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Polystyrene-b-poly(tert-butyl acrylate) and polystyrene-b-poly(acrylic acid) dendrimer-like copolymers: Two-dimensional self-assembly at the air-water interface

dc.rights.licenseopen
hal.structure.identifierDepartment of Chemistry and Center for Macromolecular Science and Engineering
dc.contributor.authorJONCHERAY, Thomas J.
hal.structure.identifierDepartment of Chemistry and Center for Macromolecular Science and Engineering
dc.contributor.authorBERNARD, Sophie A.
hal.structure.identifierDepartment of Chemistry and Center for Macromolecular Science and Engineering
hal.structure.identifierLaboratoire de Chimie des polymères organiques [LCPO]
dc.contributor.authorMATMOUR, Rachid
hal.structure.identifierInstitut de Chimie Moléculaire et des Matériaux d'Orsay [ICMMO]
dc.contributor.authorLEPOITTEVIN, Bénédicte
hal.structure.identifierInstitut de Chimie Moléculaire et des Matériaux d'Orsay [ICMMO]
dc.contributor.authorEL-KHOURI, Rita J.
hal.structure.identifierLaboratoire de Chimie des polymères organiques [LCPO]
hal.structure.identifierTeam 1 LCPO : Polymerization Catalyses & Engineering
dc.contributor.authorTATON, Daniel
hal.structure.identifierLaboratoire de Chimie des polymères organiques [LCPO]
dc.contributor.authorGNANOU, Yves
hal.structure.identifierDepartment of Chemistry and Center for Macromolecular Science and Engineering
dc.contributor.authorDURAN, Randolph S.
dc.date.accessioned2020
dc.date.available2020
dc.date.issued2007
dc.identifier.issn0743-7463
dc.identifier.urihttps://oskar-bordeaux.fr/handle/20.500.12278/20825
dc.description.abstractEnThe two-dimensional self-assembly at the air/water (A/W) interface of two dendrimer-like copolymers based on polystyrene and poly(tert-butyl acrylate) (PS-b-PtBA) or poly(acrylic acid) (PS-b-PAA) was investigated through surface pressure measurements (isotherms, isochores, and compression-expansion hysteresis experiments) and atomic force microscopy (AFM) imaging. The two dendrimer-like block copolymers have an 8-arm PS core (M-n = 10 000 g/mol, similar to 12 styrene repeat units per arm) with a 16-arm PtBA (M-n = 230 000 g/mol, similar to 112 tert-butyl acrylate repeat units per arm) or PAA (M-n = 129 000 g/mol, similar to 112 acrylic acid repeat units per arm) corona. The PS-b-PtBA sample forms stable Langmuir monolayers and aggregates into circular surface micelles up to a plateau observed in the corresponding isotherm around 24 mN/m. Beyond this threshold, the monolayers collapse above the interface, resulting in the formation of large and irregular desorbed aggregates. The PS-b-PAA sample has ionizable carboxylic acid groups, and its A/W interfacial self-assembly was therefore investigated for various subphase pH values. Under basic conditions (pH = 11), the carboxylic acid groups are deprotonated, and the PS-b-PAA sample is therefore highly water-soluble and does not form stable monolayers, instead irreversibly dissolving in the aqueous subphase. Under acidic conditions (pH = 2.5), the PS-b-PAA sample is less water-soluble and becomes surface-active. The pseudoplateau observed in the isotherm around 5 mN/m corresponds to a pancake-to-brush transition with the PAA chains dissolving in the water subphase and stretching underneath the anchoring PS cores. AFM imaging revealed the presence of circular surface micelles for low surface pressures, whereas the biphasic nature of the pseudoplateau region was confirmed with the gradual aggregation of the micellar PS cores above the PAA chains. The aggregation numbers for both samples were estimated around 3-5 dendrimer-like copolymers per circular surface micelle. These rather low values confirmed the tremendous influence of molecular architecture on the two-dimensional self-assembly of block copolymers.
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.subject.enPOLYELECTROLYTES
dc.subject.enMICELLIZATION BEHAVIOR
dc.subject.enSURFACE MICELLE FORMATION
dc.subject.enAIR/WATER INTERFACE
dc.subject.enPOLY(ACRYLIC ACID)
dc.subject.enLANGMUIR-BLODGETT MONOLAYERS
dc.subject.enSTAR BLOCK-COPOLYMERS
dc.subject.enPOLYSTYRENE-BLOCK-POLY(ETHYLENE OXIDE) STARS
dc.subject.enMETHACRYLATE) DIBLOCK COPOLYMERS
dc.subject.enMORPHOLOGY
dc.title.enPolystyrene-b-poly(tert-butyl acrylate) and polystyrene-b-poly(acrylic acid) dendrimer-like copolymers: Two-dimensional self-assembly at the air-water interface
dc.typeArticle de revue
dc.identifier.doi10.1021/la062924r
dc.subject.halChimie/Polymères
bordeaux.journalLangmuir
bordeaux.page2531-2538
bordeaux.volume23
bordeaux.hal.laboratoriesLaboratoire de Chimie des Polymères Organiques (LCPO) - UMR 5629*
bordeaux.issue5
bordeaux.institutionBordeaux INP
bordeaux.institutionUniversité de Bordeaux
bordeaux.peerReviewedoui
hal.identifierhal-00279758
hal.version1
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-00279758v1
bordeaux.COinSctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Langmuir&rft.date=2007&rft.volume=23&rft.issue=5&rft.spage=2531-2538&rft.epage=2531-2538&rft.eissn=0743-7463&rft.issn=0743-7463&rft.au=JONCHERAY,%20Thomas%20J.&BERNARD,%20Sophie%20A.&MATMOUR,%20Rachid&LEPOITTEVIN,%20B%C3%A9n%C3%A9dicte&EL-KHOURI,%20Rita%20J.&rft.genre=article


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