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X.  D. Feng,  X.  Q.  Guo,  K. Y.  Qiu  
Fig.  6 .  The  CTC  spectra  of   PMMA in TCNE/CH,Cl,  
solution.  (1)  PMMA (initiation  
by  AIBN :) , (2):  PMMA (initiation  
by  TMEDA/APS),  (3):    TMEDA/TCNE in CH,Cl,   320   
400    5  A  Inm  
Initiation mechanbm  
Based on the results discussed above, the following initiation mechanism of the 
TMEDA/persulfate system via contact charge transfer complex  ( CCT) and cyclic  transition state (C  TS) may be proposed.    -  so:- 
 1   + 'OSO,H  5       CTS  
5   + H20  - HSOa  +    HO.   6  
The free radicals 1 , 5   and 6   are responsible for the initiation of vinyl polymeriza- 
tion. In the absence of monomers, the primary free radical 1 may undergo fi-scission 
to form free radical 3 and the unstable imino compound 4 ,  which will react with water   
to form methylamine and formaldehyde6). 
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Study of the initiation mechanism o  
f the vinyl polymerizationw ith the system. .  .  83    In the case  
of a high concentration  o 
f TMEDA, a free radicalc hain transfer reac-  
tion may take place to form radica 2 l    by reaction   of radicals  
1,5  or  6  with TMEDA.  
The authors are indebted to the  
National Natural ScienceF oundation  
of  China  for  financial   support of this work.  
’) U.S.  4189370 (1980) ,  Assignee, Societe Sebia, inv.: E. Boschetti;  
Chem. Abstr.  93 ,  4104631    (  980 )  ,  2 T
1.  Tanaka,  Sci. Am.  244   ( l), 110 (1981)   , 
3 M. K.  Gupta,  R.  Bansil,  Polym. Prepr. (Am. Chem.  Soc.,  Div.  Polym. Chem.)  22   (2) .  375    (1981)   
4 ,  X.  Q. Guo,  K.  Y.  Qiu,  X.  D.  Feng,  Scientia Sinica,  B  30  ( 9) , 897 (1987)  
E. Collinson,  F. S.  Dainton,  G.  S.  McNaughton,  Trans. Faruday  SOC.  53 ,  489 (1957)   
@ J.  March,  “Advanced Organic Chemistry Reactions, Mechanism andS tructure”,  2 nd Ed.,  
McGraw-Hill, New  York  1  
977 ,  p.  806   
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