Novel multi end-functionalised polymers. Additives to modify polymer properties at surfaces and interfaces

Narrainen, Amilcar Pillay; Hutchings, Lian R.; Ansari, Imtiyaz; Clarke, Nigel; Thompson, Richard L.

doi:10.1039/b516439g

Cited by 21 publications

(32 citation statements)

References 16 publications

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“…Although a small number of previous studies have shown that low molecular weight fluorinated additives do successfully migrate to the surface during the electrospinning process 29,30 , to the best of our knowledge this is the first report of low surface energy polymeric additives being used for this purpose. We have recently shown [15][16][17][18][19]34 that polymeric fluoroalkyl additives with molecular weights as high as 40,000 gmol -1 are able to successfully surface segregate in thin films, although somewhat unsurprisingly, lower molecular additives and additives with a higher fluorine contact are more effective at generating significant changes in surface properties. Spontaneous surface segregationdriven by a reduction in surface energy -was shown to be an extremely efficient process and in some cases it was possible to generate poly(tetrafluoroethylene)-like surface properties during the spin coating of a polymer film containing substantially less that 1% (by weight) of additive 17 .…”

Section: Contact Angle Measurements Of Fibres Spun From Thfmentioning

confidence: 99%

“…Surface adsorption is spontaneous if there is an accompanying reduction in the surface energy and it is relatively straightforward to increase the hydrophobicity of polymer surfaces by the use of polymers functionalized with low surface energy fluorocarbon (CF) groups. We have recently shown in situ surface segregation to be a particularly effective approach for the surface functionalization of polymer thin films when relatively low molecular weight polymers carrying 2-4 CF groups at their chain-end are used as additives in low concentration [15][16][17][18][19] . Moreover, PTFE-like surface properties were achieved with as little as 0.1 wt % of an additive carrying 3 C 8 F 17 groups.…”

Section: Introductionmentioning

confidence: 99%

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Electrospinning Superhydrophobic Fibers Using Surface Segregating End-Functionalized Polymer Additives

et al. 2011

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. (2011) 'Electrospinning superhydrophobic bers using surface segregating end-functionalized polymer additives. ', Macromolecules., 44 (16). pp. 6461-6470. Further information on publisher's website:http://dx.doi.org/10.1021/ma200852zPublisher's copyright statement:This document is the Accepted Manuscript version of a Published Work that appeared in nal form in Macromolecules, copyright c 2011 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/ma200852z. 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. RECEIVED DATE (to be automatically inserted after your manuscript is accepted if requiredaccording to the journal that you are submitting your paper to) † Chemistry Department, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia.ABSTRACT: We describe here a facile route for the in situ modification of the surface properties of fibres produced by electrospinning polystyrene containing small quantities of compatible polymer additives, end functionalized with 1-3 fluoroalkyl groups. Such additives undergo spontaneous surface segregation during the electrospinning process resulting in fibres with low surface energy, fluorine rich, superhydrophobic surfaces. Surface properties were analyzed using static contact angle measurements (with water as the contact fluid) and X-ray photoelectron spectroscopy. We report the effect of a number of parameters on the surface properties of the resulting polystyrene fibres including the molecular weight and concentration of functionalized additive, the number of fluoroalkyl groups, the effect of annealing and spinning solvent. The majority of the fibres were successfully produced using THF as the spinning 2 solvent and fibres with a contact angle of approximately 150 degrees were attainable. However, preliminary investigations using a blend of polystyrene and 4% by weight of such an additive, endfunctionalized with 3 C 8 F 17 group in a mixed solvent of DMF/THF (3:1 v/v) resulted in a mat of fibres with a superhydrophobic surface and a contact angle of 158 degrees.

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Section: Contact Angle Measurements Of Fibres Spun From Thfmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electrospinning Superhydrophobic Fibers Using Surface Segregating End-Functionalized Polymer Additives

et al. 2011

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“…[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%

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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“…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: 99%

“…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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Novel multi end-functionalised polymers. Additives to modify polymer properties at surfaces and interfaces

Cited by 21 publications

References 16 publications

Electrospinning Superhydrophobic Fibers Using Surface Segregating End-Functionalized Polymer Additives

Electrospinning Superhydrophobic Fibers Using Surface Segregating End-Functionalized Polymer Additives

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

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