LIU Erqiang, ZHANG Zhicheng. ATOM TRANSFER RADICAL REACTION METHOD PREPARING VDF/TrFE/CTFE TERPOLYMER BY REDUCTIVE DECHLORINATION OF VDF/CTFE COPOLYMER. [J]. Acta Polymerica Sinica (9):1129-1135(2010)
DOI:
LIU Erqiang, ZHANG Zhicheng. ATOM TRANSFER RADICAL REACTION METHOD PREPARING VDF/TrFE/CTFE TERPOLYMER BY REDUCTIVE DECHLORINATION OF VDF/CTFE COPOLYMER. [J]. Acta Polymerica Sinica (9):1129-1135(2010) DOI: 10.3724/SP.J.1105.2010.10002.
ATOM TRANSFER RADICAL REACTION METHOD PREPARING VDF/TrFE/CTFE TERPOLYMER BY REDUCTIVE DECHLORINATION OF VDF/CTFE COPOLYMER
A novel catalytic hydrogenation method of dechlorination for P(VDF-co-CTFE)s to convert CTFE units into TrFE units through CuCl/2
2′-bipyridine catalyzed atom transfer radical reaction and chain transfer reaction was reported in this work.In this method
the Cl atom in VDF/CTFE copolymer has been first removed by CuCl/2
2′-bipyridine complex via reductive reaction
and P(VDF-co-CTFE) macromolecule free radicals has been generated.In the presence of chain transfer agent
the free radicals would grab an H atom and the polymer radical is terminated.As a result
Cl atom has been exchanged with H atom
and P(VDF-co-CTFE) is transferred into P(VDF-co-TrFE-co-CTFE) or P(VDF-co-TrFE) as desired.The effect of solvent
reaction temperature
reaction time and catalyst dosage on the hydrogenation of P(VDF-co-CTFE) has been well discussed.It has shown that a certain reaction temperature is required to activate the reaction
and high temperature favors the reaction rate.As reaction time prolongs
the hydrogenation ratio of CTFE units increases until they are fully converted or either the catalysts or the chain transfer agents run out.The amount of TrFE units could be exactly controlled by introducing the catalyst in desired dosage since one initiator molecule is only able to hydrogenate one CTFE molecule.The rather close limiting viscosity number of P(VDF-co-CTFE) and the resultant P(VDF-co-TrFE-co-CTFE) means that no decomposition or coupling reaction happens in the process.Generally
the new method possesses advantages such as lower cost
lower toxic
higher convenience and higher controllability compared with the previous method.