含密胺基团新型酰胺类凝胶因子的合成、 性能及Hansen溶度参数对凝胶行为的预估

doi:10.7503/cjcu20160268

摘要/Abstract

摘要：

设计合成了一种含有密胺基团的新型酰胺类凝胶因子AMOG, 其在多种常用有机溶剂中均能形成凝胶, 且在甲苯和二甲苯中形成凝胶的临界凝胶浓度(CGC)约为1 mmol/L. 采用“试管倒转法”确定了凝胶的溶剂-凝胶转变温度(T_gel), 利用SEM表征了凝胶的微观结构, 发现AMOG具有明显的溶剂效应. 运用溶剂的Hansen溶度参数探索溶剂对凝胶行为的作用机制, 发现溶剂的氢键作用参数(δ_h)对凝胶的微观结构和凝胶性质有显著影响: AMOG在1.0 MPa^1/2<δ_h<4.1 MPa^1/2的溶剂中形成透明凝胶, 在4.1 MPa^1/2<δ_h<8.0 MPa^1/2的溶剂中为不透明凝胶, 在δ_h>8.0 MPa^1/2的溶剂中为沉淀或溶液状态. 进一步将溶剂的Hansen溶度参数以三维坐标(δ_d, δ_p和δ_h)表示, 发现能使AMOG形成凝胶的溶剂主要集中在Hansen空间的特定区域内. 实验结果表明, 凝胶体系的溶液-凝胶转变温度主要受色散参数δ_d与极性参数δ_p的影响, 氢键参数δ_h对其有微调的作用.

关键词: 有机凝胶, 酰胺, 密胺, Hansen溶度参数, 溶剂效应

Abstract:

A novel amide gelator with melamine moieties(AMOG) was designed and synthesized. Gelator AMOG is capable of forming gel in various common organic solvents and the critical gelation concentration(CGC) of the gels formed in toluene and xylene are as low as 1 mmol/L. Tube inversion method is adopted to define the sol-gel transition temperature(T_gel) and the scanning electron microscope(SEM) is used to investigate micro-morphology of gels. The results of these tests exhibit obvious solvent effect on gelation behavior of AMOG. Further investigation for gelation behavior based on Hansen solubility parameters(HSPs) of solvents reveals that hydrogen bonding parameter(δ_h) has significant influence on the micro-morphology and properties of gels. 1.0 MPa^1/2<δ_h<4.1 MPa^1/2 for organic solvents is the favorable domain for transparent gels formation, opaque gels occur in the range of 4.1 MPa^1/2<δ_h<8.0 MPa^1/2 and solution/precipitation remain if δ_h is larger than 8.0 MPa^1/2. HSPs values for tested solvents are plotted as a point in Hansen space, which is constructed with δ_d, δ_p and δ_h as its three-dimensional coordinates. Most of the solvents that could form gels cluster in a certain region in above Hansen space. Sol-gel transition temperature is related to parameter δ_d and δ_p.

Key words: Organogel, Amide, Melamine, Hansen solubility parameter, Solvent effect

中图分类号:

O648.17

TrendMD:

王潇, 杨新国, 沈启立. 含密胺基团新型酰胺类凝胶因子的合成、性能及Hansen溶度参数对凝胶行为的预估. 高等学校化学学报, 2016, 37(11): 2068.

WANG Xiao, YANG Xinguo, SHEN Qili. Synthesis and Gel Properties of a Novel Amide Gelator with Melamine Moieties and Rationalizing Gelation Behavior by Hansen Solubility Parameters^†. Chem. J. Chinese Universities, 2016, 37(11): 2068.

图/表 9

参考文献 34

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Solvent	Behavior^*	CGC/(mmol·L^-1)	Solvent	Behavior^*	CGC/(mmol·L^-1)
Methylcyclohexane	Gt	2	Butyl acetate	Go	2
Toluene	Gt	1	Acetone	Go	3
Xylene	Gt	1	Ethyl acetate	Go	2
Styrene	Gt	2	Tetrahydrofuran	Go	5
Dichloromethane	Go	5	DMF	P
Chloroform	S		Methanol	P

Solvent	Behavior^*	CGC/(mmol·L^-1)	Solvent	Behavior^*	CGC/(mmol·L^-1)
Methylcyclohexane	Gt	2	Butyl acetate	Go	2
Toluene	Gt	1	Acetone	Go	3
Xylene	Gt	1	Ethyl acetate	Go	2
Styrene	Gt	2	Tetrahydrofuran	Go	5
Dichloromethane	Go	5	DMF	P
Chloroform	S		Methanol	P

Solvent	Behavior	δ	δ_d/MPa^1/2	δ_p/MPa^1/2	δ_h/MPa^1/2
Methylcyclohexane	Gt	16.0	16.0	0	1.0
Toluene	Gt	18.2	18.0	1.4	2.0
Xylene	Gt	18.1	17.8	1.0	3.1
Styrene	Gt	19.1	18.6	1.0	4.1
Methyl ethyl ketone	Go	19.1	16.0	9.0	5.1
Trichloroethylene	Gt	19.0	18.0	3.1	5.3
Methyl methacrylate	Go	17.9	15.8	6.5	5.4
Chloroform	S	18.9	17.8	3.1	5.7
Dichloromethane	Go	20.2	18.2	6.3	6.1
Butyl acetate	Go	17.4	15.8	3.7	6.3
Butyl methacrylate	Go	18.1	15.6	6.4	6.6
Acetone	Go	19.9	15.5	10.4	7.0
Ethyl acetate	Go	18.2	15.8	5.3	7.2
1,4-Dioxane	Go	20.5	19.0	1.8	7.4
Tetrahydrofuran	Go	19.5	16.8	5.7	8.0
Methacrylic acid	S	19.0	15.8	2.8	10.2
DMSO	P	26.7	18.4	16.4	10.2
DMF	P	24.9	17.4	13.7	11.3
Ethanol	P	26.5	15.8	8.8	19.4
Methanol	P	29.6	15.1	12.3	22.3

Solvent	Behavior	δ	δ_d/MPa^1/2	δ_p/MPa^1/2	δ_h/MPa^1/2
Methylcyclohexane	Gt	16.0	16.0	0	1.0
Toluene	Gt	18.2	18.0	1.4	2.0
Xylene	Gt	18.1	17.8	1.0	3.1
Styrene	Gt	19.1	18.6	1.0	4.1
Methyl ethyl ketone	Go	19.1	16.0	9.0	5.1
Trichloroethylene	Gt	19.0	18.0	3.1	5.3
Methyl methacrylate	Go	17.9	15.8	6.5	5.4
Chloroform	S	18.9	17.8	3.1	5.7
Dichloromethane	Go	20.2	18.2	6.3	6.1
Butyl acetate	Go	17.4	15.8	3.7	6.3
Butyl methacrylate	Go	18.1	15.6	6.4	6.6
Acetone	Go	19.9	15.5	10.4	7.0
Ethyl acetate	Go	18.2	15.8	5.3	7.2
1,4-Dioxane	Go	20.5	19.0	1.8	7.4
Tetrahydrofuran	Go	19.5	16.8	5.7	8.0
Methacrylic acid	S	19.0	15.8	2.8	10.2
DMSO	P	26.7	18.4	16.4	10.2
DMF	P	24.9	17.4	13.7	11.3
Ethanol	P	26.5	15.8	8.8	19.4
Methanol	P	29.6	15.1	12.3	22.3

Solvent	T_gel/℃	δ	δ_d/MPa^1/2	δ_p/MPa^1/2	δ_h/MPa^1/2
Toluene	81	18.2	18.0	1.4	2.0
Xylene	85	18.1	17.8	1.0	3.1
Styrene	67	19.1	18.6	1.0	4.1
Methyl ethyl ketone	73	19.1	16.0	9.0	5.1
Methyl methacrylate	85	17.9	15.8	6.5	5.4
Butyl acetate	89	17.4	15.8	3.7	6.3
Butyl methacrylate	94	18.1	15.6	6.4	6.6
Acetone	60	19.9	15.5	10.4	7.0
Ethyl acetate	87	18.2	15.8	5.3	7.2
1,4-Dioxane	55	20.5	19.0	1.8	7.4