Nitroxide-Mediated Radical Polymerization of 4-Vinylpyridine:  Study of the Pseudo-Living Character of the Reaction and Influence of Temperature and Nitroxide Concentration

Fischer, A.; Brembilla, Alain; Lochon, Pierre

doi:10.1021/ma990116j

Cited by 81 publications

(65 citation statements)

References 13 publications

(16 reference statements)

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“…P4VP 9615 was prepared by a method described by Fischer et al [23], and P4VP 15470 prepared according to the literature [24]. In a typical polymerization procedure, a two-necked round-bottom flask was loaded with an appropriate amount of TEMPO, 4VP, BPO, and/or (CH 3 CO) 2 O; degassed by an argon gas purge; and sealed off under vacuum.…”

Section: Preparation Of P4vpmentioning

confidence: 99%

Remarkable crystallization morphologies of poly(4-vinylpyridine) on single-walled carbon nanotubes in CO2-expanded liquids

Su¹,

Wei²,

Li³

et al. 2011

Express Polym. Lett.

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Abstract. Poly(4-vinylpyridine) (P4VP) is a widely studied polymer for applications in catalysis, humidity sensitive and antimicrobial materials due to its pyridine group exhibiting coordinative reactivity with transition metals. In this work, the non-covalent functionalization of single-walled carbon nanotubes (SWCNTs) with P4VP in CO 2 -expanded liquids (CXLs) is reported. It is found that P4VP stabilized SWCNTs show good dispersion in both organic solvent and aqueous solution (pH = 2). The ability to manipulate the dispersion state of CNTs in water with P4VP will likely benefit many biological applications, such as drug delivery and optical sensors. Furthermore, the structure and morphology of P4VP/SWCNTs composite are examined, with the focus on molecular weight of P4VP (MW-P4VP), the pressure of CXLs and the concentration of P4VP. It is amazing that the P4VP 15470 wrapping patterns undergo a notable morphological evolution from dotlike crystals to bottle brush-like, then to compact kebab-like, and then to widely-spaced dotted kebab patterns by facile pressure tuning in the higher polymer concentration series. In other words, the CXLs method enables superior control of the P4VP crystallization patterns on SWCNTs. Meanwhile, the CXL-assisted P4VP crystal growth mechanism on SWCNT is investigated, and the dominating growth mechanism is attributed to 'size dependent soft epitaxy' in P4VP 15470 /SWCNTs composites. We believe these studies would reveal great potential for P4VP in building up functional structures in CXLs that are responsive to environmental stimuli.

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Section: Preparation Of P4vpmentioning

confidence: 99%

Remarkable crystallization morphologies of poly(4-vinylpyridine) on single-walled carbon nanotubes in CO2-expanded liquids

Su¹,

Wei²,

Li³

et al. 2011

Express Polym. Lett.

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“…P4VP 8700 was prepared according to the literature [35], and P4VP 45 000 prepared by a method described by Fischer [36]. In a typical polymerization procedure, a two-necked round-bottom flask was loaded with an appropriate amount of TEMPO, 4VP, BPO, and/or (CH 3 CO) 2 O; degassed by an argon gas purge; and sealed off under vacuum.…”

Section: Preparation Of P4vpmentioning

confidence: 99%

Crystalline polymer decoration on multiwalled carbon nanotubes: MWCNT-induced P4VP periodic crystallization in CO2-expanded liquids

Liu¹,

Wei²,

Qin³

et al. 2011

Express Polym. Lett.

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Abstract. This work reports the functionalization of multi-walled carbon nanotubes (MWCNTs) with crystalline poly(4-vinylpyridine) (P4VP) in CO2-expanded liquids (CXLs). The structure and morphology of MWCNT-induced polymer crystallization are examined, with the focus on molecular weight of P4VP (MW-P4VP), the pressure of CXLs and the concentration of P4VP. First, it is observed that the crystallization morphologies for the P4VP/MWCNTs composite with a low molecular weight P4VP (LMW-P4VP) matrix could be finely controlled in CXLs, and it is surprising to find that the P4VP8700 wrapping patterns undergo a morphological evolution from dot crystals to dotted helical wrappings, and then to dense helical patterns by facile pressure tuning under lower polymer concentration. In other words, the CXLs method enables superior control of the P4VP crystallization patternings on MWCNTs, particularly efficient for LMW-P4VP at lower polymer concentration. Meanwhile, the CXL-assisted P4VP crystal growth mechanism on MWCNT is investigated, and the dominating growth mechanism is attributed to 'normal epitaxy' at lower P4VP concentration rather than 'soft epitaxy' at higher concentration. We believe that this work reports a new crystalline polymer wrapping approach in CXLs to noncovalent engineering of MWCNTs surfaces.

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“…This can be due to easier irreversible deactivation of long copolymer chains containing terminal nitroxyl groups (Scheme 2) [11,17].…”

Section: Nitroxide-terminated 4vp-an Copolymersmentioning

confidence: 99%

“…Polymers of welldefined structure and properties can be obtained using the advanced synthetic techniques, such as nitroxide-mediated radical polymerization (NMRP) [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. A quasiliving polymerization takes place at elevated temperatures (usually above 100 o C) in mixtures containing monomer, a thermal initiator [(dibenzoyl peroxide, 2,2΄-azobis(isobutyronitrile)] and a nitroxide stable radical.…”

Section: Introductionmentioning

confidence: 99%

“…Vinylpyridine polymers and their ionic derivatives rank among promising materials such as polyelectrolytes, polymeric reagents, membranes and in electrical applications [18]. So far, the NMRP studies of vinylpyridine monomers have been devoted mainly to their homopolymerization and copolymerization with styrene [11,17,19,20]. Yet the incorporation of other monomer units in polymer chains could modulate the properties of resulting products.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and quaternization of nitroxide-terminated poly(4-vinylpyridine-co-acrylonitrile) macroinitiators and related diblock copolymers

et al. 2010

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Nitroxide-terminated 4VP AN copolymers have been synthesized at 125 o C using an alkoxyamine (MAMA-SG1) as a unimolecular initiator. Their compositions were compared with those published for the conventional radical 4VP-AN copolymerization. To verify the initiation potential of the copolymers containing nitroxyl end groups, they were employed in chain extension with styrene (S). Both the prepared statistic copolymer macroinitiators and related diblock copolymers, poly(4VP-co-AN) and poly(4VP-co-AN)-block-poly(S), respectively, were quaternized with methyl iodide in N,N-dimethylformamide or methanol at ambient temperature. The size-exclusion chromatography and NMR were used for the characterization of the polymers; the completeness of the quaternization was checked by the IR spectrometry.

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Nitroxide-Mediated Radical Polymerization of 4-Vinylpyridine: Study of the Pseudo-Living Character of the Reaction and Influence of Temperature and Nitroxide Concentration

Cited by 81 publications

References 13 publications

Remarkable crystallization morphologies of poly(4-vinylpyridine) on single-walled carbon nanotubes in CO2-expanded liquids

Remarkable crystallization morphologies of poly(4-vinylpyridine) on single-walled carbon nanotubes in CO2-expanded liquids

Crystalline polymer decoration on multiwalled carbon nanotubes: MWCNT-induced P4VP periodic crystallization in CO2-expanded liquids

Synthesis and quaternization of nitroxide-terminated poly(4-vinylpyridine-co-acrylonitrile) macroinitiators and related diblock copolymers

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