Surface-active fluorocarbon end-functionalized polylactides

Narrainen, Amilcar Pillay; Eggleston, Stuart M.; Clarke, Nigel; Thompson, Richard L.

doi:10.1016/j.polymer.2006.09.050

Cited by 23 publications

(34 citation statements)

References 28 publications

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“…There is a clear increase in z* as a function of  b for every xOHdPEy, which is in keeping with our previous observations for other end-functional additives. 7,8,21 However, in contrast to many of our other studies, we observe that z* typically grows almost linearly with increasing  b up to a maximum value at  b = 0.16. In earlier studies where there was also evidence of significant micellisation, z* was seen to increase sharply with initial increasing concentration, before reaching a plateau at some value, which was consistent with the onset of aggregation.…”

Section: Surface and Interfacial Activity Of Xohdpey In Blended Filmscontrasting

confidence: 99%

“…45 The observation of aggregation numbers slightly greater than one does suggest that there is some attraction between the polar end functional groups when dispersed in a non-polar PE matrix, possibly resulting in dimer formation. Nevertheless, there was no evidence for large aggregates as we have seen previously for 4×C 8 …”

Section: I(qt) T / Pssupporting

confidence: 47%

“…[7][8][9][10][11][12][13][14][15][16] A key feature of these additives is that the judicious placement of the functional groups on the chain ends can deliver an exceptional degree of surface modification with a very small proportion of hydrophobic component in the polymer. This generic structure is very effective in terms of contributing to surface modification whilst having a relatively small tendency towards aggregation.…”

Section: Introductionmentioning

confidence: 99%

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Multihydroxyl End Functional Polyethylenes: Synthesis, Bulk and Interfacial Properties of Polymer Surfactants

et al. 2014

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(2014) 'Multihydroxyl end functional polyethylenes : synthesis, bulk and interfacial properties of polymer surfactants. ', Macromolecules., 47 (6). pp. 2062', Macromolecules., 47 (6). pp. -2071 Further information on publisher's website:http://dx.doi.org/10.1021/ma402158bPublisher's copyright statement:This document is the Accepted Manuscript version of a Published Work that appeared in nal form in Macromolecules, copyright c American Chemical Society after peer review and technical editing by the publisher. To access the nal edited and published work see http://dx.doi.org/10.1021/ma402158bAdditional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. for polar interfaces, are thermally stable up to ~ 250 °C, and to have similar crystallinity and dynamics to their unfunctionalised homopolymers analogues. The polymers segregated strongly to silicon oxide interfaces, with adsorbed layers forming spontaneously at annealed polymer interfaces, having surface excess concentrations approaching 2 R g , and a maximum areal density of approximately 0.6 adsorbed chains per nm 2 . This interfacial activity is achieved almost without detriment to the bulk physical properties of the polymer as evidenced by thermal analysis, quasi-elastic neutron scattering and smallangle neutron scattering (SANS). SANS experiments show little evidence for aggregation of the dihydroxyl functionalized polymers in blends with PE homopolymers, which is thought to explain why these additives have particularly strong interfacial adsorption, even at relatively high concentrations. A modest level of segregation of the additives to exposed blend surfaces was also seen, particularly when the additive molecular weight was significantly lower than that of the matrix. We attribute this to a combination of the relatively low molecular weight of the additives and the marginally lower surface energy associated with deuterated polymers.3

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Section: Surface and Interfacial Activity Of Xohdpey In Blended Filmscontrasting

confidence: 99%

Section: I(qt) T / Pssupporting

confidence: 47%

Section: Introductionmentioning

confidence: 99%

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Multihydroxyl End Functional Polyethylenes: Synthesis, Bulk and Interfacial Properties of Polymer Surfactants

et al. 2014

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“…Moreover, the low molecular weight polymer additive can easily be incorporated into the matrix polymer during a processing step; surface migration occurring whilst the polymer is still in the melt, above the glass transition or in the presence of solvent. This has been shown to be the case for both spin coating of thin films [27][28][29][30][31][32][33][34][35] and electrospinning of fibres. 44 The polymer additive approach offers one further advantage over the methods mentioned above in that functionalised additives, depending on the nature of the functional group, have the ability to functionalise buried interfaces as well as air-polymer surfaces.…”

Section: Introductionmentioning

confidence: 85%

“…The functionalized additives behave largely like macromolecular surfactants 27,28 in so much that the functional groups are tethered to the chain-end of a polymer which is preferably identical to (or a least compatible with) the bulk polymer whose surface is to be modified. Moreover, it is a very versatile concept and a wide range of polymer additives have been prepared by a variety of polymerization mechanisms including polystyrene and poly(methyl methacrylate) by atom transfer radical polymerization [29][30][31][32] polylactide by ring opening polymerization 33 , polystyrene, polyisoprene and polybutadiene by anionic polymerization 34 and polyethylene 35 via the hydrogenation of high 1,4-polybutadiene prepared by anionic polymerization. Whereas the addition of functional additives is by no means the only way to modify surface properties, the described concept has several advantages over other methods of surface modification such as plasma treatment, 14,[36][37][38] wet chemical modification [39][40][41] and the application of polymeric surface coatings.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterisation of end-functionalised poly(N-vinylpyrrolidone) additives by reversible addition–fragmentation transfer polymerisation

et al. 2013

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(2013) 'Synthesis and characterisation of end-functionalised poly(N-vinylpyrrolidone) additives by reversible additionfragmentation transfer polymerisation.', Polymer chemistry., 4 (9). pp. 2815-2827. Further information on publisher's website:http://dx.doi.org/10.1039/c3py00041aPublisher's copyright statement:Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. Abstract. We describe herein the synthesis of a series of multi-end functionalized poly(Nvinyl pyrrolidone) (PVP) additives bearing two or three C 8 F 17 fluoroalkyl (CF) groups, designed as additives to modify surface properties. The PVP additives were prepared by reversible addition-fragmentation transfer (RAFT) polymerization, with end functionality imparted via the use of CF functionalized chain transfer agents (CTAs). The resulting PVP additives, when used in modest quantities dispersed in thin films of an unmodified PVP matrix significantly reduce the surface energy, rendering their surfaces more hydrophobic and lipophobic. This is achieved by virtue of the low surface energy of the pendant C 8 F 17 end groups which cause the additive to spontaneously surface segregate during the spin coating process. The resulting thin films have been characterized by static contact angle measurements using dodecane as the contact fluid, and the impact of additive molecular weight, matrix molecular weight, the number of CF groups and additive concentration upon surface properties is reported herein. Significant increases in contact angle were observed with increasing additive concentration, up to a critical aggregation concentration (CAC). Increasing the number of CF groups (from 2 to 3); reducing additive molecular weight or increasing the matrix molecular weight, resulted in increased contact angles and hence surface lipophobicity. Rutherford backscattering (RBS) analysis was performed on films containing varying concentrations of additive, in order to quantitatively measure the nearsurface fluorine concentration of these films. The results of these experiments were in excellent agreement with those obtained by contact angle analysis, confirming the surface activity and low surface energy of the additives.

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Recoverable surface modification using dendritically fluorocarbon‐functionalized poly(methyl methacrylate)

Thompson

Narrainen

Eggleston

et al. 2007

J of Applied Polymer Sci

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Dendritically fluorocarbon‐functionalized poly(methyl methacrylate) (PMMA) has been explored as a robust surface‐modifying additive in PMMA blends. These functionalized materials, denoted FxPMMAy, where x is the number of C8F17 fluorocarbon groups per dendron connected to a PMMA chain of y kg/mol, have been synthesized by living radical polymerization. These materials adsorb efficiently to the surfaces of their blends with unfunctionalized PMMA, resulting in increased hydrophobicity and lipophobicity. Contact‐angle goniometry has indicated a substantial reduction in the surface energy toward polytetrafluoroethylene‐like surface properties in the case of pure F4PMMA8.6 and substantial, but incomplete fluorocarbon surface coverage at a lower FxPMMAy concentration. The partial coverage has been confirmed by Rutherford backscattering and, together with the weak dependence of the surface modification on the FxPMMAy structure, indicates incomplete equilibrium of the surface adsorption. The modified surfaces are quite durable with respect to abrasion under water but are progressively eroded when the double‐wipe test is carried out with acetone. FxPMMAy, dispersed in the remaining film, acts as a reservoir of spare functional groups, from which the damaged surface may be replenished, leading to the recovery of the modified surface properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

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Surface-active fluorocarbon end-functionalized polylactides

Cited by 23 publications

References 28 publications

Multihydroxyl End Functional Polyethylenes: Synthesis, Bulk and Interfacial Properties of Polymer Surfactants

Multihydroxyl End Functional Polyethylenes: Synthesis, Bulk and Interfacial Properties of Polymer Surfactants

Synthesis and characterisation of end-functionalised poly(N-vinylpyrrolidone) additives by reversible addition–fragmentation transfer polymerisation

Recoverable surface modification using dendritically fluorocarbon‐functionalized poly(methyl methacrylate)

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