• Macromolecular Research
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• v.15 no.2
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• pp.173-177
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• 2007

Living anionic and cationic polymerizations have been combined to prepare various types of comb-like copolymers composed of polystyrene (PS) and polyisoprene (PI) blocks, with a precisely controlled architecture. According to the relative placement of these elementary building blocks, combs with randomly distributed PS and PI or with poly(styrene-b-isoprene) diblock branches (I & II, respectively) can be prepared. The reaction procedure initially includes the synthesis of a poly(chloroethylvinyl ether) using living cationic polymerization, which is used as the reactive backbone to successively graft $PS^-Li^+$ and $PI^-Li^+$ or $PI-b-PS^-Li^+$ to obtain structures (I) or (II). The synthesis of Janus-type PS-comb-b-PI-combs (III) initially involves the synthesis of a diblock backbone using living cationic polymerization, which bears two distinct reactive functions having either a protected or activated form. Living $PS^-Li^+$ and $PI^-Li^+$ are then grafted, in two separate steps, onto each of the reactive functions of the backbone, respectively.

• Polymer(Korea)
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• v.32 no.4
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• pp.366-371
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• 2008

The controlled/living cationic polymerization of $\alpha$-methylstyrene (${\alpha}MeSt$) and sequential block copolymerization of isobutylene (IB) with ${\alpha}MeSt$ were achieved using 2-chloro-2,4,4-trimethylpentane (TMPCl)/titanium tetrachloride ($TiCl_4$)/titanium isopropoxide ($Ti(OiPr)_4$)/2,6-ditert-butylpyridine (DtBP) initiating system in $CH_3Cl$/hexane(50/50 v/v) solvent mixture at $-80^{\circ}C$. The polymerization rate decreased with increasing $[Ti(OiPr)_4]/[TiCl_4]$ ratio in the homopolymerization of ${\alpha}MeSt$. The effects of $[Ti(OiPr)_4]/[TiCl_4]$ ratios and $PIB^+$ molecular weight on the polymerization rate and blocking efficiency were also investigated. Well-defined poly(isobutylene-b-$\alpha$-methylstyrene)s were demonstrated by $^1H$-NMR and triple detection SEC; refractive index (RI), multiangle laser light scattering (MALLS) and ultraviolet (UV) detectors. Blocking efficiencies for the poly(isobutylene-b-$\alpha$-methylstyrene)s of almost 100% were obtained when ${\alpha}MeSt$ was induced by PIB's of $M_n\;{\geq}\;41000$ at $[Ti(OiPr)_4]/[TiCl_4]=1$. Differential scanning calorimetry (DSC) of the block copolymers showed two glass transition temperatures, thereby demonstrating microphase separation.

• Polymer(Korea)
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• v.35 no.1
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• pp.40-46
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• 2011

The synthesis of well-defined poly(styrene-b-isobutylene-b-styrene) (SIBS) triblock copolymers was accomplished by cationic sequential block copolymerization of isobutylene (IB) with styrene (St) using 1,4-di(2-chloro-2-propyl) benzene (DCC) /$TiCl_4$/2,6-di-tert-butylpyridine(DtBP) as an initiating system in methyl chloride ($CH_3Cl$)/methylcyclohexane(MeChx) (50/50 v/v) solvent mixture at $-80^{\circ}C$. The triblock copolymers exhibited excellent thermoplastic and elastomeric characteristics. Tensile strengths and Shore hardness increased with increasing polystyrene (PS) content, while elongation at break decreased. The blood-compatibility of SIBS was assessed by SEM observation of the platelet adhesion, blood clotting time and haemolysis ratio. The haemolysis ratios were below 5% which met the medical materials standard. The platelet adhesion test further indicated that SIBS block copolymers had a good blood compatibility.