Plastics Materials 7Th Edition塑料材料学材料科学讲义1

PlasticsPlastics MaterialsMaterials 7Th7Th EditionEdition塑料材料学材料科学讲义塑料材料学材料科学讲义1 1 PLASTICS MATERIALSSEVENTH EDITIONJ A Brydson FormerHead of the Departmentof PhysicalSciences andTechnology Polytechnic ofNorth London now knownas theUniversity ofNorth London f EI NE MA NN OXFORDAUCKLAND BOSTONJOHANNESBURG MELBOURNENEW DELHIButterworth Heinemann LinacreHouse Jordan Hill Oxford OX28DP225Wildwood Avenue Wobum MA01801 2041A divisionof ReedEducational andProfessional PublishingLtd Amember of the ReedElsevier plcgroup Firstpublished byIliffe BooksLtd1966Second edition1969Reprinted1970Third edition1975Reprinted withrevisions1977Reprinted1979Fourth editionpublished byButterworth Heinemann1982Reprinted1985Fifth edition1989Reprinted1991 1993Sixth edition1995Reprinted1995 1996 1998Seventh edition19990J A Brydson1995 1999All rightsreserved No part of this publication maybe reproducedin anymaterial form including photocopyingor storingin anymedium byelectronic meansand whetheror nottransiently orincidentally tosome otheruse of this publication without thewritten permissionof the copyright holderexcept in aordance with the provisionsof theCopyright Designsand PatentsAct1988or underthe terms of alicence issuedby theCopyright LicensingAgency Ltd 90Tottenham CourtRoad London England WlP9HE Applications for thecopyrightholder s writtenpermission toreproduce anypartof thispublicationshould beaddressed to the publisherBritish LibraryCataloguing in Publication Data Brydson J A John Andrew 1932 Plastics materials 7th ed 1 Plastics I Title668 4ISBN0750641320Library ofCongress CataloguinginPublicationDataBrydson J A Plastics materia1slJ A Brydson 7th ed p cm Includes bibliographicalreferences and index ISBN0750641320 hbk 1 Plastics I Title TP1120B799 30623668 4 dc21CIP Compositionby GenesisTypesetting Laser Quay Rochester Kent Printedand boundin GreatBritain byBiddles Lt4Guildford andKing s LynnContents Preface to the Seventh EditionPreface to the FirstEdition Acknowledgements forthe Seventh EditionAbbreviations for Plastics andRubbers1The HistoricalDevelopment of Plastics Materials1 1Natural Plastics1 2Parkesine andCelluloid1 41 5Developments since19391 6Raw Materialsfor Plastics1 7The Marketfor Plastics1 8The FutureforPlastics1 31900 1930The Evolutionof theVinyl Plastics2The ChemicalNature ofPlastics2 1Introduction2 2Thermoplastic andThermosetting Behaviour2 3Further Considerationof AdditionPolymerisation2 3 12 3 2Ionic polymerisation2 3 3Ziegler Natta and metallocene polymerisationElementary kiicsof free radical additionpolymerisation2 4Condensation Polymerisation3States ofAggregation inPolymers3 1Introduction3 2Linear AmorphousPolymers3 2 13 3Crystalline Polymers3 3 1Orientation andcrystallisation3 3 2Liquid crystalpolymers Orientationin linearamorphous polymers3 4Cross linked Structures3 5Polyblends3 6Summary xviixix xxixxiii11346791115191923242933373943434347495253535557V viContents4Relation ofStructure toThermal andMechanical Properties4 1Introduction4 2Factors Affectingthe GlassTransition Temperature4 3Factors Affectingthe Abilityto Crystallise4 4Factors Affectingthe CrystallineMelting Point4 5Some IndividualProperties4 5 1Melt viscosity4 5 2Yield strengthand modulus4 5 3Density4 5 4Impact strength5Relation ofStructure toChemical Properties5 1Introduction5 2Chemical Bonds5 3Polymer Solubility5 3 1Plasticisers5 3 2Extenders5 3 3Determination ofsolubility parameter5 3 4Thermodynamics andsolubility Effectsof Thermal Photochemical and High energy Radiation5 4Chemical Reactivity5 55 6Aging andWeathering5 7Diffusion andPermeability5 8Toxicity5 9Fire andPlastics6Relation ofStructure toElectrical andOptical Properties6 1Introduction6 26 36 4Electronic Applications of Polymers6 5Electrically ConductivePolymers6 6Optical PropertiesAppendix Electrical TestingDielectric Constant Power Factorand StructureSome QuantitativeRelationships ofDielectrics7Additives forPlastics7 1Introduction7 2Fillers7 2 1Coupling agents7 3Plasticisers andSofteners7 4Lubricants andFlow Promoters7 5Anti aging Additives7 5 1Antioxidants7 5 2Antiozonants7 5 3Stabilisers againstdehydrochlorination7 5 4Ultraviolet absorbersand relatedmaterials7 6Flame Retarders7 7Colorants7 8Blowing Agents7 9Cross linking Agents7 10Photodegradants7 112 Oxazolines5959596470737374747476767680878989939596991001031 041101101101171191xx012212412412612813113213413414314314314 5149150153154155Contents vii8Principles of the Processing ofPlastics8 1Introduction8 2Melt Processing of Thermoplastics8 2 1Hygroscopic behaviour8 2 2Granule characteristics8 2 38 2 4Thermal stability8 2 5Flow properties8 2 5 1Terminology8 2 5 2Effect ofenvironmental andmolecular factorson viscousflow properties8 2 5 3Flow inan injectionmould8 2 5 4Elastic effectsin polymermelts8 2 6Thermal propertiesaffecting cooling8 2 7Crystallisation8 2 8Orientation andshrinkage MeltProcessing ofThermosetting PlasticsProcessing in the RubberyState Solution Suspension andCasting ProcessesThermal propertiesinfluencing polymermelting8 38 48 58 6Summary9Principles ofProduct Design9 1Introduction9 2Rigidity ofPlastics Materials9 2 1The assessment of maximumservice temperature9 2 1 1Assessment of thermal stability9 2 1 2Assessment ofsoftening pointThe assessmentof impactstrength9 3Toughness9 3 19 4Stress Strain Time Behaviour9 4 1The WLFequations9 4 2Creep curves9 4 39 5Recovery fromDeformation9 6Distortion Voids andFrozen in Stress9 7Conclusions Practicalassessmentoflong term behaviour10Polyethylene10 1Introduction10 2Preparation ofMonomer10 3Polymerisation10 3 1High pressure polymerisation10 3 2Ziegler processes10 3 3The Phillipsprocess10 3 4Standard OilCompany Indiana process10 3 5Processes formaking linearlow density polyethyleneandmetallocenepolyethylene Structure and Properties of Polyethylene10 5 1Mechanical properties10 5 2Thermal properties10 5 3Chemical properties10 5 4Electrical properties10 5 510 5 6Properties of metallocene catalysed polyethylenes10 410 5Properties ofPolyethylene Properties of LLDPEand VLDPE15815815915915916116316316416717017117417 517517617918 1182184184184186186188190192195196198200 xx02204205205207208 208209210211211212217217221223226227227viii Contents10 6Additives10 7Processing10 810 9Cross linked Polyethylene10 10Chlorinated Polyethylene10 11Applications Polyethylenesof LowandHighMolecular Weight11Aliphatic Polyolefinsother thanPolyethylene and Diene Rubbers11 1Polypropylene11 1 1Preparation of polypropylene11 1 211 1 3Properties ofisotactic polypropylene11 1 4Additives forisotactic polypropylene11 1 5Processing characteristics11 1 6Applications11 1 7Atactic andsyndiotactic polypropylene11 1 8Chlorinated polypropylene11 2 1Atactic polybut 1 ene Structure and properties of polypropylene11 2Polybut 1 ene11 3Polyisobutylene11 4Poly 4 methylpent l ene 11 4 1Structure andproperties11 4 2General properties11 4 3Processing11 4 4Applications11 5Other Aliphatic Olefin Homopolymers11 6Copolymers ContainingEthylene11 6 111 6 2Ethylene cyclo olefin copolymers11 7DieneRubbersEthylene carbon monoxidecopolymers ECO 11 7 1Natural rubber11 7 2Synthetic polyisoprene IR 11 7 3Polybutadiene11 7 4Styrene butadiene rubber SBR 11 7 4 1 High styreneresins 11 7 5Nitrile rubber NBR 11 7 6Chloroprene rubbers CR 11 7 7Butadiene pentadiene rubbers11 8Thermoplastic DieneRubbers11 9AliphaticOlefinRubbers11 10Rubbery Cyclo olefin Cyclo alkene Polymers11 9 1Thermoplastic polyolefinrubbers11 10 1Aliphatic polyalkenamers11 10 2Polynorbomene11 10 3Chlorine containing copolymers11 111 2 Polybutadiene11 I2Ethylene styrene copolymers11 13Other elastomers12Vinyl ChloridePolymers12 1Introduction12 2Preparation ofVinyl Chloride12 3Polymerisation12 4Structure ofPoly viny1chloride 12 4 1Characterisation ofmercial polymers228232238239240241247247248251253260262265267268268 26926927027027227327327327527828028028528929029129429429529 62962993023043043063073073083093113113133153173xx 512 612 7 12 812 9Compounding Ingredients12 5 1Stabilisers12 5 2Plasticisers12 5 3Extende rs12 5 4Lubricants12 5 5Fillers12 5 6Pigments12 5 712 5 8Mi scellaneous additives12 5 9Formulations Properties of PVCCompounds Processing12 7 1Plasticised PVC12 7 2Unplasticised PVC12 7 3Pastes12 7 4Copolymers12 7 5Latices ApplicationsMiscellaneous Products12 9 1Crystalline PVC12 9 2Chlorinated PVC12 9 3Graft polymersbased onPVC12 9 4Vinyl chloride propylene copolymers12 9 5Vinyl chloride N cyclohexylmaleimide copolymersPolymeric impactmodifiers andprocessing aids13Fluorine containing Polymers13 1Introduction13 2Polytetrafluoroethylene13 2 I Preparation of monomer13 2 2Polymerisation13 2 3Structure andproperties13 2 4General properties13 2 5Processing13 2 6Additives13 2 7Applications 13 3Tetrafluoroethylene Hexafluoropropylene Copolymers13 4Tetrafluoroethylene Ethylene Copolymers ETFE 13 5Polychlorotrifluoroethylene Polymers PCTFE 13 6Poly viny1fluoride PVF 13 7Poly viny1id ene fluoride 13 813 9Hexafluoroisobutylene Vinylidene FluorideCopolymers13 10Fluorine containing Rubbers13 11Thermoplastic fluoroelastomers13 12Miscellaneous FluoropolymersPoly viny1acetate and itsDerivatives14 1Introduction14 2Poly viny1acetate and Copolymerswith Ethylene ECTFE Other PlasticsMaterials ContainingTetrafluoroethylene1414 2 1Preparation of the monomer14 2 2Polymerisation14 2 3Properties and uses14 3 1Structure andproperties14 3 2Applications14 3Poly viny1alcohol Conten ts ix325325330336336337338338342342345346347349350354355355359 35935936036036036336336436436436536136937137237337437437637 6377379379383384386386386386388389389390391x Contents14 4The Poly viny1acetals 14 4 1Poly viny1formal 14 4 2Poly viny1ac etal 14 4 3Poly viny1butyral 14 5Ethylene Vinyl AlcoholCopolymers14 6Poly viny1cinnamate 14 7Other OrganicVinyl Ester Polymers15Acrylic Plastics15 i15 215 315 415 515 615 715 815 915 1015 11Intro duction Poly methy1methacrylate 15 2 1Preparation ofmonomer15 2 2Polymerisation15 2 3Structure andproperties15 2 415 2 5Additives15 2 6Processing15 2 7App lications MethylMethacrylate Polymerswith EnhancedImpact Resistanceand SofteningPoint NitrileResins AcrylateRubbers ThermosettingAcrylic PolymersAcrylic AdhesivesHydrophilic PolymersPoly methacry1imide Miscellaneous Methacrylateand ChloroacrylatePolymers andCopolymers OtherAcrylic PolymersGeneral properties ofpoly methy1methacrylate 16Plastics Basedon Styrene16 116 216 316 416 516 616 716 816 916 1016 1116 121 6 13Introduction Preparation of theMonomer16 2 1Laboratory preparation16 2 2Commercial preparationPolymerisation16 3 1Mass polymerisation16 3 2Solution polymerisation16 3 3Suspension polymerisation16 3 4Emulsion polymerisation16 3 5Grades availableProperties andStructure ofPolystyrene General Properties High impact Polystyrenes HIPS Toughened Polystyrenes TPS Styrene Acrylonitrile CopolymersABS Plastics16 8 1Production ofABS materials16 8 2Processing ofABS materials16 8 3Miscellaneous Rubber modified Styrene Acrylonitrile andRelated CopolymersStyrene Maleic AnhydrideCopolymers Butadiene Styrene Block Copolymers MiscellaneousPolymers andCopolymers StereoregularPolystyrene16 13 1Syndiotactic polystyreneProperties andapplications ofABS plastics39139239339339439539739839840040040140540540940941I 41341541741841942042042142342542542642642742942943143143243 2433434437441441442447447448450450452454454Contents xi16 14Processing ofPolystyrene16 15Expanded Polystyrene16 15 1Structural foams16 16Oriented Polystyrene16 17Applications17Miscellaneous VinylThermoplastics17 1Introduction17 2Vinylidene ChloridePolymers andCopolymers17 2 117 2 2Vinylidene chloride acrylonitrile copolymersProperties andapplications ofvinylidene chloride vinyl chloridecopolymers17 3Coumarone Indene resins17 4Poly viny1carbazole 17 5Poly viny1pyrrolidone 17 6Poly viny1ethers 17 7Other VinylPolymers18Polyamides andPolyimides18 118 218 318 418 518 618 718 818 918 1018 11 18 1218 1318 1418 1518 16Polyamides Introduction Intermediatesfor Aliphatic Polyamides18 2 1Adipic acid18 2 2Hexamethylenediamine18 2 318 2 4Caprolactam18 2 5 w Aminoundecanoic acid18 2 6w Aminoenanthic acid18 2 7Dodecanelactam Polymerisation of Aliphatic Polyamides18 3 118 3 2Nylon618 3 3Nylon1118 3 4Nylon1218 3 5Nylon7Structure andProperties ofAliphaticPolyamidesGeneral Properties of the Nylons AdditivesGlass filled Nylons18 7 1Processing of theNylonsApplications Polyamidesof EnhancedSolubility OtherAliphaticPolyamidesAromatic Polyamides18 12 1Glass clear polyamides18 12 2Crystalline aromaticpolyamides Sebacicacid andAzelaic acidNylons46 66 69 610and612Comparison ofnylons6and66in glass filled positions18 12 2 1Poly rn xylylene adipamide18 12 2 2Aromatic polyamidefibres18 12 2 3Polyphthalamide plasticsPolyimides ModifiedPolyimides18 14 1Polyamide imides18 14 2Polyetherimides ElastomericPolyamides4554574 594614624664664664684704714724 74475476478478480480481481482483484485486486486487487487487 490496498500500502505507509509513513514516516521524525526Po lyesteramides 528xii Contents19Polyacetals andRelated Materials19 1Introduction19 2Preparation ofFormaldehyde19 3Acetal Resins19 3 1Polymerisationofformaldehyde19 3 219 3 3Propert ies of acetal resins19 3 4Processing19 3 5Additives19 3 6Acetal polyurethane alloys19 3 7Polyethers fromGlycols andAlkylene Oxides19 5 1Elastomeric polyethersStructure andproperties ofacetal resinsApplications of the acetalpolymers andcopolymers19 4Miscellaneous AldehydePolymers19 519 6Oxetane Polymers19 7Polysulphides20 1Introduction20 2Production ofIntermediates20 3Polymer Preparation20Polycarbonates20 3 1Ester exchange20 3 2Phosgenation processRelation ofStructure andProperties20 4 1Variations inmercial grades20 420 5GeneralProperties20 6Processing Characteristics20 720 820 920 10Miscellaneous CarbonicEsterPolymersOther ThermoplasticsContaining p Phenylene GroupsApplications ofBis phenol APolycarbonates Alloysbased onBis phenol APolycarbonates PolyesterCarbonates andBlockCopolymers2121 121 221 321 421 521 621 721 821 921 10Introduction PolyphenylenesPol y p xylylene Poly pheny1ene oxides and HalogenatedDerivatives AlkylSubstituted Poly pheny1ene oxides including PPO21 5 1Structure andproperties of21 5 221 5 321 5 4Styrenic PPOs21 5 5Processingofstyrenic PPOs21 5 6Polyamide PPOs2157Poly 2 6 dibromo l 4 phenylene oxide Polyphenylene Sulphides21 6 1Amorphous polyarylenesulphides Polysulphones21 7 121 7 2General properties of polysulphones21 7 3Processingofpolysulphones21 7 4Applicati ons21 7 5Blends based on polysulphonesPolyarylether KetonesPhenoxy ResinsLinear AromaticPolyesters poly 2 6 dimethyl p phenylene oxide PPO Processing andapplication ofPPO Blendsbased inpolyphenylene oxidesProperties andstructure ofpolysulphones53153153253353353653854254354454454654654754 95515565565575585585605615645675735755785795805845845845865 86586587589589590591592592593596596599600601601602602607607 Contents xiii21 11Polyhydantoin Resins21 12Poly parabanic acids 21 13Summary22Cellulose Plastics22 122 2Cellulose EstersNature andOurrence ofCellulose22 2 1Cellulose nitrate22 2 2Cellulose acetate22 2 3Other celluloseesters22 3 1Ethyl cellulose22 3 2Miscellaneous ethers22 3Cellulose Ethers22 4Regenerated Cellulose22 5Vulcanised Fibre60961061161361361661662162762962963263263423Phenolic Resins63523 1Introduction63523 2Raw Materials63523 2 1Phenol63623 2 2Other phenols63823 2 3Aldehydes63923 3Chemical Aspects63923 3 1Novolaks63923 3 2Resols64123 4Resin Manufacture64323 5Moulding Powders64523 5 1Compounding ingredients64623 5 2Compounding ofphenol formaldehyde mouldingpositions64823 5 3Processing characteristics64923 5 4Propertiesof phenolic mouldings65223 5 5Applications65265423 6 1The propertiesofphenolic laminates65623 6 2Applications ofphenoliclaminates65823 7Miscellaneous Applications65923 8Resorcinol Formaldehyde Adhesives66266223 9Friedel Crafts andRelated Polymers66623 10Phenolic ResinFibres23 11Polybenzoxazines66624Aminoplastics66866824 1Introduction66924 2Urea Formaldehyde Resins66924 2 1Raw materials24 2 2Theories ofresinification67024 2 3U F mouldingmaterials67167724 2 4Adhesives andrelated uses24 2 5Foams andfirelighters67924 2 6Other applications67968024 3 1Melamine68068224 3 2Resinification2 4 3 3Moulding powders68424 3 4Laminates containingmelamine formaldehyde resin68824 3 5Miscellaneous applications68823 3 3Hardening64123 6Phenolic Laminates24 3Melamine Formaldehyde Resinsxiv Contents24 4Melamine Phenolic Resins24 5Aniline Formaldehyde Resins24 6Resins ContainingThiourea25Polyesters25 i25 225 325 425 525 625 72 5 825 925 1025 1125 1225 13Introduction UnsaturatedPolyester LaminatingResins25 2 1Selection ofraw materials25 2 2Production ofresins25 2 3Curing systems25 2 4Structureandproperties25 2 5Polyester glass fibrelaminates25 2 6Water extended polyesters25 2 7Allyl resinsPolyester MouldingCompositions Fibre forming andFilm forming PolyestersPoly ethy1ene terephthalate Moulding Materials25 5 1Poly ethy1ene naphthalate PEN Poly buty1ene terephthalate Poly trimethy1ene terephthalate Poly 1 4 yclohexylenedimethyleerephthalate PCT 25 8 1Poly 1 4 yclohexylenedimethyleerephthalate co isophthalate Highly AromaticLinear Polyesters25 9 1Liquid crystalpolyesters PolyesterThermoplastic ElastomersPoly pivalo1actone Polycaprolactones SurfaceCoatings Plasticisers andRubbers26Epoxide Resins26 1Introduction26 226 3Preparation ofResins fromBis phenol ACuring ofGlycidyl EtherResins26 3 1Amine hardening systems26 3 2Acid hardeningsystems26 3 3Miscelfaneous hardenersystems26 3 4Comparison ofhardeningsystems26 4 1Miscellaneous glycidyl ether resins26 4 2Non glycidyletherepoxides Diluents Flexibilisers and other AdditivesStructureandPropertiesofCured Resins26 4Miscellaneous EpoxideResins26 526 626 7Applications27 1Introduction27 2Is ocyanates27 327 4Rubbers27Polyurethanes andPolyisocyanurates Fibresand CrystallineMoulding Compounds27 4 1Cast polyurethanerubbers27 4 2Millable gums27 4 3Properties andapplications ofcross linked polyurethanerubbers27 4 4Thermoplastic polyurethanerubbers andSpandex fibres27 5Flexible Foams27 5 1One shot polyesterfoams27 5 2Polyether