Synthesis And Characterization Of Gps And Gbs Twin Surface Active Agent

Gemini surfactants are newfashioned surfactants. Comparing to corresponding mono quaternary ammonium salts, they have higher surface activity(such as lower cmc,γcmc, and higher Pc2o).They have larger synergic effect when mixed with conventional surfactant. At the same time, they have other unique properties such as solubilization, rheological property, biology safety and so on. They can be widely used as antistatic agent, softening texitile agent, antibacterial agent, antiseptic and petroleum additive and so on. Researchers in academic and industrial circles have taken comprehensive interest and paid much attention to them. It is certain that gemini surfactants will become newfashioned surfactants in the 21th century. At present, there are many works reported about synthesis of bisquat surfactants at home and abroad, but few reports about synthesis and properties of bisquat surfactants with nitrogen heterocyclic ring and bis(sodium alkylbenzene sulfonate). So Bisquat surfactants with nitrogen heterocyclic ring and bis(sodium alkylbenzene sulfonate) have been synthesized and their properties such as surface activities,antimicrobial and inhibitive effects have been studied in this paper. The main work are listed below.1. The synthesis of quaternary ammonium salt (GPs) and evaluation of their properties.(1) A series of a-alkyl pyridines were prepared from pyridine and alkylogen through two steps. The first step was the preparation of alkyl-lithium from alkylogen and lithium. The second step was the preparation of a-alkyl pyridine from alkyl-lithium and pyridine. The structures of these compounds were identified by IR. ~1HNMR and ~13CNMR.(2) A series of bisquat surfactants with nitrogen heterocyclic ring (Fig.1) were prepared from a-alkyl pyridine and dibromide. The structures of these compounds were identified by qualitative experiments, IR, ~1HNMR, ~13CNMR. These factors that influenced the melting point of products of the bisquat surfactants were analysed. The results showed that the compounds posses higher melting points which have shorter spacers and longer alkyl chains in this structrue. It is also showed that the higher electron cloud density on the pyridine and the higher activity of dibromide, the higher production.(3) The surface activities of bisquat surfactants with nitrogen heterocyclic ring were determined by means of hanging ring. The results showed that these surfactants (except for Gpl and Gp2) have the ability in decreasing the surface tension of water to some extent. Gp5, GP6, Gp7, Gp8 and Gp9 had better surface activities in these surfactants. CMC values decrease with the carbon numbers increasing, and GP1 and GP2 are too soluble to offer meaningful CMC measurement. Compared with Ps, the corresponding monomers, the cmc of GPs is several times lower, the capability in reducing surface tension is higher and PC20 is ten times below. The synergic effect is better when mixed with sodium dodecylbenzyl sulfonate, the optimum is at the ratio 3:7 of the gemini to sodium dodecylbenzyl sulfonate, the cmc of the mixtures is as low as O.Olumol/L. And furthermore the spacer affects more the synergic effect than the length of side chain.(4) Bisquat surfactants and corresponding mono quaternary ammonium salts, were used as antibacterial agents. Staphylococcus aureus(ATCC 10231), escherichia coli(8099), bacillus subtilis(ATCC 9732), Candida albican(ATCC 10231) were used as indication bacteria to evaluate their antimicrobial activity. The results showed that these bisquat surfactants with nitrogen heterocyclic ring synthesized except Gpl and Gp2 had good and broad-spectrum bactericidal activities. With the increase of carbon numbers in a-chains, cmc get down and the antimicrobial activities get inproved. The geminis possess 5-10times as high bactericidal activities as that of the monomers. GP5, GP6, GP7 and GP8 are more active than 1227 in bactericide. We manipulate the results with mathematic ways and get the relations and curves between bactericidal efficiency and concentrations and we can calculate the bactericidal efficiency at a given concentration.(5) The inhibiting property of GPs on A3 steel in the HCl-NaCl-tfeO solution had been studied by means of mass loss. The results showed that GPs exhibit good inhibiting behavior towards A3steel at a temperature as high as 90 °C and a strong acid solution. The inhibiting efficiency of GPs for the A3 steel was up to over 90% at the concentration about 200mg/L. The reason for goodinhibiting effect of GPs may lie in the special structure___multi-absorbent centers, the nelectron of pyridine ring can be firmly absorbed onto the surface of metal and accordingly form an adsorption film. At the same time, two long hydrocarbon tails of GPs compactly arranged, and these hydrocarbon tails form physical adsorption film on the surface and accordingly inhibit effectively metals from corrosion. The inhibitive mechanism was roughly discussed by electrochemical polarization, the AE is quite near zero, so GPs is a kind of anticorrosive for both electrodes and mainly for cathodic inhibition.2. The syntheses of bis(sodium alkylbenzene sulfonate) and the determination of its surface activities.(1) A series of long chain acyl chloride were prepared by the fatty acid, sulfur oxychloride, and cyclohexane as solvent and finally through decompress distillation.(2) A series of bis-alkyl diphenones were prepared by anhydrous diphyl and acyl chloride, cycJohexane as solvent and aluminum chloride as catalyst; washed with solvent and recrystallized with chloroform.(3) A series of bis-alkyl diphyl were made by bis-alkyl diphenones, hydrazine hydrate, diglycol and hydroxide kalium, purified by recrystallizing and column chromatography.(4) Bis-(decyl benzene sulfonate) were synthesized with double decyl diphyl as material and chlorosulfuric acid as sulfonating agent. The structure is confirmed by IR, 'HNMR, and 13CNMR as follow:HO3S?O3HFig. 2 The structure of GB10(5) Turn the bis-(decyl benzene sulfonate) into corresponding salts and analyzing its cmc andY cmc- The results showed that GB10 exhibits better surface activity and efficiency in reducingsurface tension of water than common surfactant — sodium dodecylbenzyl sulfonate: PC2o is0.0016mmol/L, cmc 0.17mmol/L and Ycmc 31.2mN/m (cmc is 1.57mmol/L and ycmc 37mN/m forSDBS X When added some salt in the solution of GBIO, the cmc of the solution decreased, however magnitude of the decrease depends on the type and the concentration of the salts. It seams that NH4CI is the best among NaCl, KCl, NH4CI and CaCl2.