Thermoplastic and Rubber Compounds: Technology and Physical Chemistry

307 Pages·2008·9.409 MB·English

by  Kwang-Jea Kim James White

White/Kim
ThermoplasticandRubberCompounds
James L. White
Kwang-Jea Kim
Thermoplastic
and Rubber Compounds
Technology and Physical Chemistry
CarlHanserPublishers,Munich•HanserGardnerPublications,Cincinnati
TheAuthors:
Prof.Dr.JamesL.White,TheUniversityofAkron,250SouthForgeStreet,Akron,OH,44325-0301,USA
Dr.Kwang-JeaKim,TheUniversityofAkron,250SouthForgeStreet,Akron,OH,44325-0301,USA
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LibraryofCongressCataloging-in-PublicationData
White,JamesLindsay,1938-
Thermoplasticandrubbercompounds:technologyandphysicalchemistry/
JamesL.White,Kwang-JeaKim.
p.cm.
ISBN-13:978-1-56990-407-7(hardcover)
ISBN-10:1-56990-407-3(hardcover)
1. Thermoplastics.2. Rubber. I.Kim,Kwang-Jea,1962-II.Title.
TA455.P5W4952007
668.4‘23--dc22
2007011924
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Preface
Allcommercialpolymersarecompoundsthathaveadditivesprimarilyintendedasstabilizers.
Theseadditivesprotectthepolymerfromoxygen,heat,andotheraspectsoftheenvironment.
Manyavailablepolymerproductsarecompoundsthatinvolveawiderangeofingredients,
including commercial products such as polypropylene-based thermoplastic elastomers,
polyvinyl chloride pipes, mineral-filled polypropylene, and pneumatic tire components.
Thesecompoundscontainnotonlystabilizersbutalsootherpolymers,fillers,oils,curatives,
accelerators(forcuratives),andotheringredients.
Thecompoundingofpolymersisnotanewtechnology.Itdatesbacktothebeginningsof
therubberindustryinthefirsthalf of thenineteenthcentury.Compoundingisdiscussed
extensivelyinthememoirsof CharlesGoodyearandThomasHancock,bothpublishedin
1855–1857.Theseearlyeffortswerealmostentirelyempirical.Today,roughly150yearslater,
there is a sound scientific understanding of most modern additives’mechanisms in their
intendedapplications.
Asthepolymerproductsindustrydevelopedandbecameincreasinglylargeinthisperiod,
compoundrecipesbecamemuchmorecomplexandsophisticated.Separatecompounding
cultures developed for individual polymer types, such as elastomers, polyvinyl chloride,
polyolefins and thermoplastic elastomers. Indeed, sub-cultures, such as tire rubber com-
pounds, specialty elastomer compounds, polyethylene compounds, and polypropylene
compounds,havecomeintoexistence.Therubberindustryhasalsoinlargepartseparated
andbecomeisolatedfromthethermoplasticsindustry.
Recipes have generally been designed on the basis of considering each active ingredient
independently and presuming these ingredients do not interact.This often turns out not
to be the case. When the number of components becomes three or more, unexpected
consequencesoftenresult.Apolarsolventoradditiveintroducedintoabinarypolymerblend
willincorporateitselfpreferentiallyintothemore-polarpolymerratherthantheless-polar
polymer.Anadditivepreviouslycompoundedintoaparticularpolymercanmigrateintoa
secondpolymerduringmixingasthenumberofcomponentsinablendincreases.
Itisourpurposeinthisbooktodescribethecomponentsandcompositionofmajortypes
of polymer compounds used in both the thermoplastics and rubber industries. We will
describetheintendedmechanismsoftheseadditivesandtheirsometimesunintendedvarious
interactionswithoneanother.
This book is divided into nine chapters.Chapter1 describes the composition of polymer
compounds and the chemical nature and physical properties of ingredients. Chapters 2
through5describebinarycompoundsofpolymerswithsolidparticles(Chapter2),solvents
(polymersolutions)(Chapter3),additivessuchasstabilizersandcuratives(Chapter4),and
asecondpolymer(blends)(Chapter5).WeturntoternarycompoundsinChapters6and
7.Chapter6discussespolymerswithtwolowmolecularweightliquids,twopolymerswith
onelowmolecularweightsubstance,andthreepolymersincludingcompatibilizedpolymer
VIII Preface
blends.Chapter7considersthecombinationofpolymer,solidparticles,andlowmolecular
weightadditivesincludingcurativesandaccelerators.Chapter8considersmulticomponent
compounds and the component interactions. Chapter9 considers the mixing machinery
andmixingcyclesusedforpreparationofcompounds.Wediscussboththetechnologyand
basicmechanismsofthemajorcommercialbatchandcontinuousmixers,aswellasrelated
areassuchasreactivemixing.
Forreaderswithspecialinterestinrubberandrubbercompounding,werecommendespecially
sections1.3to1.9;2.4;3.3,3.8to3.10;4.2to4.4,4.7,4.11;5.2to5.6;6.2,6.4,6.5,6.8;7.2to
7.5;8.3,8.5;9.2to9.4.
For readers with special interest in thermoplastics we recommend especially sections 1.3,
1.4,1.6,1.7;2.4;3.3to3.5,3.11;4.2,4.3,4.5to4.11;5.1to5.11;6.3to6.9;7.2to7.4;8.4,8.6;
9.3to9.5.
2007
J.L.White,K.J.Kim
Contents
Preface........................................................................ VII
1 OverviewandCompoundIngredients.......................................... 1
1.1 Introduction............................................................. 1
1.2 PhilosophyofPolymerCompounds........................................ 1
1.3 Polymers................................................................ 4
1.3.1 Homopolymers.................................................... 4
1.3.2 Copolymers....................................................... 8
1.3.2.1 General................................................... 8
1.3.2.2 ButadieneCopolymers..................................... 9
1.3.2.3 Ethylene-OlefinCopolymers............................... 11
1.3.3 MolecularWeightDistribution..................................... 12
1.3.4 TransitionBehavior............................................... 13
1.3.5 MeltRheologicalProperties........................................ 15
1.3.6 MechanicalBehavior.............................................. 22
1.4 ParticleFillersandReinforcements........................................ 23
1.4.1 General.......................................................... 23
1.4.2 CarbonBlack..................................................... 24
1.4.3 CalciumCarbonate ............................................... 27
1.4.4 ZincOxide(ZnO) ................................................ 29
1.4.5 TitaniumDioxide................................................. 31
1.4.6 Silica ............................................................ 31
1.4.7 TalcandMica .................................................... 36
1.4.8 KaolinClays...................................................... 39
1.4.9 FibrousSilicatesandWollastonite................................... 41
1.4.10 GlassFibers...................................................... 43
1.4.11 GlassSpheres..................................................... 43
1.4.12 OrganicFillers.................................................... 44
1.4.12.1 CelluloseandCelluloseFibers.............................. 45
1.4.12.2 Starch ................................................... 51
1.4.12.3 AramidFibers............................................ 52
1.4.12.4 CarbonFibers............................................ 53
1.4.13 Nanofillers....................................................... 53
1.4.13.1 Montmorillonite.......................................... 53
1.4.13.2 CarbonNanotubes........................................ 54
1.5 OilsandPlasticizers ..................................................... 55
1.6 Antidegradents.......................................................... 56
1.7 ProcessingAids ......................................................... 57
1.8 Curatives............................................................... 60
1.9 Accelerators ............................................................ 62
X Contents
2 Polymer-ParticleFillerSystems............................................... 73
2.1 Introduction............................................................ 73
2.2 ParticlePropertiesandInteraction........................................ 73
2.2.1 ParticleDensity................................................... 73
2.2.2 ParticleSize...................................................... 75
2.2.3 ParticleShape .................................................... 77
2.3 HydrodynamicTheoryofSuspensions..................................... 78
2.3.1 General.......................................................... 78
2.3.2 Spheres.......................................................... 79
2.3.3 Ellipsoids ........................................................ 80
2.3.4 InteractingParticles............................................... 81
2.3.5 ContinuumTheories.............................................. 81
2.4 ExperimentalStudiesofCompoundProperties............................. 82
2.4.1 LargeSpheres .................................................... 82
2.4.2 LargeFibersandEllipsoids......................................... 83
2.4.2.1 Fluids ................................................... 83
2.4.2.2 Solids.................................................... 85
2.4.3 CarbonBlack..................................................... 89
2.4.3.1 ThermoplasticMelts/UncuredCompounds.................. 89
2.4.3.2 RubberVulcanizates....................................... 91
2.4.4 CalciumCarbonate(CaCO )....................................... 93
3
2.4.4.1 ThermoplasticMelts...................................... 93
2.4.4.2 SolidThermoplastics...................................... 95
2.4.5 Silica ............................................................ 96
2.4.5.1 UncuredRubberCompounds.............................. 96
2.4.5.2 RubberVulcanizates....................................... 96
2.4.6 TalcandMica .................................................... 96
2.4.6.1 ThermoplasticMelts...................................... 96
2.4.6.2 SolidPolymers ........................................... 98
2.4.7 MontmorilloniteandOrganoClays(NanoComposites) .............. 98
2.4.8 CarbonNano-Tubes .............................................. 99
2.5 Summary..............................................................100
3 PolymerSolutionsandSwollenVulcanizates..................................105
3.1 Introduction...........................................................105
3.2 LowMolecularWeightSolutions.........................................105
3.3 ThermodynamicsofPolymerSolutions:FlexibleChains....................110
3.4 SolubilityofCrystallinePolymers........................................112
3.5 SolutionsofRigidChainPolymers.......................................113
3.6 ThermodynamicsofHeterogeneousFlexibleChainPolymerSolutions.......114
3.7 PhaseSeparationandEquilibrium .......................................114
3.8 SwellingofVulcanizates.................................................117
3.9 RheologicalPropertiesofPolymerSolutions ..............................118
3.10 Oil-ExtendedRubber...................................................122
Contents XI
3.11 PlasticizedPolyvinylChloride ...........................................123
3.12 Summary..............................................................124
4 PolymerAdditiveBinarySystems............................................129
4.1 Introduction...........................................................129
4.2 SolubilityofAdditives ..................................................129
4.3 Antioxidants...........................................................131
4.3.1 General.........................................................131
4.3.2 MechanismofOxidation .........................................132
4.3.3 AntioxidantMechanisms.........................................133
4.3.4 AntioxidantMiscibility...........................................133
4.3.5 AntioxidantMigration ...........................................134
4.4 Antiozonants ..........................................................136
4.5 LightStabilizers........................................................137
4.6 HeatStabilizers ........................................................138
4.7 ProcessingAids ........................................................140
4.8 SurfacePropertyModifiers..............................................144
4.9 AntistaticAdditives.....................................................144
4.10 NucleatingAgents......................................................145
4.11 Curatives..............................................................147
4.11.1 SulfurCrosslinking ..............................................147
4.11.2 CrosslinkingbyOrganicPeroxides.................................148
4.11.3 CrosslinkingbyMetallicOxides...................................149
4.11.4 CrosslinkingbyPhenolicDerivatives...............................149
4.11.5 CrosslinkingbyHighEnergyRadiation ............................149
4.12 Summary..............................................................152
5 BinaryPolymerBlends......................................................157
5.1 Introduction...........................................................157
5.2 ThermodynamicsofPolymer-PolymerMiscibility .........................157
5.3 StatisticalThermodynamicInterpretation.................................159
5.4 MisciblePolymerBlends................................................160
5.5 PartialMiscibility ......................................................164
5.6 ProblemsWithCopolymers .............................................166
5.7 ImmisciblePolymerBlendsandInterfacialTension ........................167
5.8 PhaseMorphologyinImmiscibleBinaryPolymerBlends...................173
5.9 SpecialPolymerMeltPhaseDistributions.................................175
5.10 MechanicalPropertiesofBinaryPolymerBlends ..........................177
5.11 BlendsofRecycledPolymers.............................................177
6 TernarySystems:
PolymerBlendsplusLiquidAdditivesandCompatibilizingAgents .............181
6.1 Introduction...........................................................181
6.2 TernaryLowMolecularWeightSystems...................................181
XII Contents
6.3 PolymerPlusTwoLowMolecularWeightLiquids..........................183
6.4 LowMolecularWeightOils/AdditivesinBinaryPolymerBlends.............186
6.5 AmphiphilicMoleculesandBlockGraftCopolymersinImmisciblePolymer
Blends(CompatibilizedBlends)..........................................190
6.6 MechanicalPropertiesofCompatibilizedBlends...........................192
6.7 CompatibilizedRecycledPolymerBlends .................................194
6.8 HighImpactPolystyrene(HIPS).........................................194
6.9 TernaryPolymerBlends.................................................195
6.10 Summary..............................................................195
7 Polymer-Filler-AdditivesandCurative-AcceleratorCompounds................201
7.1 Introduction...........................................................201
7.2 MineralFillers:CarboxylicAcid-Polymer .................................201
7.3 Organic-SilaneCouplingAgentforThermosets,Thermoplastics,and
Rubber................................................................203
7.4 OrganoClayNanocomposites(Clay-OrganicAmine-Polymer)..............205
7.5 Rubber-Sulfur-Accelerator ..............................................207
7.6 CrosslinkingbyEnzymes................................................208
7.7 ParticleFillerwithTwoPolymers ........................................208
8 MulticomponentCompounds...............................................213
8.1 Introduction...........................................................213
8.2 SimpleMulticomponentCompounds ....................................213
8.3 TireCompounds.......................................................214
8.3.1 Polydiene-CarbonBlackOilCompounds...........................214
8.3.2 Polydiene-Rubber-SilicaCompounds..............................215
8.4 ThermoplasticCompounds .............................................216
8.4.1 PolyvinylChlorideCompounds...................................216
8.4.2 IsotacticPolypropyleneCompounds...............................217
8.4.3 RecycledPolymerBlendCompounds ..............................218
8.5 RubberCompoundswithSpecialMechanicalProperties....................219
8.5.1 ChlorinatedButylRubberCompounds.............................219
8.5.2 NitrileRubberCompounds.......................................222
8.5.3 Ethylene-Propylene-DieneTerpolymer(EPDM)Compounds.........224
8.6 ThermoplasticElastomer(TPE)Compounds..............................225
8.6.1 Elastomer-ModifiedPolypropylene................................225
8.6.2 SBS-TypeThermoplasticElastomer................................225
9 MixingMachinery:BatchandContinuous....................................229
9.1 Introduction...........................................................229
9.2 BatchMixers...........................................................229
9.2.1 Mills ...........................................................229
9.2.2 OpenBatchMixers...............................................230
9.2.3 InternalMixers:Non-IntermeshingRotors .........................234