Synthesis and adsorption of polymers :: control of polymer and surface structure/ Article Swipe
Polymer surface modification can be accomplished by several techniques including chemical reaction and adsorption. In Chapter I, a simple and versatile technique to introduce carboxylic acid functionality to the surfaces of three fluoropolymer film samples is described. In Chapter II, the adsorption of neutral poly(scL-lysine) (PLL) from solution to the water-fluoropolymer interface is described. Chapter III combines the methods of surface modification described in Chapters I and II and discusses the adsorption of charged PLL to a carboxylic acid-functionalized fluoropolymer film surface. The hydrophobic interaction as a driving force for adsorption is further studied in Chapter IV where the synthesis and adsorption of poly(ethylene oxide) (PEO) and its derivatives are discussed. The syntheses of carboxylic acid-functionalized fluoropolymer films rely upon a two step mechanism where unsaturation, introduced in the first step, is oxidatively removed in the second step; one acidic group per twelve to sixteen repeat units was introduced to the surface. Contact angles ($\\theta\\sb{\\rm A}$/$\\theta\\sb{\\rm R}$) of the acid-functionalized fluoropolymer films decrease with increasing pH: PVF$\\sb2$-CO$\\sb2$H (77$\\sp\\circ$/39$\\sp\\circ$ decreases to 68$\\sp\\circ$/25$\\sp\\circ$); PCTFE-CO$\\sb2$H (93$\\sp\\circ$/55$\\sp\\circ$ decreases to 93$\\sp\\circ$/43$\\sp\\circ$); and FEP-CO$\\sb2$H (101$\\sp\\circ$/78$\\sp\\circ$ decreases to 97$\\sp\\circ$/61$\\sp\\circ$). The adsorption of poly(scL-lysine) (PLL) to the water-FEP interface was controlled by pH of the aqueous solution and PLL solution conformation. Only neutral, $\\alpha$-helical PLL adsorbed to FEP (FEP-PLL). The adsorption of PLL to carboxylic acid-functionalized FEP, FEP-CO$\\sb2$H, was controlled by an electrostatic interaction; both a hydrogen bonding interaction between FEP-carboxylic acid and PLL backbone and an ionic interaction between FEP-carboxylate and PLL-ammonium enhanced adsorption. Both FEP-PLL (80$\\sp\\circ$/16$\\sp\\circ$) and FEP-CO$\\sb2$H-PLL (78$\\sp\\circ$/29$\\sp\\circ$) are more hydrophilic than FEP. FEP-PLL-$\\varepsilon$-amine reacts with 3,5-dinitrobenzoyl chloride in 65% yield whereas FEP-CO$\\sb2$H-PLL-$\\varepsilon$-amine reacts in 100% yield. Adsorption of PLL to FEP and FEP-CO$\\sb2$H improves the peel strength of adhesive joints prepared with these substrates and the adhesion and growth of biological cells on these film samples. PEO (5,000 to 50,000 g/mole and polydispersity indices of 1.07 to 1.17) was synthesized by anionic ring opening polymerization of ethylene oxide in THF with triethylene glycol monomethyl ether potassium initiation. PEO was end-capped (PEO-R) by reaction with a (perfluoro)alkyl acid chloride in THF with pyridine catalysis. A polar interaction between substrate and segment controlled adsorption at the fluoropolymer-water interface; PEO adsorbed preferentially to PVF$\\sb2$ over PCTFE and FEP. Both PEO and PEO-R adsorbed to the polystyrene latex-water interface; the latter formed a thicker adsorbed layer. PEO-R showed increased surface activity over PEO at the air-water interface; PEO-perfluorodecanoate decreased the surface tension of water to 35 dyn/cm.
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- Type
- article
- Language
- en
- Landing Page
- https://scholarworks.umass.edu/dissertations_1/802
- https://scholarworks.umass.edu/dissertations_1/802
- OA Status
- green
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- OpenAlex ID
- https://openalex.org/W2121980782
All OpenAlex metadata
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- OpenAlex ID
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https://openalex.org/W2121980782Canonical identifier for this work in OpenAlex
- DOI
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https://doi.org/10.7275/4317-9p95Digital Object Identifier
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Synthesis and adsorption of polymers :: control of polymer and surface structure/Work title
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articleOpenAlex work type
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enPrimary language
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2021Year of publication
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2021-10-26Full publication date if available
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Molly S. ShoichetList of authors in order
- Landing page
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https://scholarworks.umass.edu/dissertations_1/802Publisher landing page
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https://scholarworks.umass.edu/dissertations_1/802Direct link to full text PDF
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YesWhether a free full text is available
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greenOpen access status per OpenAlex
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https://scholarworks.umass.edu/dissertations_1/802Direct OA link when available
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Polymer, Adsorption, Polymer adsorption, Polymer science, Chemistry, Chemical engineering, Polymer chemistry, Materials science, Organic chemistry, EngineeringTop concepts (fields/topics) attached by OpenAlex
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0Total citation count in OpenAlex
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20Other works algorithmically related by OpenAlex
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| abstract_inverted_index.opening | 319 |
| abstract_inverted_index.removed | 133 |
| abstract_inverted_index.samples | 34 |
| abstract_inverted_index.segment | 355 |
| abstract_inverted_index.several | 7 |
| abstract_inverted_index.sixteen | 144 |
| abstract_inverted_index.studied | 93 |
| abstract_inverted_index.surface | 1, 60, 391, 402 |
| abstract_inverted_index.tension | 403 |
| abstract_inverted_index.thicker | 385 |
| abstract_inverted_index.whereas | 266 |
| abstract_inverted_index.Chapters | 64 |
| abstract_inverted_index.activity | 392 |
| abstract_inverted_index.adhesion | 292 |
| abstract_inverted_index.adhesive | 284 |
| abstract_inverted_index.adsorbed | 207, 363, 375, 386 |
| abstract_inverted_index.backbone | 236 |
| abstract_inverted_index.chemical | 10 |
| abstract_inverted_index.chloride | 262, 343 |
| abstract_inverted_index.combines | 56 |
| abstract_inverted_index.decrease | 162 |
| abstract_inverted_index.enhanced | 245 |
| abstract_inverted_index.ethylene | 322 |
| abstract_inverted_index.hydrogen | 228 |
| abstract_inverted_index.improves | 279 |
| abstract_inverted_index.neutral, | 204 |
| abstract_inverted_index.prepared | 286 |
| abstract_inverted_index.pyridine | 347 |
| abstract_inverted_index.reaction | 11, 338 |
| abstract_inverted_index.samples. | 301 |
| abstract_inverted_index.solution | 47, 198, 201 |
| abstract_inverted_index.strength | 282 |
| abstract_inverted_index.surface. | 81, 151 |
| abstract_inverted_index.surfaces | 29 |
| abstract_inverted_index.air-water | 397 |
| abstract_inverted_index.decreased | 400 |
| abstract_inverted_index.decreases | 168, 173, 179 |
| abstract_inverted_index.described | 62 |
| abstract_inverted_index.discusses | 69 |
| abstract_inverted_index.including | 9 |
| abstract_inverted_index.increased | 390 |
| abstract_inverted_index.interface | 51, 190 |
| abstract_inverted_index.introduce | 23 |
| abstract_inverted_index.mechanism | 123 |
| abstract_inverted_index.potassium | 331 |
| abstract_inverted_index.substrate | 353 |
| abstract_inverted_index.syntheses | 112 |
| abstract_inverted_index.synthesis | 99 |
| abstract_inverted_index.technique | 21 |
| abstract_inverted_index.versatile | 20 |
| abstract_inverted_index.water-FEP | 189 |
| abstract_inverted_index.(FEP-PLL). | 210 |
| abstract_inverted_index.Adsorption | 272 |
| abstract_inverted_index.PVF$\\sb2$ | 366 |
| abstract_inverted_index.adsorption | 41, 71, 90, 101, 183, 212, 357 |
| abstract_inverted_index.biological | 296 |
| abstract_inverted_index.carboxylic | 24, 77, 114, 216 |
| abstract_inverted_index.catalysis. | 348 |
| abstract_inverted_index.controlled | 192, 221, 356 |
| abstract_inverted_index.described. | 36, 53 |
| abstract_inverted_index.discussed. | 110 |
| abstract_inverted_index.end-capped | 335 |
| abstract_inverted_index.increasing | 164 |
| abstract_inverted_index.interface; | 361, 380, 398 |
| abstract_inverted_index.introduced | 126, 148 |
| abstract_inverted_index.monomethyl | 329 |
| abstract_inverted_index.substrates | 289 |
| abstract_inverted_index.techniques | 8 |
| abstract_inverted_index.adsorption. | 13, 246 |
| abstract_inverted_index.derivatives | 108 |
| abstract_inverted_index.hydrophilic | 255 |
| abstract_inverted_index.hydrophobic | 83 |
| abstract_inverted_index.initiation. | 332 |
| abstract_inverted_index.interaction | 84, 230, 240, 351 |
| abstract_inverted_index.latex-water | 379 |
| abstract_inverted_index.oxidatively | 132 |
| abstract_inverted_index.polystyrene | 378 |
| abstract_inverted_index.synthesized | 315 |
| abstract_inverted_index.triethylene | 327 |
| abstract_inverted_index.PLL-ammonium | 244 |
| abstract_inverted_index.accomplished | 5 |
| abstract_inverted_index.interaction; | 225 |
| abstract_inverted_index.modification | 2, 61 |
| abstract_inverted_index.conformation. | 202 |
| abstract_inverted_index.electrostatic | 224 |
| abstract_inverted_index.fluoropolymer | 32, 79, 116, 160 |
| abstract_inverted_index.functionality | 26 |
| abstract_inverted_index.poly(ethylene | 103 |
| abstract_inverted_index.unsaturation, | 125 |
| abstract_inverted_index.FEP-CO$\\sb2$H | 177, 278 |
| abstract_inverted_index.FEP-carboxylic | 232 |
| abstract_inverted_index.polydispersity | 308 |
| abstract_inverted_index.polymerization | 320 |
| abstract_inverted_index.preferentially | 364 |
| abstract_inverted_index.FEP-CO$\\sb2$H, | 219 |
| abstract_inverted_index.FEP-carboxylate | 242 |
| abstract_inverted_index.(perfluoro)alkyl | 341 |
| abstract_inverted_index.PCTFE-CO$\\sb2$H | 171 |
| abstract_inverted_index.poly(scL-lysine) | 44, 185 |
| abstract_inverted_index.$\\alpha$-helical | 205 |
| abstract_inverted_index.($\\theta\\sb{\\rm | 154 |
| abstract_inverted_index.3,5-dinitrobenzoyl | 261 |
| abstract_inverted_index.FEP-CO$\\sb2$H-PLL | 251 |
| abstract_inverted_index.acid-functionalized | 78, 115, 159, 217 |
| abstract_inverted_index.fluoropolymer-water | 360 |
| abstract_inverted_index.water-fluoropolymer | 50 |
| abstract_inverted_index.A}$/$\\theta\\sb{\\rm | 155 |
| abstract_inverted_index.PVF$\\sb2$-CO$\\sb2$H | 166 |
| abstract_inverted_index.PEO-perfluorodecanoate | 399 |
| abstract_inverted_index.FEP-PLL-$\\varepsilon$-amine | 258 |
| abstract_inverted_index.(77$\\sp\\circ$/39$\\sp\\circ$ | 167 |
| abstract_inverted_index.(93$\\sp\\circ$/55$\\sp\\circ$ | 172 |
| abstract_inverted_index.(101$\\sp\\circ$/78$\\sp\\circ$ | 178 |
| abstract_inverted_index.(78$\\sp\\circ$/29$\\sp\\circ$) | 252 |
| abstract_inverted_index.(80$\\sp\\circ$/16$\\sp\\circ$) | 249 |
| abstract_inverted_index.68$\\sp\\circ$/25$\\sp\\circ$); | 170 |
| abstract_inverted_index.93$\\sp\\circ$/43$\\sp\\circ$); | 175 |
| abstract_inverted_index.97$\\sp\\circ$/61$\\sp\\circ$). | 181 |
| abstract_inverted_index.FEP-CO$\\sb2$H-PLL-$\\varepsilon$-amine | 267 |
| cited_by_percentile_year | |
| corresponding_author_ids | https://openalex.org/A5045900479 |
| countries_distinct_count | 0 |
| institutions_distinct_count | 1 |
| citation_normalized_percentile |