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Volumn 32, Issue 6, 1999, Pages 2071-2074

More versatile route to block copolymers and other polymers of complex architecture by living radical polymerization: the RAFT process

Author keywords

[No Author keywords available]

Indexed keywords

ACRYLICS; FREE RADICAL POLYMERIZATION; MOLECULAR STRUCTURE; MOLECULAR WEIGHT; MONOMERS; POLYSTYRENES;

EID: 13044256394     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma981472p     Document Type: Article
Times cited : (938)

References (33)
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    • note
    • 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.
  • 23
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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.
  • 25
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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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