以甲基丙烯酰氧丙基三甲氧基硅烷(MAPTMS)为前驱体,利用荧光光谱、在线衰减全反射红外光谱(In-situ ATR-FT-IR),比较性地研究了在本体及气液界面条件下MAPTMS在酸性介质中的水解-缩合过程.借助于LB膜技术,测定了MAPTMS在气液界面水解-缩合反应过程中的e-A曲线.不论在本体相还是气液界面相,荧光探针芘均表现出明显的芘分子完全重叠及部分重叠的激基缔合物的荧光发射特征.结果表明:MAPTMS水解产物在水相中发生簇集,而且簇集体疏水端相互作用存在一定刚性.芘的荧光光谱随反应进行表现出显著变化,但本体相荧光光谱变化较气液界面相剧烈.ATR-FT-IR光谱在线检测表明:本体水解缩合产物具有较高的聚合度,而气液界面水解缩合产物聚合度较低.上述结果说明体系中存在簇集行为的显著变化,且在气液界面MAPTMS水解产物受限程度比本体相大.分子在气液界面上的聚集行为也由e-A曲线的结果得到进一步证实.文中依据MAPTMS水解产物具有类似表面活性剂的特性对上述实验结果给予了解释.
参考文献
| [1] | Gerhard Schottner .Hybrid Sol-Gel-Derived Polymers: Applications of Multifunctional Materials[J].Chemistry of Materials,2001(10):3422-3435. |
| [2] | Jianye Wen;Garth L. Wilkes .Organic/Inorganic Hybrid Network Materials by the Sol-Gel Approach[J].Chemistry of Materials,1996(8):1667-1681. |
| [3] | Hench L L;West J K .The sol-Gel process[J].Chemical Reviews,1990,90:33-72. |
| [4] | Ryoji Takahashi;Kazuki Nakanishi;Naohiro Soga .Aggregation Behavior of Alkoxide-Derived Silica in Sol-Gel Process in Presence of Poly(ethylene oxide)[J].Journal of Sol-Gel Science and Technology,2000(1):7-18. |
| [5] | Libor Matejka;Oxana Dukh;Drahomira Hlavata;Bohumil Meissner;Jiri Brus .Cyclization and Self-Organization in Polymerization of Trialkoxysilanes[J].Macromolecules,2001(20):6904-6914. |
| [6] | Parikh A N;Allara D L;Azouz I B et al.An intrinsic relationship between molecular structure in self-assembled nalkylsiloxane monolayers and deposition temperature[J].Journal of Physical Chemistry,1994,98(31):7577-7590. |
| [7] | ParikhAN;Schivley M A;Koo E et al.n-Alkylsiloxanes:from single monolayers to layered crystals,the formation of crystalline polymers from the hydrolysis of n-octadecyltrichlorosilane[J].Journal of the American Chemical Society,1997,119:3135. |
| [8] | Vidon S;Leblanc R M .Langrnuir study of octadecyltrimethoxysilane behavior at the air-water interface[J].Journal of Physical Chemistry B,1998,102:1279-1286. |
| [9] | Britt D W;Fllady V .Protonation,hydrolysis,and condensation of mono-and triftmctional silanes at the air/water interface[J].Langmuir,1999,15:1770-1776. |
| [10] | Piana K;Schubert U .Catalyst influence on the molar mass distribution of hydrolyzed(3-glycidoxypropyl)trimethoxysileand (3-methacryloxypropyl) trimethoxysilane[J].Chemistry of Materials,1994,6(09):1504-1508. |
| [11] | Hu D D;Croutxe-Barghom C;Feuillade M et al.Fluorescence study of the Sol-Gel process in hybrid precursors:evidence of concentration fluctuations at the local scale[J].Journal of Physical Chemistry B,2005,109:15214-15220. |
| [12] | Shu K. Shen;Dao D. Hu .Fluorescent Probe as Reporter on the Local Structure and Dynamics in Hydrolysis-Condensation Process of Organotrialkoxysilanes[J].The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical,2007(28):7963-7971. |
| [13] | Baker GA;Pandey S;Maziarz E P et al.Toward tailored xerogel composites:local dipolarity and nanosecond dynamics within binary composites derived from tetraethylorthosilane and ORMOSILs,oligorners or surfactants[J].Journal of Sol-Gel Science and Technology,1999,15:37-48. |
| [14] | Stephen R. Carino;Randolpy S. Duran;Ronald H. Baney .Chemical Cross-Linking, Surface Compressional Modulus, and Viscosity of n-Octadecyltrim3ethoxy Silane Monolayers[J].Journal of the American Chemical Society,2001(9):2103-2104. |
| [15] | Humphry-Baker R;Gratzel M;Moroi Y .Pyrene fluorescence at air/sodium dodecyl sulfate solution interface[J].Langmuir: The ACS Journal of Surfaces and Colloids,2006(26):11205-11207. |
| [16] | 周宁琳.有机硅聚合物导论[M].北京:科学出版社,2000:224. |
| [17] | Innocenzi P. .Infrared spectroscopy of sol-gel derived silica-based films: a spectra-microstructure overview[J].Journal of Non-Crystalline Solids: A Journal Devoted to Oxide, Halide, Chalcogenide and Metallic Glasses, Amorphous Semiconductors, Non-Crystalline Films, Glass-Ceramics and Glassy Composites,2003(2/3):309-319. |
| [18] | Soppera O;Croutxe-Barghorn C;Lougnot D J .New insights into photoinduced processes in hydrid sol-gel glasses containing modified titaniorn alkoxides[J].New Journal of Chemistry,2001,25:1006-1014. |
| [19] | Sassi Z;Burcau J C;BakkaliA .Spectroscopic study of TMOS-TMSM-MMA gels:Previnusly identification of the networks inside the hybrid material[J].Vibrational Spectroscopy,2002,28:299-318. |
| [20] | Britt David W.;Hlady Vladimir .Separating octadecyltrimethoxysilane hydrolysis and condensation at the air/water interface through addition of methyl stearate[J].The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical,1999(14):2749-2754. |
| [21] | 德鲁·迈尔斯;吴大诚.表面、界面和胶体--原理及应用[M].北京:化学工业出版社,2004:115-130. |
| [22] | Winnik F M;Tamai N;Yonezawa J et al.Temperature-induced phase transition of pyrene-labeled(hydroxypropyl)cellulose in water:picosecond fluorescence studies[J].Journal of Physical Chemistry,1992,96(04):1967-1972. |
| [23] | Tracey Keeling-Tucker;John D.Brennan .Fluorescent Probes as Reporters on the Local Structure and Dynamics in Sol-Gel-Derived Nanocomposite Materials[J].Chemistry of Materials,2001(10):3331-3350. |
| [24] | Yamazaki I;Tamai N;Yamazaki T .Picosecond fluorescence spectroscopy on excimer formation and excitation energy transfer of pyrene in Langmuir-Blodgett monolayer films[J].Journal of Physical Chemistry,1987,91:3572-3577. |
| [25] | 廖琳,张路,赵濉,俞稼镛.稳态荧光探针法研究Ca2+与十二烷基苯磺酸钠的相互作用[J].感光科学与光化学,2005(03):203-208. |
| [26] | Winnik F M .Photophysies of preassociated pyrenes in aqueous polymer solutions and in other organized media[J].Chemical Reviews,1993,93:587-614. |
| [27] | Wahl P;Krieger C;Schweitzer D;Staab H A .1,8-Dipyrenylnaphthalenes:syntheses,molecular structure,and spectroscopic properties[J].Chemische Berichte,1984,17:260-276. |
| [28] | Iwao Suzuki;Mihoko Ui;Akiyo Yamauchi .Supramolecular Probe for Bicarbonate Exhibiting Anomalous Pyrene Fluorescence in Aqueous Media[J].Journal of the American Chemical Society,2006(14):4498-4499. |
| [29] | Kayanasundram K.Photochemistry in Microheterogeneous Systems[M].New York:Academic Press,Inc,1987 |
上一张
下一张
上一张
下一张
计量
- 下载量()
- 访问量()
文章评分
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%