Synthesis and surface activity of high and low surface energy multi-end functional polybutadiene additives

Kimani, Solomon M.; Hardman, Sarah J.; Clarke, Nigel; Thompson, Richard L.

doi:10.1039/c2sm07361g

Cited by 21 publications

(28 citation statements)

References 39 publications

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“…This functional group modification was carried out in DMF in the presence of sodium azide (NaN 3 ) according to an analogous procedure carried out in our group and reported elsewhere [79]. The successful conversion of alkyl bromide to alkyl azide was confirmed by 1 H-NMR (figure 2) in which the complete disappearance of the peak at δ 2.7-2.85 ppm [CH 2 -Br] was observed.…”

Section: Synthesis Of the Polystyrene 'Long' Arm Macromonomer-ps90mentioning

confidence: 99%

Synthesis and temperature gradient interaction chromatography of model asymmetric star polymers by the “macromonomer” approach

Agostini¹

2013

European Polymer Journal

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. (2013) 'Synthesis and temperature gradient interaction chromatography of model asymmetric star polymers by the "macromonomer"approach.', European polymer journal., 49 (9). pp. 2769-2784. Further information on publisher's website:http://dx.doi.org/10.1016/j.eurpolymj.2013.06.021Publisher's copyright statement: NOTICE: this is the author's version of a work that was accepted for publication in European Polymer Journal. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be re ected in this document. Changes may have been made to this work since it was submitted for publication. A de nitive version was subsequently published in European Polymer Journal, 49, 9, 2013Journal, 49, 9, , 10.1016Journal, 49, 9, /j.eurpolymj.2013.021. 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-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. Abstract. We describe herein the synthesis and characterisation of a series of asymmetric three arm polystyrene stars via the "macromonomer" approach. The stars have been designed as model polymers to probe branched polymer dynamics and in particular to establish the chain-length of side-arm which precipitates a change in the rheological properties of the resulting polymers from "linear-like" to "star-like". Thus, a homologous series of three arm stars have been prepared in which the molar mass of two (long) arms are fixed at 90 000 gmol -1 and the molar mass of the remaining (short) arm is varied from below the entanglement molecular weight (M e ) to above M e . The arms were prepared by living anionic polymerisation, resulting in well-defined chain lengths with narrow molecular weight distribution. In contrast to the usual chlorosilane coupling approach, the macromonomer approach involves the introduction of reactive chain-end functionalities on each of the arms, either through the use of a functionalised (protected) initiator or a functional end-capping agent, which allows the stars to be constructed by a simple condensation coupling reaction. In this study we will compare the relative efficiency of a Williamson and 'click' coupling reaction in producing the stars. Most significantly, although this approach maybe a little more time-consuming than the more common silane coupling reaction, in the present study the "long" arm may be produced in sufficient quantity such that all of the asymmetric stars are produced with long arms of identical molecular weight -the only remaining variable being the molecular weight of th...

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Section: Synthesis Of the Polystyrene 'Long' Arm Macromonomer-ps90mentioning

confidence: 99%

Synthesis and temperature gradient interaction chromatography of model asymmetric star polymers by the “macromonomer” approach

Agostini¹

2013

European Polymer Journal

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“…It should be noted that although these polyethylenes were produced by hydrogenation of polybutadiene, the route to making these materials differs significantly from that used for our earlier work on multhydroxyl end functionalized polybutadienes. 15 The reason for this is that the previously reported functionalized polybutadienes were end-functionalized by a click reaction and the end groups were not stable with respect to catalytic hydrogenation or deuteration. In the present work we therefore used an approach to end capping polybutadiene, followed by saturation with hydrogen or deuterium, which we have previously found to be a robust method for the production of analogous fluorocarbon end functionalised polyethylenes.…”

Section: Synthesis and Characterization Of Multi-hydroxyl End Functiomentioning

confidence: 99%

“…[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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Synthesis and surface activity of high and low surface energy multi-end functional polybutadiene additives

Cited by 21 publications

References 39 publications

Synthesis and temperature gradient interaction chromatography of model asymmetric star polymers by the “macromonomer” approach

Synthesis and temperature gradient interaction chromatography of model asymmetric star polymers by the “macromonomer” approach

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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