By Jaques Roovers
The 2 spouse volumes of Advances in Polymer technology numbers 142 and 143 take care of smooth features of long-chain branching in man made polymers. The long-chain structure is now more and more used as a layout device for targetted polymer houses. the factitious facets conceal branching via cationic polymerization, uneven branching, poly(macromonomers), dendrimer-polymer hybrids and hyperbranched polymers. 3 contributions hide thought and simulation of branching, answer homes, and soften move of branched polymers, respectively.
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Extra resources for Branched Polymer I
3 Poly(isobutylene) Branches Grafting IB from PS backbone containing tert-benzylic acetate initiating sites was described by Jiang and Fréchet . The backbone was obtained by chemical modification of PS shown in Scheme 8. Polymerization of IB from the PS macroinitiator was accomplished with BCl3 as coinitiator in CH2Cl2 at –78 °C. Due to the living nature of the polymerization of IB, high grafting efficiencies (~85%) were reported. The resulting ~15% homoPIB was most probably due to initiation from adventitious moisture or direct initiation (haloboration).
In the first example, amphiphilic A2B2 type starblock copolymers (A=PIB and B=poly(MeVE) were prepared via the living coupling reaction of living PIB, using 2,2-bis[4-(1-tolylethenyl)phenyl]propane (29, BDTEP) as a living coupling agent, followed by initiation of MeVE from the di-cation at the junction of the living coupled PIB . Fractionation of the crude A2B2 star-block copolymer was carried out on a silica gel column and the purity of the crude A2B2 star-block copolymer was calculated to be=93% based on the weights of fractions.
The structure was verified using 1H NMR analysis which evidenced quantitative reaction of each enol ether group for both coupling agents. Moreover, the mole ratio of the aromatic rings in the core to the a-end methyl of the chains was found close to 1 confirming the quantitative coupling. The coupling reaction of similar but longer poly(IBVE) (DPn~50) was performed in order to study the influence of the chain length. The SEC analysis showed bimodal distributions. The major higher MW peak corresponded to the coupled product and had narrow MWD.