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Polydimethylsiloxane. 化工四 B95504050 劉邦彥 B95504048 彭子軒 B95504052 林文翔. Ring-Open Polycondensation. Yield high polymer from ROP of cyclic oligomer . Allow to synthesis high Mn with great precision. Formation of PDMS from D 4 is commonly used in industry. Two kinds of ROP:
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Polydimethylsiloxane 化工四 B95504050 劉邦彥 B95504048 彭子軒 B95504052 林文翔
Ring-Open Polycondensation • Yield high polymer from ROP of cyclic oligomer. • Allow to synthesis high Mn with great precision. • Formation of PDMS from D4 is commonly used in industry. • Two kinds of ROP: • Anionic Polymerization • Cationic Polymerization
Anionic Polymerization Initiation Propagation
Anionic Polymerization • Catalyst: KOH • Condition: 0.01% 140℃ • Product: • Mn: 8.84×105 • Rxn Time: ~90min • Conversion: ~90% • Solubility Problem
Cationic Polymerization Initiation Propagation
Cationic Polymerization • Catalyst: CF3SO3H H2SO4 • Condition: 8.7×10-4M 20℃ • Product: • Mn: 1.4×105 • Rxn Time: ~90min • Conversion: ~85% • HP Conversion: ~60% • Triflic acid: 140,000 NTD/kg
Ring-Open Polycondensation • Small cyclic siloxane will be formed. [D4]o= 1.19M; [TfOH]0 = 8.47.10-4M
Viscosity • Mn Range: 105~106 • Viscosity: • At 140℃[cP]: ~105 • At 25℃[cP]: 105~106 • PFR is available.
Future Work • Reaction constant search. • Process simulation.
Reference • P. DUBOIS, O. COULEMBIER, and J.-M. RAQUEZ, Handbook of Ring-Opening Polymerization, Wiley-VCH Verlag GmbH & Co. KGaA Weinheim 2009, pp. 65-76 • W. T. GRUBB AND ROBERT C. OSTHOF, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY77 (1955)1405-1411 • S. P. GUPTA, M. MOREAU, M. MASURE and P. SIGWALT, Polym. J.29 (1993) 15-22 • E. S. WILKS, Industrial Polymers Handbook, vol.3, Wiley-VCH Verlag GmbH & Co. KGaA Weinheim • https://www.spectrumchemical.com/OA_HTML/ibeCSrdSrchResults.jsp?cg=-200&kw=T2105&ds=0&dr=25&st=kw&cpg=0&minisite=10020&site=&respid=50577 • http://en.wikipedia.org/wiki/Viscosity