Precise synthesis and surface structures of architectural per- and semifluorinated polymers with well-defined structures

Hirao, Akira; Sugiyama, Kenji; Yokoyama, Haruki

doi:10.1016/j.progpolymsci.2007.08.001

Cited by 147 publications

(134 citation statements)

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“…Hirao [42][43][44] prepared polystyrene polymers by anionic polymerization end capped with up to 32 C 8 F 17 groups by an iterative methodology that involved many reaction steps. When these end capped polymers in their pure state -not as additives - 30 were cast into films, it was found that surface properties were (not surprisingly) strongly dependant on the number of CF groups.…”

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confidence: 99%

Multi-end functionalised polymer additives synthesised by living anionic polymerisation—the impact of additive molecular structure upon surface properties

Sarih

Thompson

2011

Polym. Chem.

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. (2011) 'Multi-end functionalised polymer additives synthesised by living anionic polymerisation-the impact of additive molecular structure upon surface properties.', Polymer chemistry., 2 (4). pp. 851-861. Further information on publisher's website:http://dx.doi.org/10.1039/c0py00362jPublisher'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 Numerous applications require specific properties at polymer surfaces that differ from the bulk. Herein we describe the novel synthesis of a series of multi-end functionalised poly(styrene) and poly(isoprene) additives carrying 1 to 3 fluoroalkyl (CF) groups. The additives 10 were prepared by end capping the living chain ends of polymers prepared via living anionic polymerisation. The resulting polymers have been used as additives to render the surface of polymer films hydrophobic/lipophobic and we have characterised these polymer films using static contact angle measurements with water as the contact fluid. We have found that additive molecular weight, the number of CF groups, additive concentration and annealing conditions have a 15 significant impact upon the resulting surface properties. Increasing the additive concentration and/or number of CF groups resulted in higher contact angles whereas increasing the molecular weight of additive reduced contact angles and surface h ydrophobicity. It has been discovered that these additives undergo rapid adsorption to the surface of a thin film in the time taken to produce the film by spin coating and the result is significantly enhanced surface properties. Annealing 20 polystyrene films above the glass transition temperature revealed some interesting behaviour in so much that it demonstrated that on many occasions it is preferable to anneal films containing very small quantities of additive rather than to simply add greater quantities of additive. In addition to contact angles measurements, Rutherford backscattering analysis (RBS) has been carried out on examples of modified poly(isoprene) films to quantitatively analyse the effect of additive 25 molecular weight and number of fluoroalkyl groups on the near surface elemental composition of the modified thin films and confirming the relationship (described above) between these additive molecular parameters and surface adsorption. Finally, we have described a model which compares the behaviour of the additives in thin films to surfactants in solution.

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confidence: 99%

Multi-end functionalised polymer additives synthesised by living anionic polymerisation—the impact of additive molecular structure upon surface properties

Sarih

Thompson

2011

Polym. Chem.

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“…[ 54 ] Especially, multi-component systems are of high priority. There are many applied opportunities for designing multiple-responsive polymers, in particular polymer brushes or nanogels serving as protein/cell adhesion sites and drug delivery platforms.…”

Section: Three-and Four-component Polymersmentioning

confidence: 99%

Smart Polymers with Special Wettability

Chang

Zhang

Sun

2016

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Surface wettability plays a key role in addressing issues ranging from basic life activities to our daily life, and thus being able to control it is an attractive goal. Learning from nature, both of its structure and function, brings us much inspiration in designing smart polymers to tackle this major challenge. Life functions particularly depend on biomolecular recognition-induced interfacial properties from the aqueous phase onto either "soft" cell and tissue or "hard" inorganic bone and tooth surfaces. The driving force is noncovalent weak interactions rather than strong covalent combinations. An overview is provided of the weak interactions that perform vital actions in mediating biological processes, which serve as a basis for elaborating multi-component polymers with special wettabilities. The role of smart polymers from molecular recognitions to macroscopic properties are highlighted. The rationale is that highly selective weak interactions are capable of creating a dynamic synergetic communication in the building components of polymers. Biomolecules could selectively induce conformational transitions of polymer chains, and then drive a switching of physicochemical properties, e.g., roughness, stiffness and compositions, which are an integrated embodiment of macroscopic surface wettabilities.

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“…[1][2][3][4][5][6][7][8][9][10][11] In particular, star polymers and dendrimer-like star-branched polymers belong to the class of well-defined hyperbranched macromolecules. Much research effort has been expended over the last three decades in the synthesis of star and dendritic polymers and the characterization of their structures and properties.…”

Section: Introductionmentioning

confidence: 99%

“…17 PMMA-G3a and PMMA-G3a were synthesized by repeating the two reactions involving a linking reaction of pre-made living anionic PMMA with either two or four 3-tert-butyldimethylsilyloxymethylphenyl groups with chain-end-functionalized PMMAs. 6,13,15 In addition, a linear PS was purchased from Varian Inc. All other chemicals were supplied from Aldrich Chemical Co. The weight-and number-average molecular weights ( and ) of all the polymers were measured by using vapor pressure osmometry and static light scattering.…”

Section: Introductionmentioning

confidence: 99%

“…The weight-and number-average molecular weights ( and ) of all the polymers were measured by using vapor pressure osmometry and static light scattering. 6,13,15,17 The and results are summarized in Table I. For each polymer sample, 1.0 wt% solutions were prepared in a good and a Θ solvent conditions: tetrahydrofuran (THF) at 25 o C was chosen as a good solvent condition for all the polymers while cyclohexane at 35 o C was used as a Θ solvent condition for the linear and star PS polymers and 4-heptanone at 25 o C was chosen as a Θ solvent condition for the PMMA-G3a and PMMA-G3a polymers.…”

Section: Introductionmentioning

confidence: 99%

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X-ray scattering studies on molecular structures of star and dendritic polymers

Jin

Yoon

et al. 2008

Macromol. Res.

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We studied the molecular shapes and structural characteristics of a 33-armed, star polystyrene (PS-33A) and two 3 r d -generation, dendrimer-like, star-branched poly(methyl methacrylate)s with different architectures (PMMA-G3a and PMMA-3Gb) and 32 end-branches under good solvent and theta (Θ) solvent conditions by using synchrotron small angle X-ray scattering (SAXS). The SAXS analyses were used to determine the structural details of the star PS and dendrimer-like, star-branched PMMA polymers. PS-33A had a fuzzy-spherical shape, whereas PMMA-G3a and PMMA-G3b had fuzzy-ellipsoidal shapes of similar size, despite their different chemical architectures. The star PS polymer's arms were more extended than those of linear polystyrene. Furthermore, the branches of the dendrimer-like, star-branched polymers were more extended than those of the star PS polymer, despite having almost the same number of branches as PS-33A. The differences between the internal chain structures of these materials was attributed to their different chemical architectures.

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Precise synthesis and surface structures of architectural per- and semifluorinated polymers with well-defined structures

Cited by 147 publications

References 133 publications

Multi-end functionalised polymer additives synthesised by living anionic polymerisation—the impact of additive molecular structure upon surface properties

Multi-end functionalised polymer additives synthesised by living anionic polymerisation—the impact of additive molecular structure upon surface properties

Smart Polymers with Special Wettability

X-ray scattering studies on molecular structures of star and dendritic polymers

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