New initiator system for the anionic polymerization of (meth)acrylates in toluene. IV. Random copolymerization of (meth)acrylates in toluene initiated by s-BuLi ligated by lithium silanolates
✍ Scribed by Catherine Zune; Thomas Zundel; Philippe Dubois; Philippe Teyssié; Robert Jérôme
- Publisher
- John Wiley and Sons
- Year
- 1999
- Tongue
- English
- Weight
- 155 KB
- Volume
- 37
- Category
- Article
- ISSN
- 0887-624X
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✦ Synopsis
Copolymerization of binary mixtures of alkyl (meth)acrylates has been initiated in toluene by a mixed complex of lithium silanolate O(s-BuMe 2 SiOLi)O and s-BuLi (molar ratio Ͼ 21) formed in situ by reaction of s-BuLi with hexamethylcyclotrisiloxane (D 3 ). Fully acrylate and methacrylate copolymers, i.e., poly(methyl acrylateco-n-butyl acrylate), poly(methyl methacrylate-co-ethyl methacrylate), poly(methyl methacrylate-co-n-butyl methacrylate), poly(methyl methacrylate-co-n-butyl methacrylate), poly(isobornyl methacrylate-co-n-butyl methacrylate), poly(isobornyl methacrylate-co-n-butyl methacrylate) of a rather narrow molecular weight distribution have been synthesized. However, copolymerization of alkyl acrylate and methyl methacrylate pairs has completely failed, leading to the selective formation of homopoly(acrylate). As result of the isotactic stereoregulation of the alkyl methacrylate polymerization by the s-BuLi/s-BuMe 2 SiOLi initiator, highly isotactic random and block copolymers of (alkyl) methacrylates have been prepared and their thermal behavior analyzed. The structure of isotactic poly(ethyl methacrylate-co-methyl methacrylate) copolymers has been analyzed in more detail by Nuclear Magnetic Resonance (NMR).