[acs symposium series] progress in controlled radical polymerization: materials and applications...
TRANSCRIPT
Subject Index
A
Adhesion process, polyelectrolyte brushespreparation, 192f
Alcohol esterification, 89sAntifouling properties, polyelectrolytebrushes preparation, 185
Arm number determination, 157ATRP kinetics, 30f
B
Bioactive glycopolymersBIEM, SCVCP, 264fbranched glycopolymers via SCVCP,263s
fluorescent glycopolymer hybridnanoparticles, 265
glucosamine-containing polymerbrushes synthesis, 259s
glycocoplymer-grafted nanoparticles,267f
glycocoplymer-grafted nanospheres,266f
glycopolymer brushes, 260fglycopolymer-grafted DVBmicrospheres synthesis, 261s
glycopolymer-grafted polystyrenenanospheres, 259
grafted microspheres, 265fhyperbranched glycopolymer coveredmicrospheres, 264s
hyperbranched glycopolymer-graftedmicrospheres, 263
magnetic glycopolymer hybridnanoparticles, 265
MAMan grafted microspheres, 262fnanoparticle synthesis, 265soverview, 257polymeric microsphere surfacemodification, 261
ungrafted microspheres, 265fBiomolecule immobilization, polymerbrushes, 251s
Block copolymer phase separation analysis,118
Block copolymersBC1 – BC5, 131fBC1 – BC5 characterization, 130tcomponent peaks, 137t
film parameters, 133tfilm preparation, 132nanostructured polymer filmspreparation, 132
XPS studies, 135films, AFM phase images, 134ffilms, high-resolution C1s spectra, 136ffilms, XPS wide-scan, 136fmorphologies, 132toverview, 127phase separation behaviour, 131SAXS diagrams, 132fsynthesis, 118, 128synthesized block copolymers, 129c
Borate, 28synthesis, 29s
Borate block copolymer micelles, 32fBoronic acid, 28synthesis, 29s
Boronium block copolymers, 28synthesis, 29s
Branched glycopolymers via SCVCP, 263sButyl trithiocarbonate end group removal,16, 18
C
CFStar1, 3 arm star PMMA, 93fCFStar2, 5 arm star PMMA, 93fCFStar3, 8-arm star PMMA, 94fCFStar4, 21 arm star PMMA, 94fChain dimension, polyelectrolyte brushespreparation, 186
Characterization, 145CN(CH3)2C-PStn, DSC curves, 23fCN(CH3)2C-PStn, radical-inducedreduction, 20t
Controlled radical polymerization (CRP)polymer primary structure control, 1polymer-inorganic hybrid materials, 163sequence-controlled CRP processes, 6
Core first PMMA star, dilute solutionproperties, 92
Core first PMMA star synthesis, 89Core first star polymers, arms numberquantification, 95
Core-functionalized star polymers,Ru-catalyzed living radicalpolymerization, 66s
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In Progress in Controlled Radical Polymerization: Materials and Applications; Matyjaszewski, K., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.
CRP. See controlled radical polymerization(CRP)
CRP system classification,polymer-inorganic hybrid materials, 165
Crystal assembly reaction, polymerbrushes, 251f
D
Diblock copolymers, Mark-Houwink plots,54f
Direct Ru-encapsulation, microgel-corestar polymers, 67s
DSC characterization, PE-b-POEGMAcopolymers, 56
DSC curvesblock copolymers BC1 – BC5, 131fCN(CH3)2C-PStn, 23fCPDB-PnBAn, 21fH-PnBAn, 21fPABTC-PnBAn, 21fPABTC-PStn, 22fPGMA macro initiator, 122fPGMA-b-PS block copolymer, 122f
DSC thermograms, 56f
F
Fabrication, polymer brushes, 242FeCl2, PPh3-Star, 70fFerrocene containing methacrylatemonomers synthesis, 199
Film preparation, block copolymers, 132nanostructured polymer filmspreparation, 132
XPS studies, 135Fluorescent glycopolymer hybridnanoparticles, 265
Fluorine-condensed star polymers, 76Fluorine-condensed star polymers,ruthenium-catalyzed living radicalpolymerization, 76f
Fluorous Molecular Recognition, 77Friction coefficient, polyelectrolyte brushespreparation, 190f
Functionality determination, 87
G
Glucosamine-containing polymer brushessynthesis, 259s
Glycidyl methacrylate-containing resistpolymer synthesis, 119
Glycocoplymer-grafted nanoparticles, 267fGlycocoplymer-grafted nanospheres, 266fGlycopolymer brushes, 260fGlycopolymer-grafted DVB microspheressynthesis, 261s
Glycopolymer-grafted polystyrenenanospheres, 259
GPC elution curves, MIs, 59fGPC elution traces, 50fGPC elution traces, run 2, 60fGraft copolymerization, PVDF, 223s, 225sGrafted microspheres, bioactiveglycopolymers, 265f
Gyration contraction factor, 85
H
1H NMR characterization, PE-b-POEGMAcopolymers, 55
1H NMR spectra, MI2, 59fHexadecane droplets, polyelectrolytebrushes preparation, 186f
High density polyethylene, 172H-PnBAn, DSC curves, 21fH-PnBAn, radical-induced reduction, 19tHyperbranched glycopolymer coveredmicrospheres, 264s
Hyperbranched glycopolymer-graftedmicrospheres, 263
Hyperbranched/linear polyethylenemacroinitiators, 46t
I
Indium tin oxide (ITO), SI-ATRP, 200Intrinsic viscosity shrink factor, 86Intrinsic viscosity study, PE-b-POEGMAcopolymers, 54
ITO. See indium tin oxide (ITO), SI-ATRPITO-g-PFcMA-b-PMMA, SI-ATRP, 205f
K
KetonesRu-PEG star-catalyzed transferhydrogenation, 72f
transfer hydrogenation, 72, 73f
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L
Lap shear adhesion strengths,polyelectrolyte brushes preparation, 192f
Linear PMMA, Mark-Houwink plot, 94fLinear synthetic polymer chains, 9fLiving radical polymerization, 74Log[η].M vs. elution volume, polymers,83f
M
M1 polymerization, 34fMagnetic glycopolymer hybridnanoparticles, 265
MALDI-TOF MS spectraω-allyl PMMA 3e, 110fω-benzoyl PBA 6, 111fω-benzoyl PMMA 3d, 109fω-benzoyl PNIPAM 8, 112fω-(δ-lacton)-substituted PMMA 4, 110,111f
ω-methylester PMMA 3c, 109fMALLS, SEC, 84MAMan grafted microspheres, bioactiveglycopolymers, 262f
Mark-Houwink plots, 86Mark-Houwink plots, diblock copolymers,54f
Metal encapsulation, 69Metal-bearing star polymers, microgel-corecatalysis, 71f
Methyl methacrylate 3 arm star polymersynthesis, 89
MI, GPC elution curves, 59fMI2, 1H NMR spectra, 59fMicelle behaviors, aqueous solution, 57Micelle size distributions, 57fMicelle solution preparation,PE-b-POEGMA copolymers, 44
Microgel-core catalysis, 70Microgel-core catalysis, metal-bearing starpolymers, 71f
Microgel-core star polymersfluorine-condensed star polymers, 76fluorous molecular recognition, 77ketones, transfer hydrogenation, 72living radical polymerization, 74metal encapsulation, 69microgel-core catalysis, 70overview, 65Ru-bearing microgel-core star polymers,66
sec-alcohols oxidation, 71
tandem catalyst interchange, 69thermoregulated phase-transfer catalysis,73
MMA polymerisation, 90sMMA polymerisation, 3 arm initiator, 90fMonocleavable BA-ss-AB type triblockcopolymer micelles, 297
Mono-cleavable brush-like symmetrictriblock copolymer synthesis, 297f
Monomer conversion, PVDF, 218fMp, various linear calibration standards,82f
Multi detector SEC, 87Multi-cleavable A(ss)n-B type blockcopolymer, 292
Multiple single scan lines, polymerbrushes, 244f
Mussel glue derived enzymesbioconjugates, 281, 281fconjugate IIIb, 282fconjugation strategy, 275NHS-functionalized chain transferreagent synthesis, 276f
overview, 271PNIPAM, 276f, 281fsynthesis, 275tyrosinase, 273f, 278ftyrosinase, circular dichroism spectra,277f
tyrosinase assay, 277ftyrosinase-PNIPAM conjugate, 279
N
Nanoparticle synthesis, bioactiveglycopolymers, 265s
nBA polymerization, 15New monomers, SI-ATRP, 206NHS-functionalized chain transfer reagentsynthesis, 276f
Nitrilotriacetic acid end-functionalizedpolystyrenes (NTA-PS)applications, 308ATRP, 306f, 306tcharacterization, 305DLS data, 311ffluorescence microscope images, 310fgel permeation chromatogram, 307f1H NMR spectra, 308fmesoporous fibres formation, 311micellar aggregates formation, 309overview, 303preparation, 305sSEM images, 309f, 312f
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synthesis, 305TEM images, 309f, 311f, 312f
Nitroxide exchange reaction, polymerbrushes, 247s
NMP initiator syntheses, 147Number-average molecular weightdependencies, 61f
O
Octadecyl acrylate (ODA), 167Octadecyl acrylate, ATRP, 168t, 169f, 170f,171f
Octadecyl acrylate, IR spectra, 171fOctadecyl acrylate polymerization, 168sOctadecyl acrylate polymerization, ATRP,169f
2-Octanone, transfer hydrogenation, 74fODA. See octadecyl acrylate (ODA)ODA polymerization, polymer-inorganichybrid materials, octadecyl acrylatepolymerization, 178, 179
OEGMA, ATRP, 47OEGMA, GPC curves, 48fOEGMA conversion vs. kinetic plots, 49fOEGMA conversion vs. polymerizationtime, 49f, 60f
OH-SS-iBuBr double-head initiatorsynthesis, 296f
Oligomers synthesis, 17Organoboron polymersborate, 28boronic acid, 28boronium block copolymers, 28organoboron quinolate blockcopolymers, 33
overview, 27star polymers, 33
Organoboron quinolate block copolymers,33
Organoboron quinolate monomers, RAFTpolymerization, 34s
Ozone pretreatment, PVDF, 223s, 225s
P
PABTC-PStn, DSC curves, 22fPABTC-PStn, radical-induced reduction,20t
PE MI synthesis, PE-b-POEGMAcopolymers, 43, 45
PE-b-POEGMA copolymers. Seepolyethylene-block-poly[oligo(ethylene
glycol) methacrylate] (PE-b-POEGMA)copolymers
PE-b-POEGMA synthesis, 52tPerfluorinated compounds, fluorousrecognition, 77f
PFcMA brushes, electrochemicalproperties of, 204
PGMA macro-initiator, 122fPGMA macro-initiator, GPC traces, 120fPGMA synthesis, 117. See poly(glycidylmethacrylate), ATRP macro initiator(PGMA) synthesis
PGMA-b-PS block copolymer, 122fPGMA-b-PS block copolymer BCP1, 121fPGMA-b-PS block copolymer phaseseparation, 123
PGMA-b-PS block copolymer synthesis,119s
PGMA-b-PS photoresist block copolymers,photolithography, 123s
PGMA-b-PS photoresist films, 123fPGMA-b-PS thin films, 124fPhosphonic acid coupling agent synthesis,SI-ATRP, 199, 200f
Photolithographic patterning, 122Photolithography, PGMA-b-PS photoresistblock copolymers, 123s
Photolithography patterning, 118PM1-b-PEO, 34fPM2-b-PEO, 34fPMMA 3-arm star polymer, 95fPMMA 5-arm star polymer, 95fPMMA 8-arm star polymer, 96fPMMA 21-arm star polymer, 96fPMMA arms, SEC curves, 68fPMMA stars, Mark-Houwink plot, 94fPMMA stars, SEC results, 92tPnBA thermal properties, 20PnBAn oligomers synthesis, 17tPNIPAM-b-PS star polymers, 36fPODA. See poly(octadecyl acrylate)(PODA)
PODA blends, 172Polyelectrolyte brushes preparationadhesion process, 192fantifouling properties, 185chain dimension, 186chemical structures, 185ffriction coefficient, 190fhexadecane droplets, 186flap shear adhesion strengths, 192foverview, 183repeatable adhesion, 191schematic representation, 187fsliding velocity dependence, 189ftribological behavior, 188
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water, 186fwettability, 185
Polyethylene-block-poly[oligo(ethyleneglycol) methacrylate] (PE-b-POEGMA)copolymersDSC characterization, 561H NMR characterization, 55intrinsic viscosity study, 54materials, 43micelle behaviors, aqueous solution, 57micelle solution preparation, 44OEGMA, ATRP, 47overview, 39PE MI synthesis, 43, 45PE-b-POEGMA synthesis, ATRP, 43synthesis, 42s
PolyFcMA brushes, SI-ATRP, 201f, 203f,204f
Poly(glycidyl methacrylate), ATRP, 120tPoly(glycidyl methacrylate), ATRP macroinitiator (PGMA) synthesis, 117
Poly(glycidyl methacrylate-block-styrene)ATRP, 120tblock copolymer phase separationanalysis, 118
block copolymer synthesis, 118glycidyl methacrylate-containing resistpolymer synthesis, 119
overview, 115PGMA synthesis, 117PGMA-b-PS block copolymer phaseseparation, 123
photolithographic patterning, 122photolithography patterning, 118
Polyhedral ogligomeric silsequioxane-corestar polystyrenearm number determination, 157characterization, 145materials, 144NMP initiator syntheses, 147overview, 141POSS-MAMA-SG1, 2, 146POSS-NH3+Cl-, 145POSS-PS star polymer cleavage, 147star polystyrene, 146star PS, DSC studies, 159star PS synthesis, 150
Polymer brushesbiomolecule immobilization, 251scrystal assembly reaction, 251ffabrication, 242multiple single scan lines, 244fnitroxide exchange reaction, 247soverview, 241polyolefin nanocompositesATRP initiator synthesis, 174, 180
2-bromoisobutyrate functional silicacolloids synthesis, 175, 180
ODA, ATRP, 175, 181radical nitroxide exchange reactions, 246schematic representation, 245fstreptavidin, 246fstructuring, 242surface initiated polymerization, 244ssurface nitroxide exchange reaction,248f
synthesis, 242zeolite L crystals, 248, 249s, 252f
Polymer primary structure controloverview, 1sequence-controlled CRP processes, 6sequence-defined polymer synthesis, 3
Polymer synthesis, polymer-inorganichybrid materials, 167
Polymeric microsphere surfacemodification, 261
Polymer-inorganic hybrid materialsATRP, 166CRP, 165CRP system classification, 165high density polyethylene, 172ODA polymerization, octadecyl acrylatepolymerization, 178, 179
overview, 163PODA blends, 172polymer brushes, polyolefinnanocompositesATRP initiator synthesis, 174, 1802-bromoisobutyrate functional silicacolloids synthesis, 175, 180
ODA, ATRP, 175polymer synthesis, 167surface modification, 174
Polymers, log[η].M vs. elution volume, 83fPoly(methyl methacrylate) (PMMA)graftingATRP grafting, 235scharacterization, 233nitrogen adsorption isotherms, 236foverview, 231pore size distributions, 236fSBA-15 initiator immobilization, 233SBA-15 synthesis, 232surface-initiated ATRP, 233weight change patterns, 237f
Poly(methyl methacrylate) star polymerscore first PMMA star, dilute solutionproperties, 92
core first PMMA star synthesis, 89core first star polymers, arms numberquantification, 95
functionality determination, 87
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gyration contraction factor, 85intrinsic viscosity shrink factor, 86MALLS, SEC, 84Mark-Houwink plots, 86methyl methacrylate 3 arm star polymersynthesis, 88
multi detector SEC, 87overview, 811,1,1-tris(methyl-o-isobutyryl bromide)ethane synthesis, 88
Poly(n-butyl acrylate) (PBA)functionalization, 105s
Poly(N-isopropylacrylamide) (PNIPAM),MALDI-TOF MS spectra, 106f
Poly(N-isopropylacrylamide) (PNIPAM)functionalization, 105s
Poly(octadecyl acrylate) (PODA), 167Poly(octadecyl acrylate), 1H-NMR, 172fPoly(octadecyl acrylate), IR spectra, 171fPoly(octadecyl acrylate), SEM, 173fPoly(vinylidene fluoride) (PVDF)functionalization via ATRP, 214s, 215functionalization via click chemistry,220
functionalization via CRP, 213s, 215s,220
functionalization via RAFTpolymerization, 214s, 219
graft copolymerization, 223s, 225smonomer conversion, 218foverview, 211ozone pretreatment, 223s, 225s
POSS-based alkoxyamine, 150fPOSS-MAMA-SG1, 148f, 149f, 152f, 153f,156f, 157f, 158f
POSS-MAMA-SG1, 2, 146POSS-MAMA-SG1 alkoxyamine 2, 151tPOSS-(MAMA-SG1)n, 150fPOSS-NH3+Cl-, 144s, 145POSS-PS star polymer cleavage, 147POSS-(SG1)8, 144sPS star polymer synthesis, 154fPSBA-b-PS self- assembly, 32fPSBBr2-b-PS, 31fPSt thermal properties, 22PSTMS-b-PS, 31fPStn oligomers synthesis, 18tPVDF-g-PDMAEMA copolymer, 217s
R
Radical nitroxide exchange reactions,polymer brushes, 246
Radical-induced reduction
CN(CH3)2C-PStn, 20tH-PnBAn, 19tPABTC-PStn, 20t
RAFT polymerization. See reversibleaddition fragmentation chain transfer(RAFT) polymerization
Repeatable adhesion, polyelectrolytebrushes preparation, 191
Reversible addition fragmentation chaintransfer (RAFT) polymerizationanalyses, 15butyl trithiocarbonate end groupremoval, 16, 18
materials, 14nBA polymerization, 15oligomers synthesis, 17overview, 13PnBA thermal properties, 20PSt thermal properties, 22styrene polymerization, 16
Ru-bearing microgel-core star polymers,66
Ru-catalyzed living radical polymerizationcore-functionalized star polymers, 66smicrogel-core star polymers, 67s
RuCpCl-star-catalyzed living radical(co)polymerization, 75t
Run 2, GPC elution traces, 60fRun 5 sample, 6 1H NMR spectra, 55fRu-PEG star-catalyzed transferhydrogenation, ketones, 72f
Ru-star polymers, SEC curves, 68f
S
Schematic representationpolyelectrolyte brushes preparation, 187fpolymer brushes, 245f
Sec-alcohol oxidation, 71, 71fSequence-controlled CRP processes, 6Sequence-controlled polymers, 2, 7fSequence-defined oligomers synthesis, 4fSequence-defined polymer, 2Sequence-defined polymer synthesis, 3Sheddable A-ss-B type biodegradableblock copolymer micelles, 295
SI-ATRP. See surface initiated atomtransfer radical polymerization(SI-ATRP)
SiO2, PODA polymer brushes, 177fSiO2-PODA, TGA, 176fSliding velocity dependence,polyelectrolyte brushes preparation, 189f
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Star polymer-catalyzed living radicalpolymerization, 74f
Star polymers, 33schematic representation, 83fSEC traces, 155fsynthesis, 35ssynthesis, ATRP, 91f
Star polystyrene, 146, 160fStar PS, DSC studies, 159Star PS synthesis, 150Stimuli-responsive degradable blockcopolymer micelles, 290f
Streptavidin, 246fStructuring, polymer brushes, 242Styrene polymerization, 16, 156f, 157fSurface initiated atom transfer radicalpolymerization (SI-ATRP)electrochemical characterization, 202ferrocene containing methacrylatemonomers synthesis, 199
ITO, 200ITO-g-PFcMA-b-PMMA, 205fnew monomers, 206overview, 197phosphonic acid coupling agentssynthesis, 199, 200f
polyFcMA brushes, 201f, 203f, 204fvinylic ProDOT monomers synthesis,206f
Surface initiated polymerization, 244sSurface modification, polymer-inorganichybrid materials, 174
Surface nitroxide exchange reaction,polymer brushes, 248f
T
Tandem catalyst interchange, 69Tellurium-metal transmetallation reaction,ω-end functionalized polymers, 101
Thermoregulated phase-transfer catalysis,73, 74f
Thiol-responsive degradable blockcopolymer micellesaqueous micellization, 289fcell viability, 298development strategies, 290monocleavable BA-ss-AB type triblockcopolymer micelles, 297
mono-cleavable brush-like symmetrictriblock copolymer synthesis, 297f
multi-cleavable A(ss)n-B type blockcopolymer, 292
OEOMA, 293tOH-SS-iBuBr double-head initiatorsynthesis, 296f
overview, 287sheddable A-ss-B type biodegradableblock copolymer micelles, 295
ssABP, 292f, 294f, 296f, 298f, 299fstimuli-responsive degradable blockcopolymer micelles, 290f
Tribological behavior, polyelectrolytebrushes preparation, 188
Triple-detector GPC, 51f1,1,1-Tris(methyl-o-isobutyryl bromide)ethane synthesis, 88
Tyrosinase, 273f, 278f
V
Vinylic ProDOT monomers synthesis,SI-ATRP, 206f
W
ω-alkynylated PNIPAM 9, 112ω-allyl PMMA 3e, 110, 110fω-benzoyl PBA 6, 110, 111fω-benzoyl PMMA 3d, 108, 109fω-benzoyl PNIPAM 8, 112, 112fω-carboxylic acid PMMA 3b, 108ω-deuterated PMMA 3a synthesis, 108ω-(δ-lacton)-substituted PMMA 4, 110,111f
ω-end functionalized polymersMALDI-TOF MS spectra, 103foverview, 99synthesis, 101s, 102t, 104tellurium-metal transmetallationreaction, 101
ω-end functionalized polymers synthesis,108
Wettability, polyelectrolyte brushespreparation, 185
ω-methylester PMMA 3c, 108, 109f
Z
Zeolite L crystals, 248, 249s, 252f
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In Progress in Controlled Radical Polymerization: Materials and Applications; Matyjaszewski, K., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.