142 Advances in Polymer Science Editorial Board: A. Abe. A.-C ...

Synthesis of Branched Polymers by Cationic Polymerization 63
Table 5. Synthesis of macromonomers by cationic polymerization
Nature of the chain Nature of the
polymerizable function
Method useda Reference
Poly(EVE) Methacrylate 30 [71–73]
Poly(SiVE) Methacrylate 30 [75]
Poly(EVE) Allyl, epoxyde 32 [73, 74]
Poly(Silyl vinyl ether) or
poly(vinyl alcohol)
Styrene 33 [76–78]
PS
Poly(p-MeS)
Methacrylate 31 [79]
Poly(a-MeS) Methacrylate 31 [80]
Poly(b-pinene)
Poly(b-pinene-b-p-MeS)
Methacrylate 31 [83]
PIB Styrene 34 [84–86]
PIB Methacrylate 35 [87, 88]
Poly(IBVE) Vinyl ether 36 [89]
Poly(AcOVE-b-IBVE) Vinyl ether 36 [90]
Poly(BVE),
Poly(IBVE),
Poly(EVE)
Methacrylate 37, 41 [91]
Poly(BVE),
Poly(IBVE),
Poly(EVE)
Allyl 38 [91]
Poly(3-[4-cyano-4'-biphenyl) Methacrylate
37
[92]
oxy]propyl vinyl ether) Allyl
39, 40
[92]
Poly(ODVE) Methacrylate 37 [93, 94]
Sequence regulated
oligomers of vinyl ethers
Vinyl ether 36 [97]
Poly(p-MOS) Methacrylate 37 [98]
Poly(tBOS) Methacrylate 37 [99]
PS Methacrylate 42 [100]
PIB Allyl, epoxyde 43 [34]
PIB Methacrylate
–
[102–105]
Cyanoacrylate
–
[106, 107]
Vinyl ether
–
[108]
a Numbers 30–35 = functional initiator; 36–43 = functional terminator; – chain end modification
Cyanoacrylate capped PIB (CA-PIB) has been synthesized by esterification of
PIB-CH 2 OH with the Diels-Alder adduct of 2-cyanoacryloyl chloride and anthracene
followed by deprotection (Scheme 15) [106, 107].
The value of F n was determined by 1 H NMR spectroscopy and found to be
close to unity. By essentially the same method, bifunctional and trifunctional
cyanoacrylate functional PIBs have also been prepared. Anionic polymerization
of CA-PIB with N,N-dimethyl-p-toluidine as initiator in solution resulted in high
MW product (M n ~35,000 g mol –1 ) [107]. Anionic copolymerization of difunctional
and trifunctional PIB yielded clear flexible films with low sol fraction. The