156645-12-4Relevant articles and documents
Main-Chain and Side-Chain Sequence-Regulated Vinyl Copolymers by Iterative Atom Transfer Radical Additions and 1:1 or 2:1 Alternating Radical Copolymerization
Soejima, Takamasa,Satoh, Kotaro,Kamigaito, Masami
, p. 944 - 954 (2016)
Main- and side-chain sequence-regulated vinyl copolymers were prepared by a combination of iterative atom transfer radical additions (ATRAs) of vinyl monomers for side-chain control and 1:1 or 2:1 alternating radical copolymerization of the obtained side-chain sequenced "oligomonomers" and vinyl comonomers for main-chain control. A complete set of sequence-regulated trimeric vinyl oligomers of styrene (S) and/or methyl acrylate (A) were first synthesized via iterative ATRAs of these monomers to a halide of monomeric S or A unit (X-S or X-A) under optimized conditions with appropriate ruthenium or copper catalysts, which were selected depending on the monomers and halides. The obtained halogen-capped oligomers were then converted into a series of maleimide (M)-ended oligomonomers with different monomer compositions and sequences (M-SSS, M-ASS, M-SAS, M-AAS, M-SSA, M-ASA, M-SAA, M-AAA) by a substitution reaction of the halide with furan-protected maleimide anion followed by deprotection of the furan units. These maleimide-ended oligomonomers were then radically copolymerized with styrene or limonene to enable the 1:1 or 2:1 monomer-sequence regulation in the main chain and finally result in the main- and side-chain sequence-regulated vinyl copolymers with high molecular weights in high yield. The properties of the sequence-regulated vinyl copolymers depended on not only the monomer compositions but also the monomer sequences. The solubility was highly affected by the outer monomer units in the side chains whereas the glass transition temperatures were primarily affected by the two successive monomer sequences.
Scope and Limitations of Aliphatic Friedel-Crafts Alkylations. Lewis Acid Catalyzed Addition Reactions of Alkyl Chlorides to Carbon-Carbon Double Bonds
Mayr, Herbert,Striepe, Wilhelm
, p. 1159 - 1165 (2007/10/02)
Lewis acid catalyzed addition reactions of alkyl halides 1 with unsaturated hydrocarbons 2 have been studied. 1:1 addition products 3 are formed if the addends 1 dissociate faster than the corresponding products 3; otherwise, polymerization of 2 takes place.For reaction conditions under which 1 and 3 exist mainly undissociated, solvolysis constants of model compounds can be used to predict the outcome of any such addition reactions if systems with considerable steric hindrance are excluded.