X-ray photoelectron spectroscopy and Raman spectroscopy were' used to determine the chemical change of polyphenylsilsesquioxane (PPSQ) during pyrolysis in flowing nitrogen. Two temperature ranges were found for py...X-ray photoelectron spectroscopy and Raman spectroscopy were' used to determine the chemical change of polyphenylsilsesquioxane (PPSQ) during pyrolysis in flowing nitrogen. Two temperature ranges were found for pyrolysed PPSQ below and above 600degreesC, respectively. The former is related to the rearrangement of PPSQ backbone and the latter reflects that most of backbone structure of PPSQ might be broken down and unorganized. Carbon formed in carbonization of PPSQ sample pyrolysed at 900degreesC should be sp(3) bonded carbon with crystallite size effects or defects.展开更多
Fluorescence spectra of ladderlike polyphenylsilsesquioxane (LPPS) and ladderlike 1,4-phenylene-bridged polyvinylsiloxane (LPPVS) have been measured as a function of temperature (4-55 degreesC), in dilute tetrahydrofu...Fluorescence spectra of ladderlike polyphenylsilsesquioxane (LPPS) and ladderlike 1,4-phenylene-bridged polyvinylsiloxane (LPPVS) have been measured as a function of temperature (4-55 degreesC), in dilute tetrahydrofuran solution. The excimer (IF) to monomer (I-M) intensity ratio (I-E/I-M) of LPPS dilute solution shows a double linear Arrhenius plot with a break point ascribable to a transition temperature Tt. This behavior has not been found for single chain polyorganosiloxanes. When In/(E) of LPPS was plotted against 1/T, it also gave a double linear plot with one break point, which was found in single chain polyorganosiloxanes. The different behaviors between LPPS and single chain polyorganosiloxanes may be mainly attributed to the relatively rigid double-chain macromolecular backbone of LPPS. However, the 1n(I-E/I-M) of dilute LPPVS solution versus 1/T shows a simple linear variation with a positive slope which confirms our proposition. The difference between the fluorescence results of LPPS and those of LPPVS may possibly derive from their structure differences and cooperative motion in backbone chain bonds.展开更多
Soluble and ordered ladder like polyphenylsilsesquioxane was synthesized by a two-step sol-gel method including hydrolysis and polycondensation. The procedure was monitored by Fourier transform infrared spectroscopy a...Soluble and ordered ladder like polyphenylsilsesquioxane was synthesized by a two-step sol-gel method including hydrolysis and polycondensation. The procedure was monitored by Fourier transform infrared spectroscopy and the presence of the ladder like structure was confirmed by X-ray techniques. 29Si NMR analysis shows a very narrow half peak width（δ4） at δ –78.866 of the main chain unit C6H5SiO3/2 of polyphenylsilsesquioxane, indicating that the polyphenylsilsesquioxane has ordered ladder like structures rather than the branched ones. The relationship between molecular weight and the time of polycondensation was also discussed.展开更多
The ladderlike structure of PPSQ synthesized by-using four kinds of catalysts (MgF2, LiF, KOH and DCC) at different polymerization conditions has been investigated by IR and NMR. In the system using MgF2 as the main c...The ladderlike structure of PPSQ synthesized by-using four kinds of catalysts (MgF2, LiF, KOH and DCC) at different polymerization conditions has been investigated by IR and NMR. In the system using MgF2 as the main catalyst, the most important factor which affects the ladderlike structure of PPSQ is the composition of the dual catalysts, MgF2 and DCC. PPSQ prepared by using KOH as the catalyst has the highest regularity of ladderlike structure among all samples. PPSQ with different degree of ladder regularity can be obtained by choice of polymerization conditions.展开更多
Soluble, high molecular weight (MW) and ladderlike polyphenylsilsesquioxane (LPPSQ) and its copolymers, ladderlike random and block copolymethyiphenylsilsesquioxanes(LR-PMPSQ and LB-PMPSQ)have been prepared by preammi...Soluble, high molecular weight (MW) and ladderlike polyphenylsilsesquioxane (LPPSQ) and its copolymers, ladderlike random and block copolymethyiphenylsilsesquioxanes(LR-PMPSQ and LB-PMPSQ)have been prepared by preamminolysis, hydrolysis and polycondensation reactions. The preparation method can be carried out easily at the temperature below 95℃ with high yield of 95 %, instead of the conventional way by using high-boiling solvent and any reaction activator or by precipitation with methanol. Three kinds of ladderlike polymers have been characterized. The MW's of the polymers reached to 10~6 without noticeable gelling. The scheme for synthetic route has been proposed.展开更多
基金The National Natural Science Foundation of China (Grant No. 20074039) and National 863 High-technology Project as well as the Science Foundation of PPLAS(No, 00-B-01) are gratefully acknowledged for the financial support to this work.
文摘X-ray photoelectron spectroscopy and Raman spectroscopy were' used to determine the chemical change of polyphenylsilsesquioxane (PPSQ) during pyrolysis in flowing nitrogen. Two temperature ranges were found for pyrolysed PPSQ below and above 600degreesC, respectively. The former is related to the rearrangement of PPSQ backbone and the latter reflects that most of backbone structure of PPSQ might be broken down and unorganized. Carbon formed in carbonization of PPSQ sample pyrolysed at 900degreesC should be sp(3) bonded carbon with crystallite size effects or defects.
基金The authors gratefully thank the National Natural Science Foundation of China (No. 29874034, 29992530, 29873060) and Dow Corning Corporation for their financial support.
文摘Fluorescence spectra of ladderlike polyphenylsilsesquioxane (LPPS) and ladderlike 1,4-phenylene-bridged polyvinylsiloxane (LPPVS) have been measured as a function of temperature (4-55 degreesC), in dilute tetrahydrofuran solution. The excimer (IF) to monomer (I-M) intensity ratio (I-E/I-M) of LPPS dilute solution shows a double linear Arrhenius plot with a break point ascribable to a transition temperature Tt. This behavior has not been found for single chain polyorganosiloxanes. When In/(E) of LPPS was plotted against 1/T, it also gave a double linear plot with one break point, which was found in single chain polyorganosiloxanes. The different behaviors between LPPS and single chain polyorganosiloxanes may be mainly attributed to the relatively rigid double-chain macromolecular backbone of LPPS. However, the 1n(I-E/I-M) of dilute LPPVS solution versus 1/T shows a simple linear variation with a positive slope which confirms our proposition. The difference between the fluorescence results of LPPS and those of LPPVS may possibly derive from their structure differences and cooperative motion in backbone chain bonds.
基金Supported by the National Natural Science Foundation of China(No.51073020)the Program for Changjiang Scholars and Innovative Research Team in University of China(No.IRT0706)
文摘Soluble and ordered ladder like polyphenylsilsesquioxane was synthesized by a two-step sol-gel method including hydrolysis and polycondensation. The procedure was monitored by Fourier transform infrared spectroscopy and the presence of the ladder like structure was confirmed by X-ray techniques. 29Si NMR analysis shows a very narrow half peak width（δ4） at δ –78.866 of the main chain unit C6H5SiO3/2 of polyphenylsilsesquioxane, indicating that the polyphenylsilsesquioxane has ordered ladder like structures rather than the branched ones. The relationship between molecular weight and the time of polycondensation was also discussed.
文摘The ladderlike structure of PPSQ synthesized by-using four kinds of catalysts (MgF2, LiF, KOH and DCC) at different polymerization conditions has been investigated by IR and NMR. In the system using MgF2 as the main catalyst, the most important factor which affects the ladderlike structure of PPSQ is the composition of the dual catalysts, MgF2 and DCC. PPSQ prepared by using KOH as the catalyst has the highest regularity of ladderlike structure among all samples. PPSQ with different degree of ladder regularity can be obtained by choice of polymerization conditions.
文摘Soluble, high molecular weight (MW) and ladderlike polyphenylsilsesquioxane (LPPSQ) and its copolymers, ladderlike random and block copolymethyiphenylsilsesquioxanes(LR-PMPSQ and LB-PMPSQ)have been prepared by preamminolysis, hydrolysis and polycondensation reactions. The preparation method can be carried out easily at the temperature below 95℃ with high yield of 95 %, instead of the conventional way by using high-boiling solvent and any reaction activator or by precipitation with methanol. Three kinds of ladderlike polymers have been characterized. The MW's of the polymers reached to 10~6 without noticeable gelling. The scheme for synthetic route has been proposed.
