双羟基Gemini表面活性剂的溶液性能及其聚集形态
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摘要
以1-溴十二烷、2-甲氨基乙醇、1,3-二溴丙烷、1,4-二溴丁烷、1,6-二溴己烷、1,8-二溴辛烷、1,10-二溴癸烷和1,12-二溴十二烷为原料,制得含有双羟基的Gemini表面活性剂〔缩写为12(OH)-s-12(OH),其中s=3、4、6、8、10和12〕。并测定了双羟基Gemini表面活性剂的热稳定性及其在水溶液中的表面张力及泡沫性能;采用耗散粒子动力学(DPD)方法预测了Gemini表面活性剂在水溶液中的聚集形态。结果表明,该类型Gemini表面活性剂具有较好的热稳定性和泡沫性能,随着连接基团长度的增加(s≤6),其在水溶液中的临界胶束浓度(CMC)从0.62mmol/L(s=3)降至0.21mmol/L(s=6)左右,且当连接基团长度s>6后CMC基本不变。随着Gemini表面活性剂摩尔分数的增加,胶束形态从球状胶束→棒状胶束→层状胶束→反胶束网络结构逐渐转变,且连接基团长度的改变几乎不影响其在水溶液中的胶束形态转变。
Gemini surfactants containing dihydroxy 〔abbreviated as 12(OH)-s-12(OH), s=3, 4, 6, 8, 10 and12〕 were synthesized using 1-bromododecane, 2-methylaminoethanol, 1,3-dibromopropane, 1,4-dibromobutane,1,6-dibromohexane, 1,8-dibromooctane, 1,10-dibromodecane and 1,12-dibromododecane as raw materials.The thermal property of Gemini surfactants and their surface tensions in aqueous solution were characterized. Their foam properties were tested. The aggregation morphology of Gemini surfactants in aqueous solution was predicted by using dissipative particle dynamics(DPD). The results indicated that these Gemini surfactants had good thermal property and foaming property. With the increase of spacer length(s≤6), the critical micelle concentration(CMC) of Gemini surfactants in aqueous solution were decreased from 0.62 mmol/L(s=3) to about 0.21 mmol/L(s=6). The CMC almost kept unchanged when the spacer length further increased(s>6). When the molar fraction of Gemini surfactant increased, the micellar morphology gradually changed from spherical micelle to rod micelle to layered micelle eventually to reverse micelle network structure. Moreover, the change of spacer group length of the Gemini surfactants hardly affected the change of its micellar morphology in aqueous solution.
Gemini surfactants containing dihydroxy 〔abbreviated as 12(OH)-s-12(OH), s=3, 4, 6, 8, 10 and12〕 were synthesized using 1-bromododecane, 2-methylaminoethanol, 1,3-dibromopropane, 1,4-dibromobutane,1,6-dibromohexane, 1,8-dibromooctane, 1,10-dibromodecane and 1,12-dibromododecane as raw materials.The thermal property of Gemini surfactants and their surface tensions in aqueous solution were characterized. Their foam properties were tested. The aggregation morphology of Gemini surfactants in aqueous solution was predicted by using dissipative particle dynamics(DPD). The results indicated that these Gemini surfactants had good thermal property and foaming property. With the increase of spacer length(s≤6), the critical micelle concentration(CMC) of Gemini surfactants in aqueous solution were decreased from 0.62 mmol/L(s=3) to about 0.21 mmol/L(s=6). The CMC almost kept unchanged when the spacer length further increased(s>6). When the molar fraction of Gemini surfactant increased, the micellar morphology gradually changed from spherical micelle to rod micelle to layered micelle eventually to reverse micelle network structure. Moreover, the change of spacer group length of the Gemini surfactants hardly affected the change of its micellar morphology in aqueous solution.
引文
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[23]Zhen L L,Liu K H,Huang D,et al.Structure-property relationship of sulfosuccinic acid diester sodium salt micelles:3D-QSAR model and DPD simulation[J].Journal of Dispersion Science and Technology,2016,37(7):941-948.
[24]Groot R D,Warren P B.Dissipative particle dynamics:Bridging the gap between atomistic and mesoscopic simulation[J].Journal of Chemical Physics,1997,107(11):4423-4435.
[25]Toma?i?V,Bili?kov N,Mihelj T,et al.Thermal behaviour and structural properties of surfactant-Picrate compounds:The effect of the ammonium headgroup number[J].Thermochimica Acta,2013,569:25-35.
[26]Alami E,Beinert G,Marie P,et al.Alkanediyl-α,ω-bis(dimethylalkylammonium bromide)surfactants.3.behavior at the air-water interface[J].Langmuir,1993,9(6):1465-1467.
[27]Sun Zhigang(孙志刚),Niu Ruixia(牛瑞霞),Dong Pengxu(董彭旭),et al.Aggregation behavior of aqueous solutions of long-chain imidazolium ionic liquids surfactant[J].Applied Chemical Industry(应用化工),2018,47(12):2620-2623.
[28]Zhu Sen(朱森).Capacity and computer simulation of gemini surfactants[D].Tianjing:Tianjing University(天津大学),2006.
[2]Sugahara T,Takamatsu Y,Bhadani A,et al.Characterization of the micelle structure of oleic acid-based gemini surfactants:Effect of stereochemistry[J].Physical Chemistry Chemical Physics,2018,20(13):8874-8880.
[3]Wang Yakui(王亚魁),Jiang Yajie(姜亚洁),Geng Tao(耿涛),et al.Synthesis and application properties of a Gemini cationic surfactant with diamide groups[J].Fine Chemicals(精细化工),2019,36(1):44-50.
[4]Jeong K J,Yethiraj A.The driving force for the association of gemini surfactants[J].Journal of Physical Chemistry B,2018,122(13):3259-3265.
[5]Deng S L,Zhao J X.Self-assembly of cationic gemini surfactants,alkanediyl-bis-(dimethyldodecyl-ammonium bromide),in cyclohexane:Effects of spacer length on their association into reverse lyotropic liquid crystalline or reverse vesicles[J].Soft Matter,2018,14:734-741.
[6]Feng L,Xie D H,Song B L,et al.Aggregate evolution in aqueous solutions of a Gemini surfactant derived from dehydroabietic acid[J].Soft Matter,2018,14:1210-1218.
[7]Wang X Y,Wang J,Wang Y L,et al.Effect of the nature of the spacer on the aggregation properties of Gemini surfactants in an aqueous solution[J].Langmuir,2004,20(1):53-56.
[8]Menger F M,Littau C A.Gemini surfactants:a new class of self-assembling molecules[J].Journal of the American Chemical Society,1993,115(22):10083-10090.
[9]Zhang Z G,Zheng P Z,Guo Y M,et al.The effect of the spacer rigidity on the aggregation behavior of two ester-containing gemini surfactants[J].Journal of Colloid and Interface Science,2012,379(1):64-71.
[10]Alami E,Levy H,Zana R,et al.Alkanediyl-alpha,omega-bis(dimethylalkylammonium bromide)surfactants.2.Structure of the lyotropic mesophases in the presence of water[J].Langmuir,1993,9(4):940-944.
[11]Wettig S D,Nowak P,Verrall R E.Thermodynamic and aggregation properties of gemini surfactants with hydroxyl substituted spacers in aqueous solution[J].Langmuir,2002,18(14):5354-5359.
[12]Pei X M,Zhao J X,Ye Y Z,et al.Wormlike micelles and gels reinforced by hydrogen bonding in aqueous cationic gemini surfactant systems[J].Soft Matter,2011,7:2953-2960.
[13]Pei X M,You Y,Zhao J X,et al.Adsorption and aggregation of2-hydroxyl-propanediyl-α,ω-bis(dimethyldodecyl ammonium bromide)in aqueous solution:Effect of intermolecular hydrogenbonding[J].Journal of Colloid and Interface Science,2010,351(2):457-465.
[14]Pei X M,Zhao J X,Wei X L.Wormlike micelles formed by mixed cationic and anionic gemini surfactants in aqueous solution[J].Journal of Colloid and Interface Science,2011,356(1):176-181.
[15]Pei X M,Zhao J X,You Y,et al.Wormlike micelle formation and rheological behavior in the aqueous solutions of mixed sulfate gemini surfactant without spacer group and dodecyltrimethylammonium bromide[J].Chinese Journal of Chemistry,2011,29(10):2003-2006.
[16]Pei Xiaomei(裴晓梅),Zhao Jianxi(赵剑曦),Wei Xilian(魏西莲).Effect of sodium salicylate on the formation and properties of wormlike micelles in aqueous cationic gemini surfactant solutions[J].Acta Phys-Chim Sin(物理化学学报),2011,27(4):913-917.
[17]Song Binglei(宋冰蕾),Chen Tao(陈涛),Tian Jinnian(田金年),et al.Lyotropic liquid crystalline phases formed by gemini surfactants in an ionic liquid[J].Chemical Industry and Engineering Progress(化工进展),2015,34(12):4348-4355.
[18]Sheng Y J,Yao J Y,Chen Q B,et al.Effect of 1D twisted water chains confined in channels formed by a gemini amphiphile on its crystal stability[J].Cryst Eng Comm,2015,17(6):1439-1447.
[19]Pei X M,Zhang Q,Liu Z,et al.Surface dilatational properties of Gemini surfactants containing multiple hydroxyl groups[J].Colloid and Polymer Science,2016,294(9):1405-1412.
[20]Pei Xiaomei(裴晓梅),Song Binglei(宋冰蕾),Xu Zonghui(许宗会),et al.Synthesis and surface activities of a novel quaternary ammonium gemini surfactant with multiple hydroxyl groups[J].Chinese Journal of Synthetic Chemistry(合成化学),2013,21(6):695-697.
[21]Lei L,Feng L,Song B L,et al.Ionic liquid crystals with novel thermal properties formed by the gemini surfactants containing four hydroxyl groups[J].RSC Advances,2016,6(101):99361-99366.
[22]Li Rong(李蓉),Sun Zheng(孙正),Zhang Ziying(张子颖),et al.Synthesis and surface properties of quaternary gemini surfactants with multiple hydroxyl groups[J].Chinese Journal of Synthetic Chemistry(合成化学),2015,23(8):707-710.
[23]Zhen L L,Liu K H,Huang D,et al.Structure-property relationship of sulfosuccinic acid diester sodium salt micelles:3D-QSAR model and DPD simulation[J].Journal of Dispersion Science and Technology,2016,37(7):941-948.
[24]Groot R D,Warren P B.Dissipative particle dynamics:Bridging the gap between atomistic and mesoscopic simulation[J].Journal of Chemical Physics,1997,107(11):4423-4435.
[25]Toma?i?V,Bili?kov N,Mihelj T,et al.Thermal behaviour and structural properties of surfactant-Picrate compounds:The effect of the ammonium headgroup number[J].Thermochimica Acta,2013,569:25-35.
[26]Alami E,Beinert G,Marie P,et al.Alkanediyl-α,ω-bis(dimethylalkylammonium bromide)surfactants.3.behavior at the air-water interface[J].Langmuir,1993,9(6):1465-1467.
[27]Sun Zhigang(孙志刚),Niu Ruixia(牛瑞霞),Dong Pengxu(董彭旭),et al.Aggregation behavior of aqueous solutions of long-chain imidazolium ionic liquids surfactant[J].Applied Chemical Industry(应用化工),2018,47(12):2620-2623.
[28]Zhu Sen(朱森).Capacity and computer simulation of gemini surfactants[D].Tianjing:Tianjing University(天津大学),2006.
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