Synthesis and Gel Properties of a Novel Amide Gelator with Melamine Moieties and Rationalizing Gelation Behavior by Hansen Solubility Parameters†

doi:10.7503/cjcu20160268

Abstract

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

CLC Number:

O648.17

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2016, 37(11): 2068.

Figures/Tables 9

References 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