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Poly(methyl methacrylate-co-ethyl acrylate) latex particles with poly(ethylene glycol) grafts: Structure and film formation

Schantz, Staffan; Carlsson, Hans T.; Andersson, Thomas; Erkselius, Stefan LU ; Larsson, Anders and Karlsson, Ola LU (2007) In Langmuir 23(7). p.3590-3602
Abstract
Water-based copolymer dispersions were prepared using methyl methacrylate (MMA), ethyl acrylate (EA) (MMA/EA = 1:2), and a series of nonionic polymerizable surfactants, i.e., "surfmers" based on poly(ethylene glycol)-(meth)acrylates. The latexes were compared with the behavior of a conventionally stabilized (nonionic nonylphenol ethoxylate, NP100 with 84 ethylene oxide units) dispersion with the same MMA-EA composition (PMMAEA). A number of techniques were employed in order to characterize structure, dynamics, and film formation properties: solution/solid-state NMR, dynamic/static light scattering (DLS/SLS), differential scanning calorimetry (DSC), tensile/shear mode dynamic mechanical thermal analysis (DMTA), and atomic force microscopy... (More)
Water-based copolymer dispersions were prepared using methyl methacrylate (MMA), ethyl acrylate (EA) (MMA/EA = 1:2), and a series of nonionic polymerizable surfactants, i.e., "surfmers" based on poly(ethylene glycol)-(meth)acrylates. The latexes were compared with the behavior of a conventionally stabilized (nonionic nonylphenol ethoxylate, NP100 with 84 ethylene oxide units) dispersion with the same MMA-EA composition (PMMAEA). A number of techniques were employed in order to characterize structure, dynamics, and film formation properties: solution/solid-state NMR, dynamic/static light scattering (DLS/SLS), differential scanning calorimetry (DSC), tensile/shear mode dynamic mechanical thermal analysis (DMTA), and atomic force microscopy (AFM). The surfmers were found to be miscible with the MMA-EA copolymer at room temperature, with 46-85 mol % of the reacted surfmer detected at the particle surfaces, and the remaining part buried in the particle bulk. In contrast, the NP100 surfactant formed a separate interphase between the copolymer particles with no mixing detected at room temperature or at 90 degrees C. For a 4.0% dry weight concentration, NP100 phase separated and further crystallized at room temperature over a period of several months. Composition fluctuations related to a limited blockiness on a length scale above similar to 2 nm were detected for PMMAEA particles, whereas the surfmer particles were found to be homogeneous also below this limit. On a particle-particle level, the dispersions tended to form colloidal crystals unless hindered by a broadened particle size distribution or, in the case of PMMAEA, by the action of NP100. Finally, a surface roughness (R-q) master plot was constructed for data above the glass transition temperature (T-g) from T-g + 11 degrees C to T-g + 57 degrees C and compared with the complex shear modulus over 11 frequency decades. Shift factors from the 2 methods obeyed the same Williams-Landel-Ferry (WLF) temperature dependence, thus connecting the long-time surface flattening process to the rheological behavior of the copolymer. (Less)
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Contribution to journal
publication status
published
subject
keywords
REACTIVE SURFACTANTS, C-13 NMR-SPECTROSCOPY, SEQUENCE DISTRIBUTION, HETEROPHASE POLYMERIZATION, ENERGY-TRANSFER, FORMATION BEHAVIOR, COPOLYMER LATEXES, CHAIN-LENGTH 3, PRESSURE-SENSITIVE ADHESIVES, ATOMIC-FORCE MICROSCOPY
in
Langmuir
volume
23
issue
7
pages
3590 - 3602
publisher
The American Chemical Society
external identifiers
  • wos:000245012900016
  • scopus:34147198325
ISSN
0743-7463
DOI
10.1021/la062802z
language
English
LU publication?
yes
id
46eaac74-824e-4d5c-8176-3a3e12f93501 (old id 541194)
alternative location
http://pubs3.acs.org/acs/journals/doilookup?in_doi=10.1021/la062802z
date added to LUP
2007-10-31 16:13:34
date last changed
2017-01-01 05:16:09
@article{46eaac74-824e-4d5c-8176-3a3e12f93501,
  abstract     = {Water-based copolymer dispersions were prepared using methyl methacrylate (MMA), ethyl acrylate (EA) (MMA/EA = 1:2), and a series of nonionic polymerizable surfactants, i.e., "surfmers" based on poly(ethylene glycol)-(meth)acrylates. The latexes were compared with the behavior of a conventionally stabilized (nonionic nonylphenol ethoxylate, NP100 with 84 ethylene oxide units) dispersion with the same MMA-EA composition (PMMAEA). A number of techniques were employed in order to characterize structure, dynamics, and film formation properties: solution/solid-state NMR, dynamic/static light scattering (DLS/SLS), differential scanning calorimetry (DSC), tensile/shear mode dynamic mechanical thermal analysis (DMTA), and atomic force microscopy (AFM). The surfmers were found to be miscible with the MMA-EA copolymer at room temperature, with 46-85 mol % of the reacted surfmer detected at the particle surfaces, and the remaining part buried in the particle bulk. In contrast, the NP100 surfactant formed a separate interphase between the copolymer particles with no mixing detected at room temperature or at 90 degrees C. For a 4.0% dry weight concentration, NP100 phase separated and further crystallized at room temperature over a period of several months. Composition fluctuations related to a limited blockiness on a length scale above similar to 2 nm were detected for PMMAEA particles, whereas the surfmer particles were found to be homogeneous also below this limit. On a particle-particle level, the dispersions tended to form colloidal crystals unless hindered by a broadened particle size distribution or, in the case of PMMAEA, by the action of NP100. Finally, a surface roughness (R-q) master plot was constructed for data above the glass transition temperature (T-g) from T-g + 11 degrees C to T-g + 57 degrees C and compared with the complex shear modulus over 11 frequency decades. Shift factors from the 2 methods obeyed the same Williams-Landel-Ferry (WLF) temperature dependence, thus connecting the long-time surface flattening process to the rheological behavior of the copolymer.},
  author       = {Schantz, Staffan and Carlsson, Hans T. and Andersson, Thomas and Erkselius, Stefan and Larsson, Anders and Karlsson, Ola},
  issn         = {0743-7463},
  keyword      = {REACTIVE SURFACTANTS,C-13 NMR-SPECTROSCOPY,SEQUENCE DISTRIBUTION,HETEROPHASE POLYMERIZATION,ENERGY-TRANSFER,FORMATION BEHAVIOR,COPOLYMER LATEXES,CHAIN-LENGTH 3,PRESSURE-SENSITIVE ADHESIVES,ATOMIC-FORCE MICROSCOPY},
  language     = {eng},
  number       = {7},
  pages        = {3590--3602},
  publisher    = {The American Chemical Society},
  series       = {Langmuir},
  title        = {Poly(methyl methacrylate-co-ethyl acrylate) latex particles with poly(ethylene glycol) grafts: Structure and film formation},
  url          = {http://dx.doi.org/10.1021/la062802z},
  volume       = {23},
  year         = {2007},
}