Table Of ContentPhysicochemical Behavior and Supramolecular
Organization of Polymers
·
Ligia Gargallo Deodato Radic´
Physicochemical Behavior
and Supramolecular
Organization of Polymers
123
Prof.Dr.LigiaGargallo Prof.Dr.DeodatoRadic´
PontificiaUniversidadCatolica PontificiaUniversidadCatolica
deChile deChile
FacultaddeQuimica FacultaddeQuimica
VicunaMackenna4860 VicunaMackenna4860
Santiago Santiago
Casilla306,Correo22 Casilla306,Correo22
Chile Chile
[email protected] [email protected]
ISBN978-1-4020-9371-5 e-ISBN978-1-4020-9372-2
DOI10.1007/978-1-4020-9372-2
LibraryofCongressControlNumber:2008942790
(cid:2)c SpringerScience+BusinessMediaB.V.2009
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Preface
Thisbookisconcernedmainlywiththephysicochemicalbehaviorandsupramolec-
ular organization of polymers. The book is split in four chapters dealing with so-
lution properties, viscoelastic behavior, physicochemical aspects at interfaces and
supramolecular structures of polymeric systems. The classical treatment of the
physicochemical behavior of polymers is presented in such a way that the book
will meet the requirements of a beginner in the study of polymeric systems in so-
lution and in some aspects of the solid state, as well as those of the experienced
workerinothertypeofmaterial.Indeedthebookisacontributiontothechemistry
of materials. Taken into account these aspects, Chapter 1 is an introduction to the
classicalconformationalandthermodynamicanalysisofpolymericsolutionswhere
thedifferenttheoriesthatdescribethesebehaviorsofpolymersareanalyzed.Owing
to the importance of the basic knowledge of the solution properties of polymers,
the description of the conformational and thermodynamic behavior of polymers is
presentedinaclassicalway.Thebasicconceptslikethetacondition,excludedvol-
ume,goodandpoorsolvents,criticalphenomena,concentrationregime,cosolvent
effectofpolymersinbinarysolvents,preferentialadsorptionarepresentedinanin-
telligibleway.Thethermodynamictheoryofassociationequilibriawhichiscapable
to describe quantitatively the preferential adsorption of polymers by polar binary
solventsisalsoanalyzed.Chapter2isadiscussionoftheviscoelasticpropertiesof
polymericmaterialwherethedifferentconceptdealingwiththefactthatpolymers
aboveglass-transitiontemperatureexhibithighentropicelasticity.Polymersexhibit
bothviscousandelasticcharacteristicswhatispresentinsystemswhenundergoing
deformation. In this Chapter the basic concepts of viscoelasticity are described at
beginnerlevel.Theanalysisofstress-straininpolymericmaterialsisofgreatprac-
ticalinterestandseveralexamplesofsomefamiliarbehaviorofpolymericmaterials
areshortlydescribed.TheChapterissplittedinfourpartsthefirstdealingwithba-
sicconceptsofviscoelasticity.Thesecondwithdielectricanddynamicmechanical
behaviorofaliphatic,cyclicsaturatedandaromaticsubstitutedpoly(methacrylate)s
withdifferentkindofsubstituentsinthesiderings.Thediscussionintermsofthe
theories that can describe the viscoelastic behavior of polymers is well explained.
The analysis of the different relaxations that take place in these systems allow to
understand the molecular origin of the different motions. By this way an interest-
ingapproachoftherelaxationalprocessesispresentedundertheexperienceofthe
v
vi Preface
authors in these polymeric systems. The third part deals with the dielectric and
dynamic mechanical behavior of poly(itaconate)s with mono and disubstitutions.
Theeffectofthesubstituentsandthefreecarboxylicgroupsinpoly(monitaconate)s
andthedisubstitutiononpoly(diitaconate)sisextensivelydiscussedandinteresting
conclusion are descrived. The fourth part is the analysis of viscolastic behavior of
poly(thiocarbonate)swherethedifferenceisthatthisfamilyofpolymerscorrespond
tocondensationpolymersinsteadofvinylpolymersliketheformers.Theeffectof
the substitution of the polymers is also analyzed. Chapter 3 is a discussion of the
behaviorofpolymersatinterfaceswheretheLangmuirmonolayersandLangmuir-
Blodgetfilmsarestudied.Amphiphilicpolymersattheair-waterinterfacearestud-
iedviatheLangmuirtechnique.Thestudyanddiscussionofsurfacepressure-area
isothermsfordifferentpolymersareperformedbyusingasurfacefilmbalanceand
the results obtained from this technique are analyzed in terms of the shape of the
isotherms.Thecollapsepressurefordifferentsystemsarediscussedintermsofthe
chemical structure of the polymer. The adsorption of polymers by spreading and
fromsolutionisalsodiscussed.Wettingofsolidsbyaliquiddescribedintermsof
the equilibrium contact angle (cid:2) and the appropriate interfacial tensions. At equi-
libriumtheforcesactingareanalyzedusingtheYoung’sequation.Chapter4deals
withtheanalysisofsupramolecularstructurescontainingpolymers.Specificallyin
this chapter the discussion about the effect of polymeric materials with different
chemical structures that form inclusion complexes is extensively studied. The ef-
fect of the inclusion complexes at the air-water interface is discussed in terms on
the nature of the interaction i.e. if the interaction is on entropic or enthalpic na-
ture.Thedescriptionoftheseinclusioncomplexesondifferentcyclodextrineswith
poly(ethylene) oxide, poly((cid:3)-caprolactone) and related polymers is an interesting
waytounderstandsomenon-covalentinteractioninthesesystems.Thediscussion
aboutthegenerationandeffectofsupramolecularstructuresonmolecularassembly
andauto-organizationprocessesisalsopresentedinasingleform.Finallytheuseof
blockcopolymersanddendronizedpolymersatinterfacesisnewaspecttobetaken
intoaccountfrombothbasicandtechnologicalinterest.Theeffectofthechemical
structureontheself-assembledsystemsisdiscussedintermsofthedifferentkinds
ofinteractionthatcanbedetected.Thisbookshouldbeapowerfultoolforstudents
andscientistsworkingbothinpolymerchemistryandphysicandinmaterialscience.
Santiago,Chile LigiaGargallo
DeodatoRadic´
Contents
1 PolymerSolutionBehavior:PolymerinPureSolventandinMixed
Solvent ........................................................ 1
1.1 Introduction:SolutionProperties............................... 1
1.2 PolymerSolutionsinGoodSolvent:ExcludedVolumeEffect....... 15
1.3 ThetaCondition:ConcentrationRegimes ........................ 17
1.4 Critical Phenomena in Polymer Solution: The Collapse
ofMacromoleculesinPoorSolvents............................ 24
1.5 Polymers in Binary Solvents. Cosolvency Effect: Preferential
AdsorptionPhenomena ...................................... 28
1.6 Preferential Adsorption Phenomena: Thermodynamical
Description.AssociationEquilibriaTheory...................... 35
References ...................................................... 40
2 ViscoelasticBehaviourofPolymers ............................... 43
2.1 Introduction ................................................ 43
2.2 TheNatureofViscoelasticity .................................. 47
2.3 MolecularTheory ........................................... 49
2.3.1 TheMechanismofCreepDependsonTemperatureandStress 54
2.3.2 MolecularMechanisms ................................ 54
2.3.3 DynamicModulus .................................... 56
2.4 ViscoelasticPropertiesofPoly(methacrylate)s.................... 60
2.4.1 Poly(methacrylate)sContainingAliphaticandSubstituted
AliphaticSideChains ................................. 61
2.4.2 Poly(methacrylate)sContainingSaturatedCyclicSideChains 63
2.4.3 Poly(methacrylate)sContainingHeterocyclicSideGroups... 96
2.4.4 Poly(methacrylate)sContainingAromaticSideChains ......112
2.5 ViscoelasticPropertiesofPoly(itaconate)s.......................131
2.5.1 Poly(itaconate)s Containing Aliphatic and Substituted
AliphaticSideChains ................................. 132
2.5.2 DielectricRelaxationalBehavior ........................138
2.5.3 DynamicMechanicalRelaxationalBehavior...............143
2.5.4 DielectricRelaxationalBehaviorofPoly(diitaconate)s ......146
vii
viii Contents
2.6 ViscoelasticPropertiesofPoly(thiocarbonate)s ...................152
References ......................................................155
3 PhysicochemicalAspectsofPolymeratInterfaces ..................163
3.1 Introduction ................................................163
3.2 LangmuirMonolayersandLangmuir-BlodgettFilms ..............167
3.3 AmphiphilicBlockCopolymerBehaviorinSolutionandInterfaces..189
3.4 PolymerAdsorptionfromSolution .............................199
3.5 WettabilityBehaviorandContactAngles ........................202
References ......................................................203
4 Supramolecular Structures: Complex Polymeric Systems –
Organization,DesignandFormationusingInterfacesandCyclicor
ComplexMolecules .............................................207
4.1 Introduction ................................................207
4.2 InclusionComplexesBetweenPolymersandCyclicMolecules
SurfaceActivity............................................. 212
4.3 Self-Assemblies,BlockCopolymersandDendronizedPolymersat
theInterfaces:EffectofMolecularArchitecture .................. 223
References ......................................................232
Index .............................................................235
Abbreviations
a activity
a.c alternatingcurrent
(cid:4) thermalexpansioncoefficient
(cid:4) relaxationassociatedtoTg
A,i=2,3,... ithvirialcoefficient
i
A area
A˚ surfacelimitingarea
o
A˚ surfacecriticalarea
c
AFM atomicforcemicroscopy
BAM BrewsterAngleMicroscopy
C concentration
c∗ concentrationatwhichentanglementssetin
c∗ overlapconcentration
C Kuhmianconcentration
k
C twodimensionalcompressibility
s
C∞ characteristicratio
CMC criticalmicelleconcentration
CD cyclodextrin
D docility
D diffusioncoefficient
(cid:5) density
(cid:5)(cid:4) universalFloryconstant
DLS dynamiclightscattering
DMA dynamicmechanicalanalysis
DMF N,N-dimethylformamide
DMSO dimethylsulfoxide
(cid:6) density
DSC differentialscanningcalorimeter
dε/dw parameterproportionaltothetotalpolarizationofthechains
(cid:7) solubilityparameterofHildebrand
(cid:7) thelaginthephaseangle.G:dynamicmodulus
dε/dt thetimederivativeofstrain.
(cid:3) staticcomprensibilitymodulus
ix
x Abbreviations
(cid:3) strainthatoccurunderthegivenstress
(cid:3)∗ complexpermittivity
(cid:3)’ dielectricpermittivity
(cid:3) dielectricpermittivity
1
ε” dielectricloss
ε relaxedpermittivity
o
ε∞ unrelaxedpermittivity
E activationenergy
a
E electrostaticmodulus(Young’smodulus)
(cid:3) strainthatoccurunderthegivenstress.
E’ realpartofviscoelasticspectra
E” imaginarypartofviscoelasticspectra.
∓
E theapparentactivationenergy
Eg glassymodulus
(cid:8)E internalenergy
(cid:8)E changeinthemolarinternalenergy
V
g phenomenologicalinteractionparameter
g ternaryparameter
T
G freeenergy
G generation
G’ dynamicstressmodulus,storagemodulus
G” dynamicstrainmodulus,lossmodulus.
(cid:8)G changeinfreeenergy
(cid:8)G changeinfreeenergybymixing
M
(cid:8)G0 changeinstandardfreeenergy
GPC gelpermeationchromatography(SEC)
f fugacity
H heat
(cid:8)H changeinenthalpy
(cid:8)H changeinthemolarenthalpy
V
F(t) relaxationfunction
F frequencyatthemaximumoftheisotherm
max
f axialconformation
ax
f equatorialconformation.
eq
F strength
FEM transmissionelectronmicroscopy
IC inclusioncomplex
I secondmomentoofareaofthecrosssection.
I intensityofscatteringradiation
I intensityofincidentradiation
0
IR infrared
J compliance
h Plank’sconstant
k(cid:4) Hugginsviscosityconstant
K Mark-Houwinkpre-exponentcoefficient
