Engineering low surface energy polymers through molecular design: synthetic routes to fluorinated polystyrene-based block copolymers

Andruzzi, Luisa; Chiellini, Emo; Galli, Giancarlo; Li, Xuefa; Kang, Seok Ho; Ober, Christopher K.

doi:10.1039/b200891b

Cited by 76 publications

(75 citation statements)

References 32 publications

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“…This hexagonal orientation is possible due to immiscibility and affinity parameters. [3,6,14,[20][21][22] It should be noted that the length and nature of the fluorocarbon chain can change the orientation of the -CF 3 groups. Finally, from the results in Table 3 it is clear that SBF exhibits enhanced roughness when compared with the precursor SB.…”

Section: Atomic Force Microscopy (Afm)mentioning

confidence: 98%

“…Side groups, -CF 2 -and -CF 3 can easily orient in the surface exhibiting high affinity with air and immiscibility with the copolymer backbone. [3,6,14,[20][21][22] Fluorocarbon groups can migrate onto the surface, creating a surface fully occupied by F atoms. From contact angle measurements SBF showed a contact angle of 113.68 higher than that of its precursor SB 1,2 (106.18).…”

Section: Contact Angle Measurementsmentioning

confidence: 99%

“…[1] Besides hydrophobicity, fluoropolymers have many other interesting properties, such as chemical inertness, thermal stability, low relative permittivity, lipophobicity, low friction coefficient. [2][3][4][5] Due to these properties, many applications such as coatings, microfiltration, microelectronics, antifouling, antiwetting and optics can be envisaged. [3,[6][7][8][9][10][11] It is therefore clear that the most significant property of fluoropolymers is their hydrophobicity which eventually leads to modified surface properties.…”

Section: Introductionmentioning

confidence: 99%

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Modified Diblock Copolymer Bearing Fluoro Groups and Evaluation of its Hydrophobic Properties

Politakos

Kortaberría

Zalakain

et al. 2012

Macromolecular Symposia

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Summary:The major scope of the presented work is the characterization and evaluation of hydrophobicity of novel copolymers of the PS-b-PB 1,2 type, modified with perfluorooctanoyl chloride [PS: polystyrene, PB 1,2 : poly(butadiene) with 100% 1,2-microstructure]. Fluoro atoms in polymers can create hydrophobic surfaces with low surface energy. The fluorinated groups can migrate and possible orient in the outermost surface of the polymeric thin film. Characterization in the modified block copolymer was conducted with carbon nuclear magnetic resonance ( 13 C-NMR) and thermogravimetric analysis (TGA) to evaluate the structure. Contact angle measurements were also conducted to verify the hydrophobicity of the fluorinated copolymer. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to depict the structure of the material. The obtained results showed that indeed the fluorinated copolymer exhibits high hydrophobicity (low surface energy material) with significant structural differences from its precursor.

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Section: Atomic Force Microscopy (Afm)mentioning

confidence: 98%

Section: Contact Angle Measurementsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Modified Diblock Copolymer Bearing Fluoro Groups and Evaluation of its Hydrophobic Properties

Politakos

Kortaberría

Zalakain

et al. 2012

Macromolecular Symposia

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“…[8] Some of us have recently investigated various free radical polymerizations [9][10][11][12] of different CDcomplexed vinyl derivatives and some other types of monomers under surfactant-free conditions in aqueous media. [13,14] Others of us are interested in liquid crystalline fluorinated materials that exhibit low surface energy properties for application in non-stick coating films, fillings, and curing resins, [15,16] polyvinylcyclopropanes being special architectures of such polymers. [17] While there are many synthetic methods to prepare such polymers, [18] so far fluorinated polyvinylcyclopropanes have never been prepared in aqueous solution.…”

Section: Introductionmentioning

confidence: 99%

Novel Polymerization of Fluorinated 2‐Vinylcyclopropane in Aqueous Solution via Cyclodextrin Complexes

Choi

Kretschmann

Ritter

et al. 2003

Macro Chemistry & Physics

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We report on the first examples of the free radical polymerization of a fluorinated 2‐vinylcyclopropane 1 and its copolymerization with an alkyl 2‐vinylcyclopropane 2 in aqueous solution via their host‐guest complexation with a random methylated β‐cyclodextrin (RAMEB) using a water‐soluble initiator (VA50). Upon polymerization, the dethreaded cyclodextrin remained in water solution, whereas the water‐insoluble polymer precipitated out and was isolated. The polymers prepared exhibited mesophase behavior over a wide range of temperature. Both Tg and Ti of the copolymers increased linearly with the amount of fluorinated co‐units.Complexation of fluorinated vinylcyclopropane 1 with RAMEB and polymerization in water solution.magnified imageComplexation of fluorinated vinylcyclopropane 1 with RAMEB and polymerization in water solution.

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“…[ 8 , 9 ] Other notable applications include generation of low-energy surfaces, solvent-resistant coatings, [10][11][12][13][14][15][16][17][18][19][20] and surface-modifi ed membranes. [ 21 ] It is well known that block copolymers microphase separate into well-ordered nanostructures if the product of χ N , where χ is the Flory-Huggins-Sakurada segmental interaction parameter and N is the total number of segments in the copolymer, is suffi ciently large.…”

mentioning

confidence: 99%

Thin Films of Semifluorinated Block Copolymers Prepared by ATRP

Irita

Chen

et al. 2011

Macro Chemistry & Physics

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A symmetric diblock copolymer, poly(pentafl uorostyrene-b -styrene) (PPFS-b -PS), is synthesized by atom transfer radical polymerization (ATRP). The behavior of PPFS-b -PS thin fi lms on silicon wafers is investigated. Lamellar microdomains oriented parallel to the fi lm surface are formed when the thin fi lms are heated to 220 ° C for 24 h, due to preferential interfacial interactions and the low surface energy of the PPFS. An electric fi eld is used to overcome the low surface energy of the fl uorinated block and preferential interactions with the substrate so as to force the lamellar microdomains to orient normal to the surface.for lithium ion conductivity in solid-state polymer battery applications. [ 8 , 9 ] Other notable applications include generation of low-energy surfaces, solvent-resistant coatings, [10][11][12][13][14][15][16][17][18][19][20] and surface-modifi ed membranes. [ 21 ] It is well known that block copolymers microphase separate into well-ordered nanostructures if the product of χ N , where χ is the Flory-Huggins-Sakurada segmental interaction parameter and N is the total number of segments in the copolymer, is suffi ciently large. The nature of the microdomain morphology ranges from body-centered cubic arrays of spheres to hexagonally packed cylinders to gyroid to lamellae, depending on the volume fraction of the components. The size scale of the microdomains is comparable to the dimensions of the polymer chain and, as such, is typically tens of nanometers in size. The size can be varied by changing the molecular weight. [ 22 ] In the case of semifl uorinated block copolymers, χ is quite large, due to the non-favorable interactions between the blocks. [ 23 ] These materials are in the strong segregation limit and the perfl uorinated block is more rigid than the protonated block and, therefore, can exhibit unique phase behavior. [ 24 ] In addition, since χ is large, then N can be made small while retaining the microphase-separated morphology and, as such, very small domain sizes can be achieved. Yet, for any application, controlling the orientation of the microdomains in thin fi lms is important and overcoming the low surface energy of the perfl uorinated block and preferential interfacial interactions is necessary. In addition, the controlled synthesis of semifl uorinated block copolymers

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Engineering low surface energy polymers through molecular design: synthetic routes to fluorinated polystyrene-based block copolymers

Cited by 76 publications

References 32 publications

Modified Diblock Copolymer Bearing Fluoro Groups and Evaluation of its Hydrophobic Properties

Modified Diblock Copolymer Bearing Fluoro Groups and Evaluation of its Hydrophobic Properties

Novel Polymerization of Fluorinated 2‐Vinylcyclopropane in Aqueous Solution via Cyclodextrin Complexes

Thin Films of Semifluorinated Block Copolymers Prepared by ATRP

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