Mechanistic Studies on Template Polymerization in Porous Isotactic Poly(methyl methacrylate) Thin Films by Radical Polymerization and Postpolymerization of Methacrylate Derivatives

Ajiro, Hiroharu; Kamei, Daisuke; Akashi, Mitsuru

doi:10.1021/ma8028634

Cited by 17 publications

(16 citation statements)

References 42 publications

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“…The C.E. of the radical polymerization in water at 70 °C was 27%, a value which corresponds well to previous work, although this value was reported from a quantitative reaction in acetonitrile/water over a short period of time, suggesting that solvent effects could be important. When the reaction time was 24 h, the C.E.…”

Section: Resultssupporting

confidence: 91%

Temperature effect on template polymerization of methacrylic acid using stereocomplex formation on quartz crystal microbalance substrates

Ajiro

Ueyama

Akashi

2014

J. Polym. Sci. Part A: Polym. Chem.

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The radical polymerization of methacrylic acid (MAA) at 0, 20, 40, and 70 C was achieved in porous isotactic (it-) poly (methyl methacrylate) (PMMA) films on quartz crystal microbalance (QCM) substrates, which were prepared by layer-by-layer assembled stereocomplex films of it-PMMA and syndiotactic (st-) poly(methacrylic acid) (PMAA), followed by the subsequent extraction of st-PMAA. The MAA polymerization yields increased from 35 to 75%, as the polymerization temperature increased from 0 to 70 C. Furthermore, infrared spectroscopy revealed that a higher polymerization temperature is necessary to form it-PMMA/st-PMAA stereocomplexes via stereoregular polymerization manner that resemble native it-PMMA/st-PMAA stereocomplexes. X-ray diffraction pattern of porous it-PMMA were also investigated for reaction fields.

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Section: Resultssupporting

confidence: 91%

Temperature effect on template polymerization of methacrylic acid using stereocomplex formation on quartz crystal microbalance substrates

Ajiro

Ueyama

Akashi

2014

J. Polym. Sci. Part A: Polym. Chem.

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“…As a consequence, the control of the stereoreglarity and of the molecular weight of it‐PMMA was realized by the template polymerization method using porous template films 124. We also cralified stability125–129 of the films and the polymerization mechanism using the porous it‐PMMA films in detail 130–132…”

Section: Stereocomplex Nanofilms and Their Biomedical Functionsmentioning

confidence: 99%

Layer‐by‐Layer Assembly Through Weak Interactions and Their Biomedical Applications

et al. 2011

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The surface design and control of substrates with nanometer- or micrometer-sized polymer films are of considerable interest for both fundamental and applied studies in the biomedical field because of the required surface properties. The layer-by-layer (LbL) technique was discovered in 1991 by Decher and co-workers for the fabrication of polymer multilayers constructed mainly through electrostatic interaction. The scope and applicability of this LbL assembly has been extended by introducing molecularly regular conformations of polymers or proteins by employing, for the first time, weak interactions such as van der Waals interactions and biological recognition. Since these weak interactions are the sum of the attractive or repulsive forces between parts of the same molecule, they allow macromolecules to be easily arranged into the most stable conformation in a LbL film. By applying this characteristic feature, the template polymerization of stereoregular polymers, stereoregular control of surface biological properties, drastic morphological control of biodegradable nano materials, and the development of three-dimensional cellular multilayers as a tissue model were successfully achieved. It is expected that LbL assembly using weak interactions will promote further interest into fundamental and applied studies on the design of surface chemistry in the biomedical field.

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“…Distilled MAA was dissolved in ultrapure water to prepare a 35 mM monomer solution, and the porous it-PMMA thin films on the QCM substrate were added to the solution. [32][33][34] Dry nitrogen gas was handled at room temperature for more than 15 min before use. Then, VA-044 was added under nitrogen atmosphere and heated to 40 1C for 2 h ([I]/[M] ¼ 1/20).…”

Section: Template Polymerization On Qcm Substratementioning

confidence: 99%

“…Surprisingly, we found that the porous film functions as an effective template for the polymerization system. [31][32][33][34] This technique gave strict control of the polymethacrylate structure, including a high stereoregularity and a low molecular weight distribution (polydispersity: PDI), measured by the radical method.…”

Section: Introductionmentioning

confidence: 99%

A study on template effects using irregular porous isotactic poly(methyl methacrylate) films constructed with syndiotactic rich poly(methacrylic acid) and isotactic poly(methyl methacrylate)

Maegawa

Ajiro

Kamei

et al. 2013

Polym J

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To investigate the stereocomplex formation efficiency with various syndiotactic-poly(methacrylic acids) (st-PMAAs) after the extraction of the syndiotactic-rich PMAA from stereocomplex film, the low syndiotacticity of PMAA (rr ¼ 78%) was used to prepare irregular isotactic poly(methyl methacrylate) (it-PMMA)/st-PMAA (rr ¼ 78%) stereocomplex thin films on substrates. The resultant irregular porous it-PMMA thin films showed effective incorporation of st-PMAA (rr ¼ 78 and 96%), suggesting a structural rearrangement of the it-PMMA main chain. However, the template polymerization in porous it-PMMA thin films with a monomer of methacrylic acid resulted in a stereoregular replica of the st-PMAA, without any rearrangement of the it-PMMA. When irregular stereocomplex formation was employed, these results demonstrated a clear difference between polymer-polymer interactions and polymer-monomer interactions and indicated that a high stereoregularity was necessary to achieve strict control of the stereoregular template polymerization on the porous thin film.

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Mechanistic Studies on Template Polymerization in Porous Isotactic Poly(methyl methacrylate) Thin Films by Radical Polymerization and Postpolymerization of Methacrylate Derivatives

Cited by 17 publications

References 42 publications

Temperature effect on template polymerization of methacrylic acid using stereocomplex formation on quartz crystal microbalance substrates

Temperature effect on template polymerization of methacrylic acid using stereocomplex formation on quartz crystal microbalance substrates

Layer‐by‐Layer Assembly Through Weak Interactions and Their Biomedical Applications

A study on template effects using irregular porous isotactic poly(methyl methacrylate) films constructed with syndiotactic rich poly(methacrylic acid) and isotactic poly(methyl methacrylate)

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