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1
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13044285876
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note
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The use of the adjective "living" to describe a radical polymerization which displays the attributes of a living polymerization is preferred over other terms that have been advocated in this context (e.g., "controlled", "living/controlled", "pseudo living", or "living polymerization with reversible deactivation"), even though some side reactions (radical-radical termination) must inevitably complicate the process.
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RACI, Polymer Division: Brisbane
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13044311925
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note
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Synthesis of poly(methyl methacrylate-block-butyl methacrylate-block-methyl methacrylate). B block: A solution of AIBN (2.5 mg), n-butyl methacrylate (3.8 mL), 1,4-bis-(dithiobenzoylprop-2-yl)benzene (7) (93.5 mg) in benzene (1.2 mL) was placed in an ampule, and the contents were degassed, sealed, and heated at 60 °C for 16 h to give poly-(n-butyl methacrylate) (conversion, 49%). A block: A solution of the above poly(n-butyl methacrylate) (300 mg; precipitated from methanol to remove residual initiator), AIBN (0.51 mg), and methyl methacrylate (0.75 mL) in benzene (0.25 mL) was degassed, sealed, and heated at 60 °C for 16 h to provide the triblock copolymer (conversion of methyl methacrylate, >95%). GPC data for these polymers are shown in Table 2 and Figure Ic.
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Synthesis of poly(benzyl methacrylate-block 2-(dimethylamino)ethyl methacrylate). A block: A solution of cumyl dithiobenzoate (1c) (2 g), azobis(isobutyronitrile) (101 mg) in benzyl methacrylate (15 mL), and benzene (5 mL) was degassed through three freeze-thaw-evacuate cycles, sealed under vacuum, and heated in a constant-temperature bath at 60 °C for 88 h. B block: A solution of dithiobenzoate-terminated poly(benzyl methacrylate) (0.4 g), azobisüsobu-tyronitrile) (4 mg), and 2-WV-dimethylamino)ethyl meth-acrylate (0.4 g) in ethyl acetate (2 mL) was degassed through three freeze-thaw-evacuate cycles, sealed under vacuum, and heated in a constant-temperature bath at 60 5C for 24 h. Removal of the solvent provided the diblock copolymer. Details of molecular weight are provide in Table 1 and Figure 1a.
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0347653375
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Moad, G.; Ercole, F.; Johnson, C. H.; Krstina, J.; Moad, C. L.; Rizzardo, E.; Spurling, T. H.; Thang, S. H.; Anderson, A. G. ACS Symp. Ser. 1998, 685, 332.
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Thang, S.H.8
Anderson, A.G.9
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25
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13044250316
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note
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An amount of dead polymer impurity equating to the number of initiating radicals generated during the course of polymerization should be formed. In a diblock synthesis, this impurity may take the form of homopolymer, dibock copolymer, or triblock copolymer depending on the species involved and whether radical-radical termination occurs by combination or disproportionation.
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n = 1.21, and the cumulative [MMA]/[BA] = 1:0.8.
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