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By Jaques Roovers
The 2 significant other volumes of Advances in Polymer technology numbers 142 and 143 take care of sleek points of long-chain branching in artificial polymers. The long-chain structure is now more and more used as a layout software for targetted polymer homes. the unreal facets disguise branching through cationic polymerization, uneven branching, poly(macromonomers), dendrimer-polymer hybrids and hyperbranched polymers. 3 contributions hide conception and simulation of branching, answer houses, and soften movement of branched polymers, respectively.
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Additional resources for Branched Polymer I
Example text
Ethers are converted to the corresponding chlorides almost instantaneously, while the conversion of esters is somewhat slow. Alcohols are inactive with TiCl4 alone but have been used in conjunction with a mixture of BCl3 and TiCl4; BCl3 converts the alcohols to the active chloride which is activated by TiCl4. , in CH3Cl or CH2Cl2/hexane (40/60 v/v) solvent mixture at –80 °C in the presence of a Lewis base. Four arm star PIB has been prepared by living polymerization with the 3,3',5,5'-tetra(2-acetoxy-isopropyl)biphenyl (TCumOAc, 18)/BCl3 initiating system in dilute solutions in the –35 to –80 °C range [35].
6 Poly(isobutylene) p-Poly(isobutylene)styrene (S-PIB) was synthesized by polymerizing IB with the p-(b-bromoethyl)cumyl chloride (34) /(CH3)3Al initiating system in CH3Cl at –55 °C, followed by dehydrobromination with tert-BuOK [84]. The polymerization proceeded in the absence of chain transfer to monomer. Although termination was operational with (CH3)3Al, it was apparently slower than propagation since the MWs could be adjusted in the 4000–34,000 g mol–1 range by changing the [monomer]/[initiator] ratio.
The best coupling efficiency was obtained with p-toluenesulfonic acid as a catalyst in mesitylene at 155 °C. The final product, which was characterized by SEC and MALDI-TOF mass spectrometry, was a mixture of the various star-shaped structures together with unreacted PEO and diblock copolymer. Table 3. Multiarm star polymers and copolymers synthesized using a multifunctional coupling agent Monomers Multi-functional coupling agent Type of star Reference IBVE 22 23 [46] [46] 28 25 A3(low yield) A4(low yield) A3 (major product) A3 A4 A6 A8 (low yield) A5 (major product) A8 (AB)4 25 29 PIB-(di)anhydride (AB)4 [54] A2B2 [55, 56] mixture of AB2, AB3, AB4 [57] IB IBVE/SiVE, CEVE/AcOVE a-MeS/SiVE IB/MeVE IB/EO 24 25 26 27 [48] [48, 49] [50] [50] [51] [53] Synthesis of Branched Polymers by Cationic Polymerization 41 The known methods to prepare star polymers and copolymers via living cationic polymerization with multifunctional coupling agents are summarized in Table 3.