, while behind the zone the negative in large excess of SDBS, and the latter is confirmed by CE being pseudo-polyanions. These experimental results and conclusions have great theoretical significance and practical value for studies of polycation-anionic surfactant systems.

Key words: Cationic cellulose, Sodium dodecylbenzenesulfonate, Complexation, Pseudo-polyanion, Capillary electrophoresis

中图分类号:

O648

TrendMD:

胡学一, 陈苗苗, 方云, 冯瑞沁, 韩慧慧. 阳离子纤维素-十二烷基苯磺酸钠的拟聚阴离子研究. 高等学校化学学报, 2019, 40(7): 1464.

HU Xueyi, CHEN Miaomiao, FANG Yun, FENG Ruiqin, HAN Huihui. Investigation on Pseudo-polyanions of Cationic Cellulose-Sodium Dodecylbenzenesulfonate^†. Chem. J. Chinese Universities, 2019, 40(7): 1464.

图/表 12

Fig.1 Appearance of JR400(2 g/L)-SDBS(A) and JR400(0.5 g/L)-SDBS(B) with the corresponding turbidity curve(A) cSDBS/(mmol·L-1): a. 0 (clear); b. 2 (clear); c. 4 (turbid); d. 6 (precipitation); e. 8 (precipitation); f. 10 (precipitation); g. 20 (precipitate); h. 30 (clear). (B) cSDBS/(mmol·L-1): a. 0.5 (clear); b. 1 (clear); c. 2 (turbid); d. 4 (precipitation); e. 6 (precipitation); f. 8 (clear); g. 9 (clear).

Table 1 Concentration thresholds of JR400-SDBS complexes including the corresponding precipitation zone(PZ)*

ρ/(g·L^-1)	c_SDBS/(mmol·L^-1)
ρ/(g·L^-1)	Precipitation zone	c₁	psp	c₂
0.05	0.4—0.8	0.1	—	4.0
0.10	0.6—1.0	0.2	—	6.0
0.50	2.0—6.0	0.4	2.0	8.0

Fig.2 Zeta potential profiles of JR400(0.05 g/L)-SDBS(A), JR400(0.1 g/L)-SDBS(B) and JR400(0.5 g/L)-SDBS(C) complexes PZ: precipitation zone.

Fig.3 Surface tension curves of JR400-SDBS complexes and the corresponding areas of precipitation zoneρ/(g·L-1): (A) 0.05; (B) 0.1; (C) 0.5.

Scheme 1 Molecular structure of cationic celluloses

Table 2 Properties of the tested cationic celluloses

Cationic cellulose	Mass fraction(%)	Viscosity/(mPa·s)	N content(%)	SD/(cation per unit)	CD^*/(mmol e·g^-1)
JR125	2	75—175	1.5—2.2	0.42	1.33(0.42)
JR400	2	300—500	1.5—2.2	0.42	1.33(0.42)
JR30M	2	25000—35000	1.5—2.2	0.42	1.33(0.42)
LR400	2	300—500	0.8—1.1	0.17	0.62(0.17)

Fig.4 Effects of molecular mass and substitution degrees of cationic celluloses on zeta potential variation of the cationic cellulose-SDBS complexesPZ: precipitation zone. (A) JR125(0.05 g/L)-SDBS; (B) JR125(0.1 g/L)-SDBS; (C) JR125(0.5 g/L)-SDBS; (D) JR30 M(0.05 g/L)-SDBS; (E) JR30M(0.1 g/L)-SDBS; (F) JR30M(0.5 g/L)-SDBS; (G) LR400(0.1 g/L)-SDBS.

Fig.5 Effect of molecular mass and substitution degrees of cationic celluloses on surface tension variation of the cationic cellulose-SDBS complexesPZ: precipitation zone. ρ/(g·L-1): (A) 0.05; (B) 0.1; (C) 0.5; (D) 0.05; (E) 0.1; (F) 0.5; (G) 0.1.

Table 3 More concentration thresholds of various cationic cellulose-SDBS complexes including the corresponding precipitation zone*

Complex	ρ/(g·L^-1)	c_SDBS/(mmol·L^-1)
Complex	ρ/(g·L^-1)	Precipitation zone	c₁	psp	c₂
JR125-SDBS	0.05	0.4—0.8(6.0—12.0)	0.2	—	4.0
	0.10	0.6—1.0(4.5—7.5)	0.2	—	6.0
	0.50	2.0—6.0(3.0—9.0)	0.4	2.0	8.0
JR30M-SDBS	0.05	0.4—0.8(6.0—12.0)	0.2	—	4.0
	0.10	0.6—1.0(4.5—7.5)	0.4	—	6.0
	0.50	2.0—6.0(3.0—9.0)	0.4	2.0	8.0
LR400-SDBS	0.10	0.6—1.0(9.7—16.1)	0.2	—	6.0

Fig.6 Electropherograms of various cationic cellulose-SDBS complexes(A) JR125(0.05 g/L)-SDBS; (B) JR125(0.1 g/L)-SDBS; (C) JR400(0.05 g/L)-SDBS; (D) JR400(0.1 g/L)-SDBS; (E) JR400(0.05 g/L)-SDBS; (F) JR400(0.1 g/L)-SDBS; (G) JR400(0.1 g/L)-SDBS.cSDBS/(mmol·L-1): a. 8; b. 6; c. 4; d. 2; e. 1.

Table 4 Effective electrophoretic mobility(μe) of various cationic cellulose-SDBS complexes

Complex	ρ/(g·L^-1)	μ_e/(cm²·kV^-1·s^-1)
Complex	ρ/(g·L^-1)	1 mmol/L SDBS	2 mmol/L SDBS	4 mmol/L SDBS	6 mmol/L SDBS	8 mmol/L SDBS
JR125	0.05	-0.36	-0.37	-0.37	-0.38	-0.37
	0.10		-0.35	-0.36	-0.36	-0.37
JR400	0.05	-0.33	-0.38	-0.38	-0.38	-0.39
	0.10		-0.37	-0.38	-0.38	-0.38
JR30M	0.05	-0.34	-0.36	-0.37	-0.37	-0.37
	0.10		-0.36	-0.36	-0.37	-0.37
LR400	0.10		-0.37	-0.38	-0.38	-0.38

Fig.7 Schematic illustration of chemical species evolution in cationic cellulose-SDBS complexes

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