4.3 Graft Copolymer
Conventional graft copolymers containing condensation polymers were produced
by polycondensation of AA and BB monomers, one of which carried a side-chain
polymer such as a vinyl polymer or polysiloxane [76–79]. Since those reports,
CGCP of phosphoranimine was used to synthesize polymers grafted with welldefined polyphosphazene [80–83]. We recently prepared polystyrene grafted with
well-defined poly( p-benzamide) and examined its thermal properties [84]. Styryl
macromonomer 30 containing poly(N-OOB-p-benzamide) was first synthesized by
CGCP of methyl 4-(OOB-amino)benzoate 14b with phenyl 4-vinylbenzoate as an
initiator. Free radical copolymerization of 30 and styrene in the presence of AIBN
at 60
C gave polystyrene-g-poly(N-OOB-p-benzamide), from which the OOB
groups on amide nitrogen were removed with TFA (Scheme 35). The T g value of
polystyrene-g-poly(N-H-p-benzamide) was dramatically increased from that of
polystyrene (109
C) to 172
C in the case of the graft copolymer containing
4.4 mol% of the grafted poly( p-benzamide) chains.
A well-defined aromatic polyamide backbone grafted with conventional
polymer was also synthesized. Methyl 4-aminobenzoate bearing polyTHF, which
was obtained by quenching the living cationic propagating group of poly(THF)
with methyl 4-aminobenzoate, underwent CGCP with LiHMDS to yield a graft
copolymer with well-defined polyamide main chain and poly(THF) side chain
(Scheme 36) [85].
Scheme 35 Synthesis of polystyrene grafted with poly( p-benzamide)
Scheme 36 Synthesis of polyamide grafted with poly(THF)
Chain-Growth Condensation Polymerization for Controlled Synthesis of Polymers
219
Conventional graft copolymers containing condensation polymers were produced
by polycondensation of AA and BB monomers, one of which carried a side-chain
polymer such as a vinyl polymer or polysiloxane [76–79]. Since those reports,
CGCP of phosphoranimine was used to synthesize polymers grafted with welldefined polyphosphazene [80–83]. We recently prepared polystyrene grafted with
well-defined poly( p-benzamide) and examined its thermal properties [84]. Styryl
macromonomer 30 containing poly(N-OOB-p-benzamide) was first synthesized by
CGCP of methyl 4-(OOB-amino)benzoate 14b with phenyl 4-vinylbenzoate as an
initiator. Free radical copolymerization of 30 and styrene in the presence of AIBN
at 60
C gave polystyrene-g-poly(N-OOB-p-benzamide), from which the OOB
groups on amide nitrogen were removed with TFA (Scheme 35). The T g value of
polystyrene-g-poly(N-H-p-benzamide) was dramatically increased from that of
polystyrene (109
C) to 172
C in the case of the graft copolymer containing
4.4 mol% of the grafted poly( p-benzamide) chains.
A well-defined aromatic polyamide backbone grafted with conventional
polymer was also synthesized. Methyl 4-aminobenzoate bearing polyTHF, which
was obtained by quenching the living cationic propagating group of poly(THF)
with methyl 4-aminobenzoate, underwent CGCP with LiHMDS to yield a graft
copolymer with well-defined polyamide main chain and poly(THF) side chain
(Scheme 36) [85].
Scheme 35 Synthesis of polystyrene grafted with poly( p-benzamide)
Scheme 36 Synthesis of polyamide grafted with poly(THF)
Chain-Growth Condensation Polymerization for Controlled Synthesis of Polymers
219