| With the development of science and technology,there are specific requirements for the efficacy of surfactants.For example,in the industrial fields of industrial cleaning,printing and dyeing,there are new requirements for its low foam(or medium foam)and foam inhibition performance.If a large amount of foam is produced,it will lead to confusion such as difficult operation and control of production process,waste of raw materials,easy residue on the surface of objects,and difficult rinsing.Therefore,low foaming(or medium foaming)surfactants have broad application fields.In this thesis,three series of 12 new double-head tertiary amine surfactants containing sulfonic acid were synthesized using fatty amine,1,3-propane sultone,acrylamide,acrylic acid,2-acrylamide-2-methylpropane sulfonic acid(AMPS),sodium hydroxide(or potassium hydroxide)as raw materials.The aggregation behavior,foam performance,emulsifying performance in aqueous solution and thermal stability were studied.The main contributions were:(1)Synthesis and properties of double-head surfactants containing sodium sulfonate groups:Four novel double-head surfactants containing sodium sulfonate groups were synthesized by two-step reactions.Firstly,the intermediates of N,N-bis(propanesulfonic acid)alkylamines were obtained by the reaction of fatty amine(CnH2n+1NH2,n=12,14.16.18)with 1,3-propane sultone.Then,the products of N,N-bis(sodium propanesulfonate)alkylamines(BPS-m,m=1,2.3,4)were obtained by the reaction of the intermediates with sodium hydroxide.The yields of BPS-1,BPS-2,BPS-3 and BPS-4 were 68.6%,79.6%,69.3%and 87.3%.respectively.The structures of the BPS-m products were characterized by infrared spectroscopy(FTIR),hydrogen nuclear magnetic resonance spectroscopy(1H NMR).carbon nuclear magnetic resonance spectroscopy(13C NMR)and mass spectrometry(HRMS).The critical micelle concentration(CMC)of the target products BPS-m was determined by platinum ring method and electrical conductivity method.The CMC values of BPS-m were all at the level of 10-4-10-5 mol/L.By measuring the conductivity values of the target products BPS-m at different temperatures and concentrations,the effect of temperature on CMC value and β value of products BPS-m was small.According to the calculation of thermodynamic function.both ΔGmθ and ΔHmθ of products BPS-m were negative.TΔSmθ was greater than the absolute value of ΔHmθ.The formation of micelles in the products BPS-m aqueous solution was an entropy-dominated and spontaneous exothermic process.The curves of molar conductivity,apparent activation energy with concentration showed that the product BPS-m double-head surfactant containing sodium sulfonate would undergo pre-micellization in aqueous solution.The aggregation particle size of 10CMC in aqueous solution of BPS-m surfactants were basically in the range of 10-50 nm(vesicles)and 100-2000 nm(spongy like aggregates)measured by dynamic light scattering(DLS)technique.The isoelectric point of BPS-m series surfactants was in the range of pH=3.0 to pH=11.0.The emulsification ability experiment and foam experiment showed that the product BPS-m had strong emulsification ability,but not high foam inhibition ability.It belonged to medium-foaming surfactant.The influence of the length of hydrophobic carbon chain on the emulsification performance of the product BPS-m was investigated.The thermogravimetric analysis showed that the BPS-m series surfactants had good thermal stability and were easy to participate in the formation of char residue during heating.(2)Synthesis and properties of double-head surfactant containing amide and sulfonic acid groups:Four novel double-head surfactants containing amide and sulfonic acid groups were synthesized by two-step reactions.Firstly,the intermediates of N-propionamide long-chain alkyl secondary amines(PSAM-m,m=1,2,3,4)were obtained by the reaction of fatty amine with acrylamide.Then,the products of N,N-propionamide propyl sulfonic acid tertiary amines(PSA-m,m=1,2,3,4)were obtained by the reaction of the intermediates PSAM-m with 1,3-propane sultone.The yields of PSA-1,PSA-2,PSA-3 and PSA-4 were 46.4%,65.1%,67.1%and 73.0%,respectively.The structures of the PSA-m products were characterized by FTIR.1H NMR,13C NMR and HRMS.The CMC of the target products PSA-m was determined by platinum ring method and electrical conductivity method.The CMC values of PSA-m were all at the level of 10-4-10-5 mol/L.By measuring the conductivity values of the target products PSA-m at different temperatures and concentrations,the effect of temperature on CMC value and β value of products PSA-m was small.According to the calculation of thermodynamic function,bothΔGmθ and ΔHmθ of products PSA-m were negative.TΔSmθ was greater than the absolute value of ΔHmθ.The formation of micelles in the products PSA-m aqueous solution was an entropy-dominated and spontaneous exothermic process.The curves of molar conductivity.apparent activation energy with concentration showed that the product PSA-m double-head surfactant containing amide and sulfonic acid groups would undergo pre-micellization in aqueous solution.The aggregation particle size of 10CMC in aqueous solution of PSA-m surfactants were basically in the range of 5-20nm(micelles).40-600 nm(vesicles)and 700-3000 nm(spongy like aggregates)measured by DLS technique.The isoelectric point of PSA-m series surfactants was in the range of pH=3.0 to pH=11.0.The emulsification ability experiment and foam experiment showed that the product PSA-m had strong emulsification ability,but not high foam inhibition ability.It belonged to low-foaming surfactant.The influence of the length of hydrophobic carbon chain on the emulsification performance of the product PSA-m was investigated.The thermogravimetric analysis showed that the thermal stability of PSA-m series surfactants was slightly worse than that of BPS-m series surfactants,and it was difficult to participate in the formation of char residue during heating.(3)Synthesis and properties of double-head surfactant containing amido sulfonic acid and carboxylic acid groups:Four novel double-head surfactants containing amido sulfonic acid and carboxylic acid groups were synthesized by two-step reactions.Firstly,the intermediates of 2alkyliminopropylamide-2-methylpropane sulfonic acid(PAM-m,m=1,2,3,4)were obtained by the reaction of fatty amine with 2-acrylamide-2-methylpropane sulfonic acid(AMPS).Then,the products of N,N-propionyl-N’-(1,1-dimethylethylsulfonic acid)propionamidoalkyl tertiary amines(PA-m,m=1,2,3,4)were obtained by the reaction of the intermediates PAM-m with acrylic acid.The yields of PA-1,PA-2,PA-3 and PA-4 were 68.6%,61.0%,78.0%and 77.9%,respectively.The structures of the PA-m products were characterized by FTIR,1H NMR,13C NMR and HRMS.The CMC of the target products PA-m was determined by platinum ring method and electrical conductivity method.The CMC values of PA-m were all at the level of 10-4-10-5 mol/L.By measuring the conductivity values of the target products PA-m at different temperatures and concentrations,the effect of temperature on CMC value and β value of products PA-m was small.According to the calculation of thermodynamic function,bothΔGmθ and ΔHmθ of products PA-m were negative.TΔSmθ was greater than the absolute value of ΔHmθ.The formation of micelles in the products PA-m aqueous solution was an entropy-dominated and spontaneous exothermic process.The curves of molar conductivity and apparent activation energy with concentration showed that the product PA-m double-head surfactant containing amido sulfonic acid and carboxylic acid groups would undergo pre-m,icellization in aqueous solution.The aggregation particle size of 10CMC in aqueous solution of PA-m surfactants were basically in the range of 50-1000 nm(vesicles)measured by DLS technique.The isoelectric point of PA-m series surfactants was in the range of pH=3.0 to pH=11.9(or 13.3).The emulsification ability experiment and foam experiment showed that the product PA-m had strong emulsification ability and high foam inhibition ability.It belonged to low-foaming surfactant.The influence of the length of hydrophobic carbon chain on the emulsification performance of the product PA-m was investigated.The thermogravimetric analysis showed that the thermal stability of PA-m series surfactants was slightly worse than that of BPS-m series surfactants,and it was easy to participate in the formation of char residue during heating. |
