Synthesis and characterization of block copolymers of polyvinylpyridine (PVP) or polyalphamethylstyrene (PAMS) with polydimethylsiloxane (PDMS), and self assembly of PVP-PDMS and polyvinylphenol

Narrow distribution poly(2-vinylpyridine)-poly(dimethylsiloxane) (P2VP-PDMS) and poly(4-vinylpyridine)-poly(dimethylsiloxane) AB and ABA block copolymers containing PVP blocks were synthesized by anionic polymerization of 2VP or 4VP inititated, by an acetal functionalized alkyllithium. This was followed by acid hydrolysis of the acetal and titration of the resulting hydroxyl group triphenyllithium (Ph3Cli) and addition of hexamethylcyclotrisiloxane (D3) producing the living PVP-b-PDMSLi block copolymers that were terminated or coupled with Me3SiCl and Me2SiCl 2 respectively to give the AB and ABA PVP-PDMS block copolymers. Alternatively the vinylpyridines were initiated with lithium carbanions and alkylated with a bromo-functionalized acetal followed by hydrolosis, titration with Ph 3Cli and addition of D3 followed by termination or coupling.;The polymers were characterized by SEC and NMR. The P2VP or P4VP blocks had molecular masses of between 800 and 6,200 whereas block copolymers ranged between 2,200 and 290,000 Daltons.