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1. 3 4 R 3 R R 4 O J SO O 5 52. 4 3 2 2 1 4 M 4 1 12
3. 8 2005 Estimation of monomer reactivities in the Synthesis of poly styrene sulfone derivatives Using COmDputer aided chemistry Tsutomu SHINODA Hiroshi UENO Yoshio SHINDOH and Kenichi SHIMIZU Abstract It is reported that some vinyl monomers react with sulfur dioxide to form polysulfones in liquid SO We found that 4 trimethylsilyloxystyrene IMSOSt copolymerized to give an alternating 1 1 copolymer whereas 4 7e77 butoxystyrene homopolymerized The copolymerization was initiated by 7e77 butyl hydroperoxide and was considered to proceed by a free radical mechanism We focused our attention on the nucleophilic attack of a monomer radical on SO The SOMO Singly Occupied Molecular Orbital energies of monomer radicals and their electron densites at c carbon atoms of vinyl moieties were calculated by the MOPACin CAChe They were treated at the PM5 level The TMSOSt monomer radical Which is reactive in a polysulfone formation had both a high SOMO energy and a high electron density With a dihedral angle of 180 to 180 between the benzene ring and the vinyl radical moiety the electron density varied by 51 while the SOMO energy changed by only 4 6 KeywordS Sulfur d
4. 2 12 18 HOMO Highest Occupied Molecular Orbital HOMO LUMO Lowest Unoccupied Molecular Orbital LUMO HOMO LUMO 6 6 3 3 S C 1 43A C S C 115 5 S C 1 475 1 35 3 72 debye
5. S C 1 43A C S C 119 3 1 63 debye 2 3 12 35 285 8 2005 34 846 20 804 16 050 15 898 15 059 12 037 11 888 10 039 2 302 0 893 0 264 eV HOMO 9 10 0399 eV LUMO 2 302 eV LUMO 2 40 0 53 eV LUMO 7 CO 0 53 eV SO 2 30 eV 7 3 4 SOMO Singly Occupied Molecular Orbita
6. 1977 4 4 II 649 II 576 1993 17 8 3 8 2005
7. SOMO 8b 2 CH3 CHe Cipso Cortho 8 SOMO 8a SOMO 2 8b 9 2 SOMO a 2 OO 10 SOMO 2 2 a 51 0 i ey hp ni a SOMO 64 1 4 a mA A 3 67 0 4 3 68 Cap 0 2 69 0 180 120 60 0 60 120 180 2 9 SOMO a 2 08r 7 0 6 A 0 4 0 2 180 120 60 0 60 120 180 2 10 SOMO a
8. 2 4 a aR SOMO a 180 180 2 I 4 6 oc 51 CAChe 6 1 Windows User Guide Limitations of computer anded chemistry CAChe for Windows was designed to help skilled experimental chemlsts explore questions that can be addressed by computational chemistry Your chemical intuition Will help you Compose the right questions and CAChe for Windows will help you interpret the answers 1 A H Fawcett Olefin Sulfur Dioxide Copolymers in Encyclopedia of Polym Sci Eng 2 Ed H F Mark N ML Bikales C G Overberger G Menges J 1 Kroschwitz Eds John Wiley 1985 1990 p 408 432 2 T Shinoda M Yoshikawa T Nishiwaki Polym J 28 282 283 1996 3 p 278
9. MOPAC 20 000 30 000 1 PM5 3 1 PM5 8 2005 3 1 2 terxt 80 C 1 1 2 2
10. ioxide Polysulfone 4 Trimethylsilyloxystyrene 4 7e77 butoxystyrene Free radical Nucleophilic attack SOMO energy Electron density MOPAC CAChe PM5 Dihedral angle 1 Alfrey Price ON eg 3 OO 0 2 ey 0 45 e 0 64 1 0 e 0 80 Q e 2 CAChe 6 1 Windows MOPAC PM5 User Guide AE 2
11. l 8 SOMO ce 2 Final heat of formation 2 SOMO a bp 10 0 C 1 1 2 SUMO Energy SOMO Density 4 4 tert 7 4 tert 7 2 AFLY 4 7 8 2005 SOMO a 3 5 2 TMSOSt 2 SOMO 8a
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