TY - JOUR
T1 - Synthesis, Characterization and Bulk Properties of Amphiphilic Copolymers Containing Fluorinated Methacrylates from Sequential Copper-Mediated Radical Polymerization
AU - Hansen, Natanya Majbritt Louie
AU - Gerstenberg, Michael
AU - Haddleton, David M.
AU - Hvilsted, Søren
PY - 2008
Y1 - 2008
N2 - ABSTRACT: The partly fluorinated monomers, 2,2,2-trifluoroethyl methacrylate
(3FM), 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate (8FM), and 1,1,2,2-tetrahydroperfluorodecyl
methacrylate (17FM) have been used in the preparation of block
copolymers with methyl methacrylate (MMA), 2-methoxyethyl acrylate (MEA), and
poly(ethylene glycol) methyl ether methacrylate (PEGMA) by Atom Transfer Radical
Polymerization. A kinetic study of the 3FM homopolymerization initiated with ethyl
bromoisobutyrate and Cu(I)Br/N-(n-propyl)-2-pyridylmethanimine reveals a living/
controlled polymerization in the range 80-110 °C, with apparent rate constants of
1.6 . 10-4 S-l to 2.9 . 10-4 S-l. Various 3FM containing block copolymers with MMA
are prepared by sequential monomer addition or from a PMMA macroinitiator in all
cases with controlled characteristics. Block copolymers of 3FM and PEGMA resulted
in block copolymers with PDI <1.22, whereas block copolymers from 3FM and MEA
have less controlled characteristics. The block copolymers based on MMA with 8FM
and 17 FM have PDI's <1.30. The glass transition temperatures of the block copolymers
are dominated by the majority monomer, as the sequential monomer addition
results in too short pure blocks to induce observable microphase separation. The
thermal stability of the fluorinated poly((meth)acrylate)s in inert atmosphere is less
than that of corresponding nonfluorinated poly((meth)acrylate)s. The presence of
fluorinated blocks significantly increases the advancing water contact angle of thin
films compared to films of the nonfluorinated poly((meth)acrylate)s.
AB - ABSTRACT: The partly fluorinated monomers, 2,2,2-trifluoroethyl methacrylate
(3FM), 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate (8FM), and 1,1,2,2-tetrahydroperfluorodecyl
methacrylate (17FM) have been used in the preparation of block
copolymers with methyl methacrylate (MMA), 2-methoxyethyl acrylate (MEA), and
poly(ethylene glycol) methyl ether methacrylate (PEGMA) by Atom Transfer Radical
Polymerization. A kinetic study of the 3FM homopolymerization initiated with ethyl
bromoisobutyrate and Cu(I)Br/N-(n-propyl)-2-pyridylmethanimine reveals a living/
controlled polymerization in the range 80-110 °C, with apparent rate constants of
1.6 . 10-4 S-l to 2.9 . 10-4 S-l. Various 3FM containing block copolymers with MMA
are prepared by sequential monomer addition or from a PMMA macroinitiator in all
cases with controlled characteristics. Block copolymers of 3FM and PEGMA resulted
in block copolymers with PDI <1.22, whereas block copolymers from 3FM and MEA
have less controlled characteristics. The block copolymers based on MMA with 8FM
and 17 FM have PDI's <1.30. The glass transition temperatures of the block copolymers
are dominated by the majority monomer, as the sequential monomer addition
results in too short pure blocks to induce observable microphase separation. The
thermal stability of the fluorinated poly((meth)acrylate)s in inert atmosphere is less
than that of corresponding nonfluorinated poly((meth)acrylate)s. The presence of
fluorinated blocks significantly increases the advancing water contact angle of thin
films compared to films of the nonfluorinated poly((meth)acrylate)s.
KW - Copolymerization
KW - Amphiphiles
KW - Atom transfer radical polymerization (ATRP)
KW - Block copolymers
KW - Fluoropolymers
U2 - 10.1002/pola.23107
DO - 10.1002/pola.23107
M3 - Journal article
SN - 0887-624X
VL - 46
SP - 8097
EP - 8111
JO - Journal of Polymer Science. Part A, Polymer Chemistry
JF - Journal of Polymer Science. Part A, Polymer Chemistry
IS - 24
ER -