GPs和GBs双子表面活性剂的合成与性能表征
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摘要
双子表面活性剂是一种新型的表面活性剂,与其对应的普通表面活性剂相比,具有更高的表面活性(低的cmc、γ cmc和高的PC20值等)、与普通的表面活性剂复配能产生更大的协同效应,以及其他一些独特的性能如水溶助长性、流变性和生物安全性等。能够广泛用作抗静电剂、织物柔软剂、杀菌剂、防腐剂以及石油添加剂等,已引起学术界和工业界人士的广泛兴趣和关注,“最有可能成为21世纪的新型表面活性剂”。目前,国内外有一些关于双子表面活性剂的合成报道,但是对含氮杂环的双子季铵盐表面活性剂、双烷基苯磺酸盐的合成和性质研究还未见报道,本论文探索了一系列含氮杂环的双子季铵盐表面活性剂和双烷基苯磺酸合成方法,并对其表面活性、杀菌活性和防腐性能进行了表征,具体工作如下:
1.GPs双子季铵盐表面活性剂的合成及性能研究
(1)以吡啶和长链卤代烷为原料,通过以下两步反应:RBr与Li在无水操作的条件下,生成RLi;RLi与吡啶反应生成α-烷基吡啶,通过减压蒸馏,柱色谱分离提纯,得到一系列α-烷基吡啶。其结构已被IR、1HNMR、13CNMR所证实。
(2)以α-烷基吡啶和二溴卤代烷为原料,合成了一系列氮杂环双子季铵盐表面活性剂(结构式如下),利用定性实验、IR、1HNMR、13CNMR、LCMS和元素分析等现代仪器手段对其结构进行了表征。并且对影响这一系列氮杂环双子季铵盐表面活性剂的熔点、收率的因素进行了分析,得出以下的结论:在一定范围内,柔性联结基团越短,产品的熔点越高;对带有烷基链的产品,烷基链越长,产品熔点越高;二溴卤代烷的反应活性越高,反应产率越高;吡啶环上的位阻越小,反应产率越高;吡啶环上电子云密度越大,反应产率越高。GP1:n=0,m=4;GP2:n=0,m=6;GP3:n=8,m=4;GP4:n=8,m=6;GP5:n=10,m=4;GP6:n=10,m=6;GP7:n=12,m=4;GP8:n=12,m=6;GP9:n=14,m=4.
(3)利用吊环法对所合成的一系列氮杂环双子季铵盐表面活性剂的表面活性进行了测定,测试结果表明:所合成的氮杂环双子季铵盐表面活性剂(GP1和GP2除外)均有一定的降低水表面张力的能力,其中GP5、GP7、GP8和Gp9的表面活性较高;随着碳原子数的增加,cmc值有下降的趋势。与相应的普通表面活性剂(Ps)相比,GPs的cmc值比Ps要低几倍,降低水表面张力的能力也比相应的单体要强,其PC_(20)比相应的单体要低一个数量级。与十二烷基苯磺酸的协同效果好,复配比例为3:7时协同效应达到最佳,此时其cmc低达0.01μmmol/L;
(4)以合成的氮杂环双子季铵盐表面活性剂和对应的单季铵盐表面活性剂为杀菌剂,以金黄色葡萄球菌(ATCC 6538)、大肠杆菌(8099)、枯草杆菌黑色变种芽胞(ATCC 9732)、
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 A3
steel 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 for
SDBS 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.
1.GPs双子季铵盐表面活性剂的合成及性能研究
(1)以吡啶和长链卤代烷为原料,通过以下两步反应:RBr与Li在无水操作的条件下,生成RLi;RLi与吡啶反应生成α-烷基吡啶,通过减压蒸馏,柱色谱分离提纯,得到一系列α-烷基吡啶。其结构已被IR、1HNMR、13CNMR所证实。
(2)以α-烷基吡啶和二溴卤代烷为原料,合成了一系列氮杂环双子季铵盐表面活性剂(结构式如下),利用定性实验、IR、1HNMR、13CNMR、LCMS和元素分析等现代仪器手段对其结构进行了表征。并且对影响这一系列氮杂环双子季铵盐表面活性剂的熔点、收率的因素进行了分析,得出以下的结论:在一定范围内,柔性联结基团越短,产品的熔点越高;对带有烷基链的产品,烷基链越长,产品熔点越高;二溴卤代烷的反应活性越高,反应产率越高;吡啶环上的位阻越小,反应产率越高;吡啶环上电子云密度越大,反应产率越高。GP1:n=0,m=4;GP2:n=0,m=6;GP3:n=8,m=4;GP4:n=8,m=6;GP5:n=10,m=4;GP6:n=10,m=6;GP7:n=12,m=4;GP8:n=12,m=6;GP9:n=14,m=4.
(3)利用吊环法对所合成的一系列氮杂环双子季铵盐表面活性剂的表面活性进行了测定,测试结果表明:所合成的氮杂环双子季铵盐表面活性剂(GP1和GP2除外)均有一定的降低水表面张力的能力,其中GP5、GP7、GP8和Gp9的表面活性较高;随着碳原子数的增加,cmc值有下降的趋势。与相应的普通表面活性剂(Ps)相比,GPs的cmc值比Ps要低几倍,降低水表面张力的能力也比相应的单体要强,其PC_(20)比相应的单体要低一个数量级。与十二烷基苯磺酸的协同效果好,复配比例为3:7时协同效应达到最佳,此时其cmc低达0.01μmmol/L;
(4)以合成的氮杂环双子季铵盐表面活性剂和对应的单季铵盐表面活性剂为杀菌剂,以金黄色葡萄球菌(ATCC 6538)、大肠杆菌(8099)、枯草杆菌黑色变种芽胞(ATCC 9732)、
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 A3
steel 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 for
SDBS 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.
引文
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