Introduction to Polymer Science and Chemistry : A Problem-Solving Approach, Second Edition.

754 Pages·2013·8.753 MB·English

by  Chanda, Manas

Polymer Science
S e c o n d e d i t i o n
Introduction to
Polymer Science
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and Chemistry S n Introduction to
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i r
A Problem-Solving Approach
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Polymer Science
n
d
S e c o n d e d i t i o n
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u
e
c and Chemistry
Industry and academia remain fascinated with the diverse properties and applications

of polymers. However, most introductory books on this enormous and important field t
a
do not stress practical problem solving or include recent advances, which are critical i
o
for the modern polymer scientist-to-be. Updating the popular first edition of “the polymer n
book for the new millennium,” Introduction to Polymer Science and Chemistry: A
n
Problem-Solving Approach, Second Edition seamlessly integrates exploration of the d
A Problem-Solving Approach
fundamentals of polymer science and polymer chemistry.

t
See what’s new in the second edition: C
o
• Chapter on living/controlled radical polymerization, using a unique h

problem-solving approach
P
• Chapter on polymer synthesis by “click” chemistry, using a unique e
problem-solving approach
m o
• Relevant and practical work-out problems and case studies
• Examples of novel methods of synthesis of complex polymer molecules l
y
by exciting new techniques i
• Figures and schematics of the novel synthetic pathways described in s
m Manas Chanda
the new examples t
r
Author Manas Chanda takes an innovative problem-solving approach in which the text
e
y
presents worked-out problems or questions with answers at every step of the development
of a new theory or concept, ensuring a better grasp of the subject and scope for r
self study. Containing 286 text-embedded solved problems and 277 end-of-chapter
home-study problems (fully answered separately in a Solutions Manual), the book
provides a comprehensive understanding of the subject. These features and more set
this book apart from other currently available polymer chemistry texts. S ec o n d
e dition
K15289
ISBN-13: 978-1-4665-5384-2
90000
9 781466 553842
K15289_Cover_mech.indd 1 11/9/12 2:22 PM
Introduction to
Polymer Science
and Chemistry
A Problem-Solving Approach
K15289_FM.indd 1 11/16/12 3:48 PM
TThhiiss ppaaggee iinntteennttiioonnaallllyy lleefftt bbllaannkk
S e c o n d e d i t i o n
Introduction to
Polymer Science
and Chemistry
A Problem-Solving Approach
Manas Chanda
Boca Raton London New York
CRC Press is an imprint of the
Taylor & Francis Group, an informa business
K15289_FM.indd 3 11/16/12 3:48 PM
CRC Press
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Dedicated to the memory
of my beloved father and mentor
Narayan Chandra Chanda
TThhiiss ppaaggee iinntteennttiioonnaallllyy lleefftt bbllaannkk
Contents
Preface xvii
Author xxi
1 IntroductoryConcepts 1
1.1 BasicDefinitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.1 Polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.2 Monomer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1.3 MolecularWeightandMolarMass. . . . . . . . . . . . . . . . . . . . . 3
1.1.4 EndGroups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.5 DegreeofPolymerization . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.1.6 Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2 PolymerizationandFunctionality. . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.3 PolymerizationProcesses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.1 AdditionorChainPolymerization . . . . . . . . . . . . . . . . . . . . . 7
1.3.2 StepPolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.3.3 SupramolecularPolymerization . . . . . . . . . . . . . . . . . . . . . . 13
1.4 MolecularArchitecture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1.5 ClassificationofPolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.5.1 ThermoplasticsandThermosets . . . . . . . . . . . . . . . . . . . . . . 22
1.6 Plastics,Fibers,andElastomers. . . . . . . . . . . . . . . . . . . . . . . . . . . 26
1.7 PolymerNomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Referenc.e.s. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Exercise.s. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2 ChainDimensions,Structures,andTransitionalPhenomena 35
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.2 PolymerChains: StructuresandDimensions . . . . . . . . . . . . . . . . . . . 35
2.2.1 ConformationalChanges . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.2.1.1 Polyethylene . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.2.1.2 Polyisobutylene . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.2.1.3 Polypropylene . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.2.2 PolymerConformationsinCrystals . . . . . . . . . . . . . . . . . . . . 40
2.2.3 PolymerSizeintheAmorphousState . . . . . . . . . . . . . . . . . . . 42
2.2.3.1 FreelyJointedChains . . . . . . . . . . . . . . . . . . . . . . 43
2.2.3.2 RealPolymerChains . . . . . . . . . . . . . . . . . . . . . . 44
vii
viii Contents
2.3 ConstitutionalandConfigurationalIsomerism . . . . . . . . . . . . . . . . . . . 47
2.3.1 ConstitutionalIsomerism . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.3.2 ConfigurationalIsomerism . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.3.2.1 GeometricalIsomerism . . . . . . . . . . . . . . . . . . . . . 50
2.3.2.2 Stereoisomerism . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.4 CrystallinityinPolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
2.4.1 StructureofBulkPolymers. . . . . . . . . . . . . . . . . . . . . . . . . 59
2.4.1.1 Spherulites . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
2.5 ThermalTransitionsinPolymers . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.5.1 T andT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
g m
2.5.2 First-andSecond-OrderTransitions . . . . . . . . . . . . . . . . . . . . 63
2.6 RegionsofViscoelasticBehavior . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2.7 FactorsAffectingT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
g
2.8 FactorsAffectingT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
m
2.9 RelationBetweenT andT . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
m g
2.10 TheoreticalTreatmentofGlassTransition . . . . . . . . . . . . . . . . . . . . . 69
2.10.1 QuantitativeEffectsofFactorsonT . . . . . . . . . . . . . . . . . . . . 74
g
2.11 ChainMovementsinAmorphousState . . . . . . . . . . . . . . . . . . . . . . . 80
2.11.1 TheReptationModel . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.12 ThermodynamicsofRubberElasticity . . . . . . . . . . . . . . . . . . . . . . . 83
2.12.1 Stress-StrainBehaviorofCrosslinkedElastomers . . . . . . . . . . . . . 85
2.12.2 NonidealNetworks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
2.12.2.1 NetworkDefects . . . . . . . . . . . . . . . . . . . . . . . . . 91
2.12.2.2 ElasticallyActiveChainSections . . . . . . . . . . . . . . . . 91
Referenc.e.s. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
Exercise.s. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3 PolymersinSolution 101
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
3.2 ThermodynamicsofLiquidMixtures . . . . . . . . . . . . . . . . . . . . . . . . 101
3.2.1 Low-Molecular-WeightMixtures: vanLaarModel . . . . . . . . . . . . 104
3.2.2 Polymer-SolventMixtures: Flory-HugginsModel . . . . . . . . . . . . 107
3.2.2.1 Flory-HugginsExpressionsforThermodynamicFunctions . . 111
3.2.2.2 ColligativePropertiesandInteractionParameterΧ . . . . . . . 113
3.2.2.3 VirialCoefficients . . . . . . . . . . . . . . . . . . . . . . . . 117
3.2.2.4 ModificationofFlory-HugginsTheory . . . . . . . . . . . . . 119
3.2.2.5 Flory-KrigbaumTheory . . . . . . . . . . . . . . . . . . . . . 121
3.2.2.6 ExcludedVolumeTheory . . . . . . . . . . . . . . . . . . . . 122
3.3 PhaseEquilibriainPoorSolvents. . . . . . . . . . . . . . . . . . . . . . . . . . 126
3.3.1 UpperandLowerCriticalSolutionTemperatures . . . . . . . . . . . . . 129
3.4 SolubilityBehaviorofPolymers . . . . . . . . . . . . . . . . . . . . . . . . . . 131
3.5 SwellingofCrosslinkedPolymers . . . . . . . . . . . . . . . . . . . . . . . . . 138
3.5.1 DeterminationofΧfromSwelling . . . . . . . . . . . . . . . . . . . . . 142
3.6 FrictionalPropertiesofPolymerMolecules
inDiluteSolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
3.6.1 ViscosityofDilutePolymerSolutions . . . . . . . . . . . . . . . . . . . 145
3.6.1.1 DeterminationofPolymerMolecularDimensionsfromViscosity 148
Referenc.e.s. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Contents ix
Exercise.s. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
4 PolymerMolecularWeights 159
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
4.2 MolecularWeightAverages. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
4.2.1 ArithmeticMean . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
4.2.2 Number-AverageMolecularWeight . . . . . . . . . . . . . . . . . . . . 160
4.2.3 Weight-AverageMolecularWeight. . . . . . . . . . . . . . . . . . . . . 162
4.3 MolecularWeightsinTermsofMoments . . . . . . . . . . . . . . . . . . . . . 163
4.3.1 RatioofFirstandZerothMoments. . . . . . . . . . . . . . . . . . . . . 164
4.3.2 RatiosofHigherMoments . . . . . . . . . . . . . . . . . . . . . . . . . 165
4.4 MolecularWeightDetermination . . . . . . . . . . . . . . . . . . . . . . . . . . 166
4.4.1 End-GroupAnalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
4.4.2 ColligativePropertyMeasurement . . . . . . . . . . . . . . . . . . . . . 168
4.4.2.1 Ebulliometry(BoilingPointElevation) . . . . . . . . . . . . . 168
4.4.2.2 Cryoscopy(FreezingPointDepression). . . . . . . . . . . . . 169
4.4.2.3 MembraneOsmometry . . . . . . . . . . . . . . . . . . . . . 169
4.4.2.4 Vapor-PhaseOsmometry . . . . . . . . . . . . . . . . . . . . 176
4.4.3 Light-ScatteringMethod . . . . . . . . . . . . . . . . . . . . . . . . . . 180
4.4.3.1 RayleighRatio . . . . . . . . . . . . . . . . . . . . . . . . . . 181
4.4.3.2 TurbidityandRayleighRatio . . . . . . . . . . . . . . . . . . 183
4.4.3.3 TurbidityandMolecularWeightofPolymer . . . . . . . . . . 184
4.4.3.4 DissymmetryofScattering . . . . . . . . . . . . . . . . . . . 188
4.4.3.5 ZimmPlots . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
4.4.4 DiluteSolutionViscometry. . . . . . . . . . . . . . . . . . . . . . . . . 194
4.4.4.1 CalibrationoftheMark-Houwink-SakuradaEquation . . . . . 196
4.4.4.2 MeasurementofIntrinsicViscosity . . . . . . . . . . . . . . . 197
4.4.5 GelPermeationChromatography . . . . . . . . . . . . . . . . . . . . . 200
4.4.5.1 DataInterpretationandCalibration . . . . . . . . . . . . . . . 202
Referenc.e.s. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
Exercise.s. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
5 Condensation(Step-Growth)Polymerization 213
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
5.2 RatesofPolycondensationReactions . . . . . . . . . . . . . . . . . . . . . . . . 214
5.2.1 IrreversiblePolycondensationKinetics . . . . . . . . . . . . . . . . . . 216
5.2.2 ReversiblePolycondensationKinetics . . . . . . . . . . . . . . . . . . . 222
5.3 Number-AverageDegreeofPolymerization . . . . . . . . . . . . . . . . . . . . 224
5.4 ControlofMolecularWeight . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
5.4.1 QuantitativeEffectofStoichiometricImbalance. . . . . . . . . . . . . . 228
5.5 MolecularWeightDistribution(MWD) . . . . . . . . . . . . . . . . . . . . . . 232
5.5.1 BreadthofMWD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
5.6 NonlinearStepPolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
5.6.1 Branching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
5.6.2 CrosslinkingandGelation . . . . . . . . . . . . . . . . . . . . . . . . . 243
5.6.2.1 StatisticalApproach . . . . . . . . . . . . . . . . . . . . . . . 246
5.6.2.2 ModelforGelationProcess . . . . . . . . . . . . . . . . . . . 255
5.6.2.3 MolecularSizeDistribution . . . . . . . . . . . . . . . . . . . 255