一种新型阳离子三硅氧烷表面活性剂的合成及其表面性能
|
摘要
以1,2-环氧-9癸烯(ED)和1,1,1,3,5,5,5-七甲基三硅氧烷(MDHM)为原料,在氯铂酸催化下,经硅氢加成反应先制得烷基环氧基三硅氧烷(AETS),再将AETS与二乙醇胺(DEA)进行开环反应合成了一种新型阳离子三硅氧烷表面活性剂(CTSS)。通过IR和1H NMR对CTSS的结构进行了表征,测定了CTSS的表面张力、润湿性和对pH值的稳定性。同时对AETS及CTSS的合成条件进行了优化,优化后的工艺条件为:合成AETS的最佳条件为n(ED)∶n(MDHM)(n为物质的量)为1.1∶1,催化剂用量为n(MDHM)的0.075%,反应时间为5 h,反应温度为80℃;合成CTSS的最佳条件为n(AETS)∶n(DEA)=1∶1.05,反应时间3 h,反应温度80℃。性能测试结果表明,CTSS在临界胶束浓度(CMC)为1.3×10-3mol/L时,可以将水的表面张力降低至20.0 mN/m,同时具有良好的润湿性,另外,CTSS在pH值为6.5~8.0时稳定存在。
Me3SiOSiMeROSiMe3( R = CH2( CH2)7CHOCH2)( AETS) has been synthesized through a hydrosilation of 1,2-eposy-9-decene( ED) with 1,1,1,3,5,5,5-heptamethyltrisiloxane( MDHM) in the presence of hexachloroplatinic( Ⅳ) acid as the catalyst. Then a novel cationic trisiloxane surfactant with the formula Me3SiOSiMeR2OSiMe3( R2= CH2( CH2)7CHOHCH2N( CH2CH2OH)2)( CTSS) has been prepared through the ring-opening reaction of diethanolamine( DEA) with AETS. The structure of CTSS was characterized by IR and1 H NMR. The surface intension,wettability and stability in different pH of CTSS were investigated. The effect of reaction conditions on the synthesis of AETS and CTSS were investigated respectively.The optimized reaction conditions for the preparation of AETS are that the molar ratio of ED and MDHM is1. 1∶1,the catalyst loading is 0. 075% of the n( MDHM),the reaction time is 5 hours and the reaction temperature is 80 ℃. While the optimized reaction conditions to obtain CTSS are that the ratio of n( AETS) to n( DEA) is 1∶ 1. 05,the reaction time is 3 h and the reaction temperature is 80 ℃. CTSS can reduced the surface tension of distilled water to 20. 0 mN /m at the critical micelle concentration( CMC) of 1. 3 ×10- 3mol /L.In addition,CTSS also has better wettability and maintains stable in pH 6. 5 ~ 8. 0.
Me3SiOSiMeROSiMe3( R = CH2( CH2)7CHOCH2)( AETS) has been synthesized through a hydrosilation of 1,2-eposy-9-decene( ED) with 1,1,1,3,5,5,5-heptamethyltrisiloxane( MDHM) in the presence of hexachloroplatinic( Ⅳ) acid as the catalyst. Then a novel cationic trisiloxane surfactant with the formula Me3SiOSiMeR2OSiMe3( R2= CH2( CH2)7CHOHCH2N( CH2CH2OH)2)( CTSS) has been prepared through the ring-opening reaction of diethanolamine( DEA) with AETS. The structure of CTSS was characterized by IR and1 H NMR. The surface intension,wettability and stability in different pH of CTSS were investigated. The effect of reaction conditions on the synthesis of AETS and CTSS were investigated respectively.The optimized reaction conditions for the preparation of AETS are that the molar ratio of ED and MDHM is1. 1∶1,the catalyst loading is 0. 075% of the n( MDHM),the reaction time is 5 hours and the reaction temperature is 80 ℃. While the optimized reaction conditions to obtain CTSS are that the ratio of n( AETS) to n( DEA) is 1∶ 1. 05,the reaction time is 3 h and the reaction temperature is 80 ℃. CTSS can reduced the surface tension of distilled water to 20. 0 mN /m at the critical micelle concentration( CMC) of 1. 3 ×10- 3mol /L.In addition,CTSS also has better wettability and maintains stable in pH 6. 5 ~ 8. 0.
引文
[1]HUANG Liangxian,DING Yang,HUANG Jie,et al.Synthesis of Anionic Trisiloxane Surfactant and Its Properties[J].Chinese J Appl Chem,2011,28(6):722-726(in Chinese).黄良仙,丁洋,黄洁,等.阴离子型三硅氧烷表面活性剂的合成及其性能[J].应用化学,2011,28(6):722-726.
[2]YIN Danna,ZHENG Cheng,ZHANG Liping,et al.Synthesis and Characterization of Polyether Modified Trisiloxanes[J].CIESC J,2010,61(6):1565-1570(in Chinese).尹丹娜,郑成,张丽萍,等.聚醚改性三硅氧烷表面活性剂的合成与表征[J].化工学报,2010,61(6):1565-1670.
[3]LUO Ruxian,HE Shanshan.Synthesis of Quaternary Ammonium Organic Silicon Gemini Surfactant and Interfacial Properties[J].Fine Chem,2013,30(3):268-272(in Chinese).罗儒显,何姗姗.季铵盐型有机硅双子表面活性剂的合成与界面性能[J].精细化工,2013,30(3):268-272.
[4]Knoche M,Tamura H,Bukovac M J.Stability of the Organosilicone Surfactant Silwet L-77 in Growth Regulator Sprays[J].Hortscience,1991,26(1):1498-1500.
[5]ZHANG Yue,ZHANG Gaoyong,HAN Fu.Spreading Mechanism of New Glucosamide-based Trisiloxane Surfactant on LowEnergy Surface[J].Acta Chim Sin,2007,65(5):465-469(in Chinese).张越,张高勇,韩富.新型三硅氧烷表面活性剂在低能表面的铺展机理[J].化学学报,2007,65(5):465-469.
[6]WU Jianfen,SHAO Junlin,ZHAO Ke,et al.Synthesis of Polyether Modified Trisiloxane[J].Silicone Mater,2012,26(5):316-319(in Chinese).吴建芬,邵均林,赵柯,等.聚醚改性三硅氧烷表面活性剂的合成工艺研究[J].有机硅材料,2012,26(5):316-319.
[7]Wu Y F,Rosen M J.Surperspreading of Trisiloxane Surfactants Mixtures on Hydrophobic Surfaces 2.Interaction and Spreading of Aqueous Trisiloxane Surfactant-N-Alkyl-Pyrrolidinone Mixtures in Contact with Polyethylene[J].Langmuir,2002,18:2205-2215.
[8]Zhang Y,Zhang G Y,Han F.The Spreading and Superspreading Behavior of New Glucosamide-based Trisiloxane Surfactants on Hydrophobic Foliage[J].Colloids Surf A,2006,276:100-106.
[9]Radulovic J,Sefiane K,Shanahan M E R.Ageing of Trisiloxane Solutions[J].Chem Eng Sci,2010,65:5251-5255.
[10]Radulovic J,Sefiane K,Shanahan M E R.Spreading and Wetting Behaviour of Trisiloxanes[J].J Bionic Eng,2009,6:341-349.
[11]Policello G A.Terminally Modified,Amino,Polyether Siloxanes:US,6235681B1[P],2011-5-22.
[12]Leatherman M D,Policello G A,Peng W N,et al.Hydrolysis Resistant Organomodified Trisiloxane Ionic Surfactants:US,20090176893A1[P],2009.7.
[13]HUANG Liangxian,AN Qiufeng,LI Xianqi,et al.Synthesis and Interfacial Properties of Cationic Trisiloxane Surfactant[J].Fine Chem,2010,27(7):642-645(in Chinese).黄良仙,安秋凤,李献起,等.阳离子型三硅氧烷表面活性剂的合成及其界面性能[J].精细化工,2010,27(7):642-645.
[14]YIN Yan.Synthesis of a Self-emulsification Defoaming Agent-siloxane Oxyalkylene Copolymers[D].Zhejiang:Zhejiang University,2006(in Chinese).银燕.自乳化型聚醚改性聚硅氧烷消泡剂的研制[D].浙江:浙江大学,2006.
[15]YANG Yan.Synthesis of Epoxy Polysiloxane and Its Application in Flameretar PBT[D].Guangzhou:South China University Technol,2012(in Chinese).杨燕.环氧基聚硅氧烷的制备及其在阻燃PBT中的应用[D].广州:华南理工大学,2012.
[16]CUI Mengzhong.The Properties,Manufacture and Applications of Silicone Surfactants[J].App Sci Tech,2008,16(17):11-18(in Chinese).崔孟忠.有机硅表面活性剂及其应用[J].应用科技,2008,17(16):11-18.
[2]YIN Danna,ZHENG Cheng,ZHANG Liping,et al.Synthesis and Characterization of Polyether Modified Trisiloxanes[J].CIESC J,2010,61(6):1565-1570(in Chinese).尹丹娜,郑成,张丽萍,等.聚醚改性三硅氧烷表面活性剂的合成与表征[J].化工学报,2010,61(6):1565-1670.
[3]LUO Ruxian,HE Shanshan.Synthesis of Quaternary Ammonium Organic Silicon Gemini Surfactant and Interfacial Properties[J].Fine Chem,2013,30(3):268-272(in Chinese).罗儒显,何姗姗.季铵盐型有机硅双子表面活性剂的合成与界面性能[J].精细化工,2013,30(3):268-272.
[4]Knoche M,Tamura H,Bukovac M J.Stability of the Organosilicone Surfactant Silwet L-77 in Growth Regulator Sprays[J].Hortscience,1991,26(1):1498-1500.
[5]ZHANG Yue,ZHANG Gaoyong,HAN Fu.Spreading Mechanism of New Glucosamide-based Trisiloxane Surfactant on LowEnergy Surface[J].Acta Chim Sin,2007,65(5):465-469(in Chinese).张越,张高勇,韩富.新型三硅氧烷表面活性剂在低能表面的铺展机理[J].化学学报,2007,65(5):465-469.
[6]WU Jianfen,SHAO Junlin,ZHAO Ke,et al.Synthesis of Polyether Modified Trisiloxane[J].Silicone Mater,2012,26(5):316-319(in Chinese).吴建芬,邵均林,赵柯,等.聚醚改性三硅氧烷表面活性剂的合成工艺研究[J].有机硅材料,2012,26(5):316-319.
[7]Wu Y F,Rosen M J.Surperspreading of Trisiloxane Surfactants Mixtures on Hydrophobic Surfaces 2.Interaction and Spreading of Aqueous Trisiloxane Surfactant-N-Alkyl-Pyrrolidinone Mixtures in Contact with Polyethylene[J].Langmuir,2002,18:2205-2215.
[8]Zhang Y,Zhang G Y,Han F.The Spreading and Superspreading Behavior of New Glucosamide-based Trisiloxane Surfactants on Hydrophobic Foliage[J].Colloids Surf A,2006,276:100-106.
[9]Radulovic J,Sefiane K,Shanahan M E R.Ageing of Trisiloxane Solutions[J].Chem Eng Sci,2010,65:5251-5255.
[10]Radulovic J,Sefiane K,Shanahan M E R.Spreading and Wetting Behaviour of Trisiloxanes[J].J Bionic Eng,2009,6:341-349.
[11]Policello G A.Terminally Modified,Amino,Polyether Siloxanes:US,6235681B1[P],2011-5-22.
[12]Leatherman M D,Policello G A,Peng W N,et al.Hydrolysis Resistant Organomodified Trisiloxane Ionic Surfactants:US,20090176893A1[P],2009.7.
[13]HUANG Liangxian,AN Qiufeng,LI Xianqi,et al.Synthesis and Interfacial Properties of Cationic Trisiloxane Surfactant[J].Fine Chem,2010,27(7):642-645(in Chinese).黄良仙,安秋凤,李献起,等.阳离子型三硅氧烷表面活性剂的合成及其界面性能[J].精细化工,2010,27(7):642-645.
[14]YIN Yan.Synthesis of a Self-emulsification Defoaming Agent-siloxane Oxyalkylene Copolymers[D].Zhejiang:Zhejiang University,2006(in Chinese).银燕.自乳化型聚醚改性聚硅氧烷消泡剂的研制[D].浙江:浙江大学,2006.
[15]YANG Yan.Synthesis of Epoxy Polysiloxane and Its Application in Flameretar PBT[D].Guangzhou:South China University Technol,2012(in Chinese).杨燕.环氧基聚硅氧烷的制备及其在阻燃PBT中的应用[D].广州:华南理工大学,2012.
[16]CUI Mengzhong.The Properties,Manufacture and Applications of Silicone Surfactants[J].App Sci Tech,2008,16(17):11-18(in Chinese).崔孟忠.有机硅表面活性剂及其应用[J].应用科技,2008,17(16):11-18.