Ullmann’s Polymersand Plastics

Ullmann’s Polymersand PlasticsProducts and Processes

Editor in Chief:

Dr. Barbara Elvers, Hamburg, Germany

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Preface

This handbook features selected articles from the 7th edition of ULLMANN’S Encyclopedia ofIndustrial Chemistry, including newly written articles that have not been published in a printed editionbefore. True to the tradition of the ULLMANN’S Encyclopedia, polymers and plastics are addressedfrom an industrial perspective, including production figures, quality standards and patent protectionissues where appropriate. Safety and environmental aspects which are a key concern for modernprocess industries are likewise considered.

More content on related topics can be found in the complete edition of the ULLMANN’SEncyclopedia.

About ULLMANN’S

ULLMANN’S Encyclopedia is the world’s largest reference in applied chemistry, industrial chemis-try, and chemical engineering. In its current edition, the Encyclopedia contains more than 30,000pages, 15,000 tables, 25,000 figures, and innumerable literature sources and cross-references, offeringa wealth of comprehensive and well-structured information on all facets of industrial chemistry.

1,100 major articles cover the following main areas:

• Agrochemicals• Analytical Techniques• Biochemistry and Biotechnology• Chemical Reactions• Dyes and Pigments• Energy• Environmental Protection and Industrial Safety• Fat, Oil, Food and Feed, Cosmetics• Inorganic Chemicals• Materials• Metals and Alloys• Organic Chemicals• Pharmaceuticals• Polymers and Plastics• Processes and Process Engineering• Renewable Resources• Special Topics

First published in 1914 by Professor Fritz Ullmann in Berlin, the Enzyklopädie der TechnischenChemie (as the German title read) quickly became the standard reference work in industrial chemistry.Generations of chemists have since relied on ULLMANN’S as their prime reference source. Threefurther German editions followed in 1928–1932, 1951–1970, and in 1972–1984. From 1985 to 1996,the 5th edition of ULLMANN’S Encyclopedia of Industrial Chemistry was the first edition to bepublished in English rather than German language. So far, two more complete English editions havebeen published in print; the 6th edition of 40 volumes in 2002, and the 7th edition in 2011, againcomprising 40 volumes. In addition, a number of smaller topic-oriented editions have been published.

Since 1997, ULLMANN’S Encyclopedia of Industrial Chemistry has also been available inelectronic format, first in a CD-ROM edition and, since 2000, in an enhanced online edition. Bothelectronic editions feature powerful search and navigation functions as well as regular content updates.

Preface V

Contents

Volume 1 .......................................................Symbols and Units ................................... IXConversion Factors .................................. XIAbbreviations ......................................... XIIICountry Codes ...................................... XVIIIPeriodic Table of Elements ..................... XIX

Part 1: Fundamentals ................................ 1Plastics, General Survey, 1. Definition,

Molecular Structure and Properties ....... 3Plastics, General Survey, 2. Production of

Polymers and Plastics ........................ 149Plastics, General Survey, 3. Supermolecular

Structures ........................................... 187Plastics, General Survey, 4. Polymer

Composites ........................................ 205Plastics, General Survey, 5. Plastics and

Sustainability ..................................... 223Plastics, Analysis .................................... 231Polymerization Processes, 1. Fundamentals 265Polymerization Processes, 2. Modeling of

Processes and Reactors ...................... 315Plastics, Processing, 1. Processing of

Thermoplastics .................................. 367Plastics, Processing, 2. Processing of

Thermosets ........................................ 407Plastics Processing, 3. Machining, Bonding,

Surface Treatment .............................. 439Plastics, Properties and Testing ............... 471Plastics, Additives ................................... 527Plasticizers ............................................... 581

Volume 2 .......................................................Part 2: Organic Polymers ...................... 601Fluoropolymers, Organic ......................... 603Polyacrylamides and Poly(Acrylic Acids) 659Polyacrylates ............................................ 675Polyamides .............................................. 697Polyaspartates and Polysuccinimide ........ 733Polybutenes ............................................. 747Polycarbonates ......................................... 763Polyester Resins, Unsaturated ................. 781Polyesters ................................................. 791Polyethylene ............................................ 817Polyimides ............................................... 859Polymethacrylates .................................... 885

Polyoxyalkylenes ..................................... 899Polyoxymethylenes .................................. 911Poly(Phenylene Oxides) ......................... 927Polypropylene .......................................... 937

Volume 3 .......................................................Polystyrene and Styrene Copolymers ..... 981Polyureas ............................................... 1029Polyurethanes ........................................ 1051Poly(Vinyl Chloride) ............................ 1111Polyvinyl Compounds, Others .............. 1141Poly(Vinyl Esters) ................................ 1165Poly(Vinyl Ethers) ................................ 1175Poly(Vinylidene Chloride) .................... 1181Polymer Blends .................................... 1197Polymers, Biodegradable ....................... 1231Polymers, Electrically Conducting ....... 1261Polymers, High-Temperature ................ 1281Reinforced Plastics ............................... 1325Specialty Plastics .................................. 1343Thermoplastic Elastomers ...................... 1365

Volume 4 .......................................................Part 3: Films, Fibers, Foams ............... 1405Films ...................................................... 1407Fibers, 4. Polyamide Fibers ................... 1435Fibers, 5. Polyester Fibers ...................... 1453Fibers, 6. Polyurethane Fibers ............... 1487Fibers, 7. Polyolefin Fibers .................... 1495Fibers, 8. Polyacrylonitrile Fibers .......... 1513Fibers, 9. Polyvinyl Fibers ..................... 1529Fibers, 10. Polytetrafluoroethylene Fibers 1539High-Performance Fibers ....................... 1541Foamed Plastics ..................................... 1563

Part 4: Resins ....................................... 1595Alkyd Resins ......................................... 1597Amino Resins ........................................ 1615Epoxy Resins ......................................... 1643Phenolic Resins ..................................... 1733Resins, Synthetic .................................. 1751

Part 5: Inorganic Polymers ................. 1775Inorganic Polymers ................................ 1777

Author Index ........................................ 1817Subject Index ....................................... 18 3

Contents VII

2

Symbols and Units

Symbols and units agree with SI standards (for conversion factors see page XI). The following list gives the mostimportant symbols used in the encyclopedia. Articles with many specific units and symbols have a similar list asfront matter.

Symbol Unit Physical Quantity

aB activity of substance BAr relative atomic mass (atomic weight)A m2 areacB mol/m3, mol/L (M) concentration of substance BC C/V electric capacitycp, cv J kg�1 K�1 specific heat capacityd cm, m diameterd relative density (ϱ/ϱwater)D m2/s diffusion coefficientD Gy (=J/kg) absorbed dosee C elementary chargeE J energyE V/m electric field strengthE V electromotive forceEA J activation energyf activity coefficientF C/mol Faraday constantF N forceg m/s2 acceleration due to gravityG J Gibbs free energyh m heighth W�s2 Planck constantH J enthalpyI A electric currentI cd luminous intensityk (variable) rate constant of a chemical reactionk J/K Boltzmann constantK (variable) equilibrium constantl m lengthm g, kg, t massMr relative molecular mass (molecular weight)n20

D refractive index (sodium D-line, 20 °C)n mol amount of substanceNA mol�1 Avogadro constant (6.023× 1023 mol�1)P Pa, bar* pressureQ J quantity of heatr m radiusR JK�1 mol�1 gas constantR Ω electric resistanceS J/K entropyt s, min, h, d, month, a timet °C temperatureT K absolute temperatureu m/s velocityU V electric potential

Symbols and Units IX

Symbols and Units (Continued from p. IX)

Symbol Unit Physical Quantity

U J internal energyV m3, L, mL, μL volumew mass fractionW J workxB mole fraction of substance BZ proton number, atomic numberα cubic expansion coefficientα Wm�2K�1 heat-transfer coefficient (heat-transfer number)α degree of dissociation of electrolyte[α] 10�2deg cm2g�1 specific rotationη Pa�s dynamic viscosityθ °C temperatureϰ cp/cvλ Wm�1K�1 thermal conductivityλ nm, m wavelengthμ chemical potentialν Hz, s�1 frequencyν m2/s kinematic viscosity (η/ϱ)π Pa osmotic pressureϱ g/cm3 densityσ N/m surface tensionτ Pa (N/m2) shear stressφ volume fractionχ Pa�1 (m2/N) compressibility

*The official unit of pressure is the pascal (Pa).

X Symbols and Units

Conversion Factors

SI unit Non-SI unit From SI to non-SI multiply by

Masskg pound (avoirdupois) 2.205kg ton (long) 9.842� 10�4

kg ton (short) 1.102� 10�3

Volumem3 cubic inch 6.102� 104

m3 cubic foot 35.315m3 gallon (U.S., liquid) 2.642� 102

m3 gallon (Imperial) 2.200� 102

Temperature�C �F �C� l.8� 32

ForceN dyne 1.0� 105

Energy, WorkJ Btu (int.) 9.480� 10�4

J cal (int.) 2.389� 10�1

J eV 6.242� 1018

J erg 1.0� 107

J kW�h 2.778� 10�7

J kp�m 1.020� 10�1

PressureMPa at 10.20MPa atm 9.869MPa bar 10kPa mbar 10kPa mm Hg 7.502kPa psi 0.145kPa torr 7.502

Powers of Ten

E (exa) 1018 d (deci) 10�1

P (peta) 1015 c (centi) 10�2

T (tera) 1012 m (milli) 10�3

G (giga) 109m (micro) 10�6

M (mega) 106 n (nano) 10�9

k (kilo) 103 p (pico) 10�12

h (hecto) 102 f (femto) 10�15

da (deca) 10 a (atto) 10�18

Conversion Factors XI

Abbreviations

The following is a list of the abbreviations used in the text. Common terms, the names of publicationsand institutions, and legal agreements are included along with their full identities. Other abbreviationswill be defined wherever they first occur in an article. For further abbreviations, see page IX, Symbolsand Units; page XVII, Frequently Cited Companies (Abbreviations), and page XVIII, Country Codesin patent references. The names of periodical publications are abbreviated exactly as done by ChemicalAbstracts Service.

abs. absolutea.c. alternating currentACGIH American Conference of Governmental

Industrial HygienistsACS American Chemical SocietyADI acceptable daily intakeADN accord européen relatif au transport

international des marchandises danger-euses par voie de navigation interieure(European agreement concerning the in-ternational transportation of dangerousgoods by inland waterways)

ADNR ADN par le Rhin (regulation concerningthe transportation of dangerous goods onthe Rhine and all national waterways ofthe countries concerned)

ADP adenosine 5´-diphosphateADR accord européen relatif au transport

international des marchandises danger-euses par route (European agreementconcerning the international transporta-tion of dangerous goods by road)

AEC Atomic Energy Commission (UnitedStates)

a.i. active ingredientAIChE American Institute of Chemical

EngineersAIME American Institute of Mining,

Metallurgical, and Petroleum EngineersANSI American National Standards InstituteAMP adenosine 5´-monophosphateAPhA American Pharmaceutical AssociationAPI American Petroleum InstituteASTM American Society for Testing and

MaterialsATP adenosine 5´-triphosphateBAM Bundesanstalt für Materialprüfung

(Federal Republic of Germany)BAT Biologischer Arbeitsstofftoleranzwert

(biological tolerance value for a work-ing material, established by MAKCommission, see MAK)

Beilstein Beilstein’s Handbook of Organic Chem-istry, Springer, Berlin – Heidelberg –

New YorkBET Brunauer – Emmett – Teller

BGA Bundesgesundheitsamt (FederalRepublic of Germany)

BGB1. Bundesgesetzblatt (Federal Republicof Germany)

BIOS British Intelligence Objectives Subcom-mittee Report (see also FIAT)

BOD biological oxygen demandbp boiling pointB.P. British PharmacopeiaBS British Standardca. circacalcd. calculatedCAS Chemical Abstracts Servicecat. catalyst, catalyzedCEN Comité Européen de Normalisationcf. compareCFR Code of Federal Regulations (United

States)cfu colony forming unitsChap. chapterChemG Chemikaliengesetz (Federal Republic

of Germany)C.I. Colour IndexCIOS Combined Intelligence Objectives Sub-

commitee Report (see also FIAT)CLP Classification, Labelling and PackagingCNS central nervous systemCo. CompanyCOD chemical oxygen demandconc. concentratedconst. constantCorp. Corporationcrit. criticalCSA Chemical Safety Assessment according

to REACHCSR Chemical Safety Report according to

REACHCTFA The Cosmetic, Toiletry and

Fragrance Association (United States)DAB Deutsches Arzneibuch, Deutscher

Apotheker-Verlag, Stuttgartd.c. direct currentdecomp. decompose, decompositionDFG Deutsche Forschungsgemeinschaft

(German Science Foundation)dil. dilute, diluted

Abbreviations XIII

DIN Deutsche Industrienorm (Federal Republicof Germany)

DMF dimethylformamideDNA deoxyribonucleic acidDOE Department of Energy (United States)DOT Department of Transportation –

Materials Transportation Bureau(United States)

DTA differential thermal analysisEC effective concentrationEC European Communityed. editor, edition, editede.g. for exampleemf electromotive forceEmS Emergency ScheduleEN European Standard (European

Community)EPA Environmental Protection Agency

(United States)EPR electron paramagnetic resonanceEq. equationESCA electron spectroscopy for chemical

analysisesp. especiallyESR electron spin resonanceEt ethyl substituent (�C2H5)et al. and othersetc. et ceteraEVO Eisenbahnverkehrsordnung (Federal

Republic of Germany)exp ( . . .) e(. . . ), mathematical exponentFAO Food and Agriculture Organization

(United Nations)FDA Food and Drug Administration

(United States)FD&C Food, Drug and Cosmetic Act

(United States)FHSA Federal Hazardous Substances Act

(United States)FIAT Field Information Agency, Technical

(United States reports on the chemicalindustry in Germany, 1945)

Fig. figurefp freezing pointFriedländer P. Friedländer, Fortschritte der

Teerfarbenfabrikation und verwandterIndustriezweige Vol. 1–25, Springer,Berlin 1888–1942

FT Fourier transform(g) gas, gaseousGC gas chromatographyGefStoffV Gefahrstoffverordnung (regulations in

the Federal Republic of Germany con-cerning hazardous substances)

GGVE Verordnung in der BundesrepublikDeutschland über die Beförderunggefährlicher Güter mit der Eisenbahn

(regulation in the Federal Republic ofGermany concerning the transportationof dangerous goods by rail)

GGVS Verordnung in der BundesrepublikDeutschland über die Beförderunggefährlicher Güter auf der Straße(regulation in the Federal Republic ofGermany concerning the transportationof dangerous goods by road)

GGVSee Verordnung in der BundesrepublikDeutschland über die Beförderunggefährlicher Güter mit Seeschiffen(regulation in the Federal Republic ofGermany concerning the transportationof dangerous goods by sea-goingvessels)

GHS Globally Harmonised System of Chemi-cals (internationally agreed-upon system,created by theUN, designed to replace thevarious classification and labeling stan-dards used in different countries by usingconsistent criteria for classification andlabeling on a global level)

GLC gas-liquid chromatographyGmelin Gmelin’s Handbook of Inorganic

Chemistry, 8th ed., Springer, Berlin –

Heidelberg –New YorkGRAS generally recognized as safeHal halogen substituent (�F, �Cl, �Br, �I)Houben-

WeylMethoden der organischenChemie, 4th ed., Georg Thieme Verlag,Stuttgart

HPLC high performance liquidchromatography

H statement hazard statement in GHSIAEA International Atomic Energy AgencyIARC International Agency for Research on

Cancer, Lyon, FranceIATA-DGR International Air Transport

Association, Dangerous GoodsRegulations

ICAO International Civil AviationOrganization

i.e. that isi.m. intramuscularIMDG International Maritime Dangerous

Goods CodeIMO Inter-Governmental Maritime Consul-

tive Organization (in the past: IMCO)Inst. Institutei.p. intraperitonealIR infraredISO International Organization for

StandardizationIUPAC International Union of Pure and

Applied Chemistryi.v. intravenous

XIV Abbreviations

Kirk-Othmer

Encyclopedia of Chemical Technology,3rd ed., 1991–1998, 5th ed., 2004–2007,John Wiley & Sons, Hoboken

(1) liquidLandolt-

BörnsteinZahlenwerte u. Funktionen aus Physik,Chemie, Astronomie, Geophysik u.Technik, Springer, Heidelberg 1950–1980; Zahlenwerte und Funktionen ausNaturwissenschaften und Technik,Neue Serie, Springer, Heidelberg,since 1961

LC50 lethal concentration for 50 % of the testanimals

LCLo lowest published lethal concentrationLD50 lethal dose for 50 % of the test animalsLDLo lowest published lethal doseln logarithm (base e)LNG liquefied natural gaslog logarithm (base 10)LPG liquefied petroleum gasM mol/LM metal (in chemical formulas)MAK Maximale Arbeitsplatzkonzentration

(maximum concentration at the work-place in the Federal Republic ofGermany); cf. Deutsche Forschungsge-meinschaft (ed.): Maximale Arbeits-platzkonzentrationen (MAK) undBiologische Arbeitsstofftoleranzwerte(BAT), WILEY-VCH Verlag,Weinheim (published annually)

max. maximumMCA Manufacturing Chemists Association

(United States)Me methyl substituent (�CH3)Methodicum

ChimicumMethodicum Chimicum, Georg ThiemeVerlag, Stuttgart

MFAG Medical First Aid Guide for Use inAccidents Involving Dangerous Goods

MIK maximale Immissionskonzentration(maximum immission concentration)

min. minimummp melting pointMS mass spectrum, mass spectrometryNAS National Academy of Sciences (United

States)NASA National Aeronautics and Space

Administration (United States)NBS National Bureau of Standards

(United States)NCTC National Collection of Type Cultures

(United States)NIH National Institutes of Health

(United States)NIOSH National Institute for Occupational

Safety and Health (United States)NMR nuclear magnetic resonance

no. numberNOEL no observed effect levelNRC Nuclear Regulatory Commission

(United States)NRDC National Research Development

Corporation (United States)NSC National Service Center (United States)NSF National Science Foundation

(United States)NTSB National Transportation Safety Board

(United States)OECD Organization for Economic Cooperation

and DevelopmentOSHA Occupational Safety and Health

Administration (United States)p., pp. page, pagesPatty G.D. Clayton, F.E. Clayton (eds.):

Patty’s Industrial Hygiene andToxicology, 3rd ed., Wiley Interscience,New York

PB Publication Board Report (U.S.report Department of Commerce, Scientific

and Industrial Reports)PEL permitted exposure limitPh phenyl substituent (—C6H5)Ph. Eur. European Pharmacopoeia, Council of

Europe, Strasbourgphr part per hundred rubber (resin)PNS peripheral nervous systemppm parts per millionP statement precautionary statement in GHSq.v. which see (quod vide)REACH Registration, Evaluation, Authorisation

and Restriction of Chemicals (EU regu-lation addressing the production and useof chemical substances, and theirpotential impacts on both human healthand the environment)

ref. refer, referenceresp. respectivelyRf retention factor (TLC)R.H. relative humidityRID réglement international concernant le

transport des marchandises dangereusespar chemin de fer (international conven-tion concerning the transportation ofdangerous goods by rail)

RNA ribonucleic acidR phrase risk phrase according to

(R-Satz) ChemG and GefStoffV (FederalRepublic of Germany)

rpm revolutions per minuteRTECS Registry of Toxic Effects of

Chemical Substances, edited by theNational Institute of Occupational Safetyand Health (United States)

(s) solid

Abbreviations XV

SAE Society of Automotive Engineers(United States)

SAICM Strategic Approach on InternationalChemicals Management (internationalframework to foster the soundmanagement of chemicals)

s.c. subcutaneousSI International System of UnitsSIMS secondary ion mass spectrometryS phrase safety phrase according to

(S-Satz) ChemG and GefStoffV (FederalRepublic of Germany)

STEL Short Term Exposure Limit (see TLV)STP standard temperature and pressure (0°C,

101.325 kPa)Tg glass transition temperatureTA Luft Technische Anleitung zur Reinhaltung

der Luft (clean air regulation in FederalRepublic of Germany)

TA Lärm Technische Anleitung zum Schutzgegen Lärm (low noise regulation inFederal Republic of Germany)

TDLo lowest published toxic doseTHF tetrahydrofuranTLC thin layer chromatographyTLV Threshold Limit Value (TWA

and STEL); published annually bythe American Conference of Govern-mental Industrial Hygienists (ACGIH),Cincinnati, Ohio

TOD total oxygen demandTRK Technische Richtkonzentration

(lowest technically feasible level)TSCA Toxic Substances Control Act

(United States)TÜV Technischer Überwachungsverein

(Technical Control Board of the FederalRepublic of Germany)

TWA Time Weighted AverageUBA Umweltbundesamt (Federal

Environmental Agency)Ullmann Ullmann’s Encyclopedia of Industrial

Chemistry, 6th ed., Wiley-VCH, Wein-heim 2002; Ullmann’s Encyclopedia ofIndustrial Chemistry, 5th ed., VCHVerlagsgesellschaft, Weinheim1985–1996; Ullmanns Encyklopädie

der Technischen Chemie, 4th ed., VerlagChemie, Weinheim 1972–1984; 3rd ed.,Urban und Schwarzenberg, München1951–1970

USAEC United States Atomic EnergyCommission

USAN United States Adopted NamesUSD United States DispensatoryUSDA United States Department of AgricultureU.S.P. United States PharmacopeiaUV ultravioletUVV Unfallverhütungsvorschriften der Ber-

ufsgenossenschaft (workplace safetyregulations in the Federal Republic ofGermany)

VbF Verordnung in der BundesrepublikDeutschland über die Errichtung undden Betrieb von Anlagen zurLagerung, Abfüllung und Beförderungbrennbarer Flüssigkeiten (regulation inthe Federal Republic of Germany con-cerning the construction and operation ofplants for storage, filling, and transpor-tation of flammable liquids; classificationaccording to the flash point ofliquids, in accordance with the classifi-cation in the United States)

VDE Verband Deutscher Elektroingenieure(Federal Republic of Germany)

VDI Verein Deutscher Ingenieure (FederalRepublic of Germany)

vol volumevol. volume (of a series of books)vs. versusWGK Wassergefährdungsklasse (water hazard

class)WHO World Health Organization (United

Nations)Winnacker-

KüchlerChemische Technologie, 4th ed., CarlHanser Verlag, München, 1982-1986;Winnacker-Küchler, ChemischeTechnik: Prozesse und Produkte,Wiley-VCH, Weinheim, 2003–2006

wt weight$ U.S. dollar, unless otherwise stated

XVI Abbreviations

Frequently Cited Companies(Abbreviations)

AirProducts

Air Products and Chemicals

Akzo Algemene Koninklijke ZoutOrganon

Alcoa Aluminum Company of AmericaAllied Allied CorporationAmer. American CyanamidCyanamid CompanyBASF BASF AktiengesellschaftBayer Bayer AGBP British Petroleum CompanyCelanese Celanese CorporationDaicel Daicel Chemical IndustriesDainippon Dainippon Ink and Chemicals Inc.Dow

ChemicalThe Dow Chemical Company

DSM Dutch Staats MijnenDu Pont E.I. du Pont de Nemours & CompanyExxon Exxon CorporationFMC Food Machinery & Chemical

CorporationGAF General Aniline & Film CorporationW.R.

GraceW.R. Grace & Company

Hoechst Hoechst AktiengesellschaftIBM International Business Machines

CorporationICI Imperial Chemical Industries

IFP Institut Français du PétroleINCO International Nickel Company3M Minnesota Mining and

Manufacturing CompanyMitsubishi Mitsubishi Chemical Industries

ChemicalMonsanto Monsanto CompanyNippon Nippon Shokubai Kagaku Kogyo

ShokubaiPCUK Pechiney Ugine KuhlmannPPG Pittsburg Plate Glass IndustriesSearle G.D. Searle & CompanySKF Smith Kline & French LaboratoriesSNAM Societá Nazionale MetandottiSohio Standard Oil of OhioStauffer Stauffer Chemical CompanySumitomo Sumitomo Chemical CompanyToray Toray Industries Inc.UCB Union Chimique BelgeUnion

CarbideUnion Carbide Corporation

UOP Universal Oil Products CompanyVEBA Vereinigte Elektrizitäts- und Bergwerks-

AGWacker Wacker Chemie GmbH

Frequently Cited Companies (Abbreviations) XVII

Country Codes

The following list contains a selection of standard country codes used in the patent references.

AT AustriaAU AustraliaBE BelgiumBG BulgariaBR BrazilCA CanadaCH SwitzerlandCS CzechoslovakiaDD German Democratic RepublicDE Federal Republic of Germany

(and Germany before 1949)∗

DK DenmarkES SpainFI FinlandFR FranceGB United KingdomGR GreeceHU HungaryID Indonesia

IL IsraelIT ItalyJP Japan∗

LU LuxembourgMA MoroccoNL Netherlands∗

NO NorwayNZ New ZealandPL PolandPT PortugalSE SwedenSU Soviet UnionUS United States of AmericaYU YugoslaviaZA South AfricaEP European Patent Office∗

WO World Intellectual PropertyOrganization

∗For Europe, Federal Republic of Germany, Japan, and the Netherlands, the type of patent is specified: EP (patent),EP-A (application), DE (patent), DE-OS (Offenlegungsschrift), DE-AS (Auslegeschrift), JP (patent), JP-Kokai(Kokai tokkyo koho), NL (patent), and NL-A (application).

XVIII Country Codes

Part 1

Fundamentals

Ullmann’s Polymers and Plastics: Products and Processes 2016 Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimISBN: 978-3-527-33823-8 / DOI: 10.1002/14356007

Plastics, General Survey, 1. Definition, MolecularStructure and Properties

HANS-GEORG ELIAS, Michigan Molecular Institute, Midland, United States

ROLF MÜLHAUPT, Institute for Macromolecular Chemistry, Freiburg, Germany

1. Introduction . . . . . . . . . . . . . . . 51.1. Polymers . . . . . . . . . . . . . . . . . . 51.1.1. Fundamental Terms . . . . . . . . . . . 51.1.2. Nomenclature . . . . . . . . . . . . . . . 61.2. Plastics . . . . . . . . . . . . . . . . . . . 81.2.1. Fundamental Terms . . . . . . . . . . . 81.2.2. Designations. . . . . . . . . . . . . . . . 91.3. History of Plastics . . . . . . . . . . . 151.4. Economic Importance . . . . . . . . 162. Molecular Structure of Polymers

. . . . . . . . . . . . . . . . . . . . . . . . . 182.1. Constitution . . . . . . . . . . . . . . . 182.1.1. Homopolymers . . . . . . . . . . . . . . 182.1.2. Copolymers . . . . . . . . . . . . . . . . 192.1.3. Branched Polymers . . . . . . . . . . . 202.1.4. Ordered Chain Assemblies . . . . . . 212.1.5. Unordered Networks . . . . . . . . . . 222.2. Molar Masses and Molar Mass

Distributions . . . . . . . . . . . . . . . 232.2.1. Molar Mass Average . . . . . . . . . . 232.2.2. Determination of Molar Mass . . . . 232.2.3. Molar Mass Distributions . . . . . . . 252.2.4. Determination of Molar Mass

Distributions. . . . . . . . . . . . . . . . 272.3. Configurations. . . . . . . . . . . . . . 282.4. Conformations. . . . . . . . . . . . . . 292.4.1. Microconformations. . . . . . . . . . . 292.4.2. Conformations in Ideal Polymer

Crystals . . . . . . . . . . . . . . . . . . . 312.4.3. Conformations in Polymer Solutions 322.4.4. Unperturbed Coils . . . . . . . . . . . . 322.4.5. Perturbed Coils . . . . . . . . . . . . . . 332.4.6. Wormlike Chains . . . . . . . . . . . . 333. Polymer Manufacture . . . . . . . . 343.1. Raw Materials. . . . . . . . . . . . . . 343.1.1. Wood . . . . . . . . . . . . . . . . . . . . 343.1.2. Coal . . . . . . . . . . . . . . . . . . . . . 353.1.3. Natural Gas and Fracking. . . . . . . 353.1.4. Petroleum. . . . . . . . . . . . . . . . . . 35

3.1.5. Other Renewable Resources andBiorefineries . . . . . . . . . . . . . . . . 35

3.2. Polymer Syntheses: Overview. . . 373.2.1. Classifications. . . . . . . . . . . . . . . 373.2.2. Functionality . . . . . . . . . . . . . . . 393.2.3. Cyclopolymerizations . . . . . . . . . 403.3. Chain-Growth Polymerization . . 403.3.1. Thermodynamics. . . . . . . . . . . . . 403.3.2. Free-Radical Polymerizations . . . . 413.3.3. Anionic Polymerizations . . . . . . . 473.3.4. Cationic Polymerizations . . . . . . . 483.3.5. Ziegler-Natta, ROMP and ADMET

Catalysis . . . . . . . . . . . . . . . . . . 483.3.6. Copolymerizations. . . . . . . . . . . . 563.4. Polycondensations and

Polyadditions. . . . . . . . . . . . . . . 573.4.1. Bifunctional Polycondensations . . . 573.4.2. Multifunctional Polycondensations

and Hyperbranched Polymers . . . . 603.4.3. Polyaddition . . . . . . . . . . . . . . . . 603.5. Polymer Reactions . . . . . . . . . . . 613.5.1. Polymer Transformations . . . . . . . 613.5.2. Block and Graft Formations . . . . . 623.5.3. Cross-Linking Reactions . . . . . . . 623.5.4. Degradation Reactions . . . . . . . . . 624. Plastics Manufacture . . . . . . . . 634.1. Homogenization and

Compounding . . . . . . . . . . . . . . 634.2. Additives. . . . . . . . . . . . . . . . . . 634.2.1. Overview . . . . . . . . . . . . . . . . . . 634.2.2. Chemofunctional Additives. . . . . . 644.2.3. Processing Aids . . . . . . . . . . . . . 654.2.4. Extending and Functional Fillers . . 654.2.5. Plasticizers . . . . . . . . . . . . . . . . . 684.2.6. Colorants . . . . . . . . . . . . . . . . . . 684.2.7. Blowing Agents . . . . . . . . . . . . . 684.3. Processing . . . . . . . . . . . . . . . . . 695. Supermolecular Structures . . . . 705.1. Noncrystalline States . . . . . . . . . 70

Ullmann’s Polymers and Plastics: Products and Processes 2016 Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimISBN: 978-3-527-33823-8 / DOI: 10.1002/14356007.a20_543.pub2

5.1.1. Structure . . . . . . . . . . . . . . . . . . 705.1.2. Orientation . . . . . . . . . . . . . . . . . 705.2. Polymer Crystals . . . . . . . . . . . . 715.2.1. Introduction . . . . . . . . . . . . . . . . 715.2.2. Crystal Structures . . . . . . . . . . . . 715.2.3. Crystallinity . . . . . . . . . . . . . . . . 725.2.4. Morphology . . . . . . . . . . . . . . . . 725.3. Mesophases and Liquid-

Crystalline Polymers . . . . . . . . . 765.3.1. Introduction . . . . . . . . . . . . . . . . 765.3.2. Types of Liquid Crystals . . . . . . . 765.3.3. Mesogens. . . . . . . . . . . . . . . . . . 775.3.4. Lyotropic Liquid-Crystalline

Polymers . . . . . . . . . . . . . . . . . . 795.3.5. Thermotropic Liquid Crystal

Polymers . . . . . . . . . . . . . . . . . . 815.3.6. Block Copolymers. . . . . . . . . . . . 815.3.7. Ionomers . . . . . . . . . . . . . . . . . . 825.4. Gels . . . . . . . . . . . . . . . . . . . . . 835.5. Polymer Surfaces. . . . . . . . . . . . 845.5.1. Structure . . . . . . . . . . . . . . . . . . 845.5.2. Interfacial Tension. . . . . . . . . . . . 845.5.3. Adsorption . . . . . . . . . . . . . . . . . 846. Thermal Properties . . . . . . . . . . 856.1. Molecular Motion . . . . . . . . . . . 856.1.1. Thermal Expansion . . . . . . . . . . . 856.1.2. Heat Capacity . . . . . . . . . . . . . . . 856.1.3. Heat Conductivity . . . . . . . . . . . . 866.2. Thermal Transitions and

Relaxations . . . . . . . . . . . . . . . . 866.2.1. Overview . . . . . . . . . . . . . . . . . . 866.2.2. Crystallization. . . . . . . . . . . . . . . 886.2.3. Melting . . . . . . . . . . . . . . . . . . . 896.2.4. Liquid Crystal Transitions . . . . . . 906.2.5. Glass Transitions. . . . . . . . . . . . . 916.2.6. Other Transitions and

Relaxations . . . . . . . . . . . . . . . . 926.2.7. Technical Methods . . . . . . . . . . . 926.3. Transport . . . . . . . . . . . . . . . . . 926.3.1. Self-Diffusion . . . . . . . . . . . . . . . 926.3.2. Permeation . . . . . . . . . . . . . . . . . 937. Rheological Properties . . . . . . . 957.1. Introduction . . . . . . . . . . . . . . . 957.2. Shear Viscosities at Rest . . . . . . 957.2.1. Fundamentals . . . . . . . . . . . . . . . 957.2.2. Molar Mass Dependence . . . . . . . 967.2.3. Concentrated Solutions . . . . . . . . 967.3. Non-Newtonian Shear

Viscosities . . . . . . . . . . . . . . . . . 977.3.1. Overview . . . . . . . . . . . . . . . . . . 977.3.2. Flow Curves. . . . . . . . . . . . . . . . 98

7.3.3. Melt Viscosities . . . . . . . . . . . . . 987.4. Extensional Viscosities . . . . . . . . 1007.4.1. Fundamentals . . . . . . . . . . . . . . . 1007.4.2. Melts. . . . . . . . . . . . . . . . . . . . . 1007.4.3. Solutions . . . . . . . . . . . . . . . . . . 1018. Mechanical Properties

. . . . . . . . . . . . . . . . . . . . . . . . . 1018.1. Introduction . . . . . . . . . . . . . . . 1018.1.1. Deformation of Polymers . . . . . . . 1018.1.2. Tensile Tests . . . . . . . . . . . . . . . 1028.1.3. Moduli and Poisson Ratios. . . . . . 1048.2. Energy Elasticity . . . . . . . . . . . . 1048.2.1. Theoretical Moduli . . . . . . . . . . . 1048.2.2. Real Moduli . . . . . . . . . . . . . . . . 1058.2.3. Temperature Dependence . . . . . . . 1058.3. Entropy Elasticity . . . . . . . . . . . 1068.4. Viscoelasticity . . . . . . . . . . . . . . 1078.4.1. Fundamentals . . . . . . . . . . . . . . . 1078.4.2. Time-Temperature

Superposition . . . . . . . . . . . . . . . 1088.5. Dynamic Behavior . . . . . . . . . . . 1098.5.1. Fundamentals . . . . . . . . . . . . . . . 1098.5.2. Molecular Interpretations . . . . . . . 1108.6. Fracture . . . . . . . . . . . . . . . . . . 1118.6.1. Overview . . . . . . . . . . . . . . . . . . 1118.6.2. Theoretical Fracture Strength . . . . 1118.6.3. Real Fracture Strength . . . . . . . . . 1128.6.4. Impact Resistance . . . . . . . . . . . . 1148.6.5. Stress Cracking. . . . . . . . . . . . . . 1148.6.6. Fatigue . . . . . . . . . . . . . . . . . . . 1158.7. Surface Mechanics. . . . . . . . . . . 1158.7.1. Hardness . . . . . . . . . . . . . . . . . . 1158.7.2. Friction . . . . . . . . . . . . . . . . . . . 1158.7.3. Abrasion and Wear . . . . . . . . . . . 1169. Electric Properties . . . . . . . . . . 1169.1. Dielectric Properties . . . . . . . . . 1169.1.1. Relative Permittivity . . . . . . . . . . 1169.1.2. Dielectric Loss . . . . . . . . . . . . . . 1179.1.3. Dielectric Strength and Tracking

Resistance . . . . . . . . . . . . . . . . . 1189.1.4. Electrostatic Charging . . . . . . . . . 1199.2. Electrical Conductivity. . . . . . . . 1199.3. Photoconductivity . . . . . . . . . . . 12110. Optical Properties . . . . . . . . . . 12111. Polymer Composites . . . . . . . . . 12211.1. Introduction . . . . . . . . . . . . . . . 12211.1.1. Overview . . . . . . . . . . . . . . . . . . 12211.1.2. Mixture Rules. . . . . . . . . . . . . . . 12311.2. Filled Polymers . . . . . . . . . . . . . 12611.2.1. Microcomposites . . . . . . . . . . . . . 12611.2.2. Molecular Composites . . . . . . . . . 128

4 Plastics, General Survey, 1. Definition, Molecular Structure and Properties Vol. 1

11.2.3. Macrocomposites . . . . . . . . . . . . 12811.2.4. Nanocomposites . . . . . . . . . . . . . 12911.3. Homogeneous Blends . . . . . . . . . 13111.3.1. Thermodynamics. . . . . . . . . . . . . 13111.3.2. Plastification. . . . . . . . . . . . . . . . 13211.3.3. Rubber Blends . . . . . . . . . . . . . . 13311.3.4. Plastic Blends . . . . . . . . . . . . . . . 13411.4. Heterogeneous Blends . . . . . . . . 13411.4.1. Compatible Polymers. . . . . . . . . . 13411.4.2. Blend Formation . . . . . . . . . . . . . 13411.4.3. Toughened Plastics . . . . . . . . . . . 13511.4.4. Thermoplastic Elastomers. . . . . . . 13611.5. Expanded Plastics . . . . . . . . . . . 13612. Plastics and Sustainability . . . . . 13712.1. Plastics and Environment. . . . . . 137

12.2. Green Polymer Chemistry and LifeCycle Assessment. . . . . . . . . . . . 139

12.3. Plastics Waste Recycling . . . . . . 14012.3.1. Mechanical Recycling . . . . . . . . . 14012.3.2. Feedstock Recycling . . . . . . . . . . 14112.3.3. Energy Recycling . . . . . . . . . . . . 14112.3.4. Biodegradation and Bio-based

Plastics . . . . . . . . . . . . . . . . . . . 14112.3.5. Plastics from Carbon Dioxide . . . . 14212.4. Polymers for Sustainable

Development . . . . . . . . . . . . . . . 143References. . . . . . . . . . . . . . . . . 144

1. Introduction

Plastics are commercially used materials that arebased on polymers or prepolymers. The nameplastics refers to their easy processibility andshaping (Greek: plastein = to form, to shape).Plastics and polymers, also termed macromole-cules (Greek: macro= large), are not synonyms.Polymers or prepolymers are raw materials forplastics; they become plastics only after proc-essing. The same polymers may be used asplastics or as fibers, paints, rubbers, coatings,adhesives, thickeners, surfactants, and ion-exchange membranes. Properties of polymersare engineered by varying the molecular archi-tecture or the formulation, combining them withdifferent materials in multicomponent and mul-tiphase systems. Typically, plastics containadditives that are needed to enhance their sta-bility and to tune their properties. Unparalleledby any other material, polymers are exceptionalregarding their attractive combination of facileprocessing with low mass and high versatilityin terms of properties, applications, flexiblechoice of feedstocks, and recycling. The sys-tem integration of functional polymers repre-sents the key to the development of advancedtechnologies with applications ranging fromlightweight engineering to packaging, con-struction, aerospace and automotive industries,as well as biomedical engineering. Whereasmost plastics are passive, advanced functional

plastics are rendered interactive and capable ofresponding to environmental stimuli. Today,highly cost-, resource-, eco-, and energy-efficient polymers play a prominent role insustainable development of advanced materi-als and technologies.

1.1. Polymers

1.1.1. Fundamental Terms [1–16]

The term polymer refers to macromoleculescomposed of many units (Greek: poly =many, meros = parts). As first proposed byHERMANN STAUDINGER in 1920, who wasawarded the Nobel Price of Chemistry forhis groundbreaking concept in 1953, macro-molecules consist of many atoms, usually athousand or more, thereby having high molarmasses. Prior to STAUDINGER, the term poly-mer was not related to high molar mass. Forexample, benzene was originally called apolymer which was “polymerized” from threeacetylene molecules. What is now called apolymer consists of molecules with hundredsand thousands of such units; it was thereforetermed “high polymer” in the ancient litera-ture. The term polymer carries with it theconnotation of molecules composed ofmany equal “mers”, such as the ethylene units

Vol. 1 Plastics, General Survey, 1. Definition, Molecular Structure and Properties 5

in polyethylene, R´(CH2CH2)nR´´. The num-ber n of monomer units in the polymer mole-cule is called the degree of polymerization X.There are, however, many polymer molecules(especially biopolymer molecules) with verydifferent types of monomers per molecule,such as protein molecules H(NH–CHR–

CO)nOH with up to 20 different R substitu-ents. In accordance with STAUDINGER’s view, aless constraining and more general term forpolymer molecule is thus macromolecule.However, there is no sharp dividing linewith respect to the number of units per mole-cule between macromolecules and low molarmass compounds. In principle, linear thermo-plastic polymers are considered polymerswhen entanglement occurs, thus accountingfor the viscoelastic properties typical forpolymeric thermoplastics.

It was HERMANN STAUDINGER who recognizedthat polymers in industry and in nature aresynthesized according to the same blueprint.Similar to pearls in a pearl necklace, monomermolecules are linked together by covalent bondformation. In the early days of polymer sci-ences and engineering, all polymers were bio-based, because efficient synthetic polymeriza-tion processes were not at hand. Prominentexamples of biopolymers include proteins, pol-ynucleotides, cis-1,4-polyisoprene as naturalrubber, polysaccharides (carbohydrates) withcellulose as the most abundant polymer andmajor component of biomass. Wood is a com-posite of two biopolymers, i.e., cellulose andlignin. As pointed out by STAUDINGER andothers, most silicates are inorganic polymersderived by polymerization of silicic acid and itsderivatives. Some of these naturally occurringpolymers are used by man without furtherchemical transformation (e.g., cellulose forpaper and cardboard). Yet, the chemical trans-formation of natural polymers with retention oftheir chain structures leads to solution and evenmelt processable semisynthetic materials, forexample, cellulose acetates from cellulose.Chains of other natural polymers are cross-linked before commercial use. Examples arethe hardening of casein (a protein) by formal-dehyde to produce galalith (plastic) or thevulcanization of cis-1,4-polyisoprene (naturalrubber) to afford an elastomer.

Today, most polymers are synthesizedchemically from synthetic monomers. Exam-ples include the preparations of polyethylenefrom ethylene, poly(vinyl chloride) from vinylchloride, nylon 6 from ε-caprolactam, or nylon66 from adipic acid and hexamethylenedi-amine. Whereas the majority of monomersare derived from oil and gas in petrochemistry,the progress in biotechnology and the quest forgreen economy are stimulating the productionof bio-based synthetic monomers, such asbutadiene, ethylene, propene, acrylic acid, gly-col, and lactic acid in biorefineries using bio-mass as feedstock. Some industrial polymersresult from the chemical conversion of othersynthetic polymers, for example, poly(vinylalcohol) from poly(vinyl acetate). In contrastto natural polymer syntheses and bio-technology, most large scale commercial syn-thetic polymers are produced in the absence ofwater either in bulk or gas phase. Moreover,compared to biopolymers, synthetic polymers,including the synthetic bio-based polymersderived from renewable feedstocks, aremuch easier to tailor with respect to their molarmass distribution, short- and long-chainbranching and stereochemistry, thus meetingthe demands of polymer melt processing andpolymer applications. In contrast to proteinsynthesis, where polypeptide chains are pro-duced with identical molar mass andcomonomer sequence distribution, is ratherproblematic to produce thermoplastics withshear thinning resulting from long chainbranching and multimodal molar mass distri-bution with enzyme-catalyzed reactions.

1.1.2. Nomenclature [1, 5, 17–19]

The nomenclature of individual polymers andplastics is as confusing as their classificationaccording to properties. Various systems ofnomenclature are used simultaneously.Abbreviations and acronyms abound, some-times with different meanings for the sameletter combinations and other times withoutexplanation. In addition, many thousands oftrade names are used worldwide for plastics,fibers, elastomers, and polymeric additives.Furthermore, a polymer from a certain

6 Plastics, General Survey, 1. Definition, Molecular Structure and Properties Vol. 1

company may come in many different gradesdepending on the processibility and applica-tion, sometimes up to 100 per polymer type.Some of these grades may even bear differenttrade names for various applications. Thefollowing nomenclature systems are com-monly used for polymers.

Long-known Natural Polymers often have Triv-ial Names. Examples are cellulose, the poly-meric sugar (-ose) of the plant cell; casein, themost important protein of milk and cheese(Latin: caseus = cheese); nucleic acids, theacids found in the cell nucleus; catalase, acatalyzing enzyme.

Synthetic Polymers are often Named after TheirMonomers. Polymers of ethylene thus lead topolyethylene, styrene to polystyrene, vinylchloride to poly(vinyl chloride), and lacticacid to a polylactic acid. This “polymonomer”nomenclature has the disadvantage that theconstitution of monomeric units of the polymermolecules is not identical with the constitutionof the monomers themselves. For example, thepolymerization of ethylene, CH2=CH2, leadsto ∼(CH2–CH2)n∼, a saturated compound andthus a polyalkane, not an unsaturated “ene” asthe name polyethylene may suggest. Thepolymerization of lactams (cyclic amides)does not give macromolecules with intact lac-tam rings in the polymer chains but gives open-chain polyamides, etc. This polymonomerscheme is also ambiguous if a monomer canlead to more than one characteristic unit in apolymer. An example is acrolein, CH2=CH(CHO), which can polymerize via the ethylenicdouble bond to give ∼[CH2–CH(CHO)]n∼, viathe aldehyde group to ∼[O–CH(CH=CH2)]n,or via both to give six-membered rings inpolymer chains.

For trade purposes, certain polymer namesmay denote not only homopolymers but alsocopolymers, contrary to what the “chemical”names imply. For example, the copolymers ofethylene with up to 10% butene-1, hexene-1, oroctene-1 are known as linear low-density poly-ethylenes (LLDPEs). The commonly usedchemical names of plastics thus often do notindicate the true chemical structure of the

monomeric units of the polymers on whichthey are based.

Polymers are often Named after CharacteristicGroups in Their Repeating Units. Polyamidesare thus polymers with amide groups –NHCO–

in their repeating units; for example ∼[NHCO(CH2)5]n∼ = polyamide 6 = nylon 6 = poly(ε-caprolactam). Other examples are polyesterswith ester groups –COO– or polyurethaneswith urethane groups –NH–CO–O– in thechains. A disadvantage is that this namingscheme is identical with that of organic chem-istry where a polyisocyanate denotes a lowmolar mass compound with more than oneisocyanate group per molecule [e.g.,C6H3(NCO)3]. A macromolecular polyisocya-nate would thus be a polymer with many intactisocyanate groups per chain, for example, poly(vinyl isocyanate) ∼[CH2–CH(NCO)]n∼. Thepolyisocyanates of polymer chemistry, on theother hand, possess polymerized isocyanategroups as, for example, in ∼(NR–CO)n∼.Such compounds are unfortunately also oftencalled polyisocyanates.

IUPAC Names. IUPAC recommends the useof constitutive names, similar to those used ininorganic and organic chemistry. The nomen-clature of low and high molar mass inorganicmolecules follows the additivity principle;those of low molar mass organic moleculesthe substitution principle. The nomenclature oforganic macromolecules is a hybrid of bothprinciples: The smallest repeating units arethought of as biradicals according to the sub-stitution principle; then their names are addedaccording to the additivity principle, put inparentheses, and prefixed with “poly.” Namesof repeating units are written without spacesbetween words. The polymer ∼[O–CH2]n∼from formaldehyde, H2C=O, is thus calledpoly(oxymethylene), abbreviated as POM.The polycondensation of ethylene glycolHO–CH2–CH2–OH with terephthalic acidHOOC–(p-C6H4)–COOH leads to a polymer∼[O–CH2CH2–O–OC(p-C6H4)CO]n∼ with thesystematic name poly(oxyethyleneoxyterephtha-loyl). The trivial names of this polymer are poly(ethylene terephthalate) and poly(ethylene glycolterephthalate). It is also known as PET

Vol. 1 Plastics, General Survey, 1. Definition, Molecular Structure and Properties 7

(an acronym) or PETP (an abbreviation) in theplastics literature, by the acronym PES in thefiberliterature, and as PETE for recycling purposes.

With exception of POM, IUPAC names arerarely used in the plastics literature. They arehowever important for systematic searches inChemical Abstracts and other literatureservices.

1.2. Plastics

1.2.1. Fundamental Terms [20–56]

Early plastics resembled natural resins. Naturalresin refers mainly to oleoresins from tree sapbut is also used for shellac, insect exudations,and mineral hydrocarbons (→ Resins, Natu-ral). Early plastics were thus sometimes calledsynthetic resins. The word resin is today occa-sionally used for any organic chemical com-pound with medium to high molar mass thatserves as a raw material for plastics (for adefinition of the term resin according to currentstandards, see → Resins, Synthetic). Resin isnot to be confused with rosin, which refers tomixtures of C20 fused-ring monocarboxylicacids, such as pine oil, tall oil, and kauri resin.Rosin is the main component of naval stores(→ Resins, Natural).

Plastics are usually divided into two groupsaccording to their hardening processes. Thosethat yield solid materials by simple cooling of apolymer melt (a physical process) and softenwhile being heated are called thermoplastics.Thermosets, on the other hand, harden throughchemical cross-linking reactions between poly-mer molecules; when heated, they do not softenbut decompose chemically (→ Thermosets).The shaping of a thermoplastic is thus a revers-ible process: The same material can be meltedand processed again. A thermoset cannot beremelted and reshaped; its formation isirreversible.

Thermoplastics are normally composed offairly high molar mass molecules becausemany physical properties effectively becomemolar mass independent only above a certainmolar mass enabling chain entanglement.Examples are melting temperatures and themoduli of elasticity. Other properties, however,

increase with increasing molar mass and entan-glement (e.g., melt viscosities).

Thermosets are usually generated from fairlylow molar mass polymers, called oligomers(science) or prepolymers (industry). Oligomerscontaining functional endgroups are named tele-chelics, and telechelics containing polymeriz-able endgroups are termed macromonomers.High molar masses are unnecessary herebecause chemical reactions between prepolymermolecules lead to an interconnection of thesemolecules (cross-linking or advancement,respectively) and thus to a giant moleculewith 100% conversion of the prepolymer. Pre-polymers are thus thermosetting materials andbecome true thermosets only after the hardeningreaction.

Plastics are usually divided into four groups:Commodity plastics (also called standard plas-tics or bulk plastics), engineering plastics(sometimes referred to as technical plastics ortechnoplastics), high-performance plastics, andfunctional plastics (or specialty plastics). Acommodity, engineering, or high-performanceplastic may have many different applications,whereas a functional plastic has one very spe-cific application. Polyethylene, a commodityplastic, may according to its type or grade beused for containers, as packaging film, as agri-cultural mulch, etc. Poly(ethylene–co–vinylalcohol) with a high content of vinyl alcoholunits, on the other hand, is a functional plasticthat is used only as an oxygen barrier resin.Other functional plastics are employed in opto-electronics, as resists, as piezoelectric materials,etc. Functional plastic is not synonymous withfunctional polymer or functionalized polymer,because the latter terms refer to polymers withfunctional chemical groups (i.e., groups withspecific chemical reactivities).

Commodity plastics are manufactured ingreat amounts at low cost; hence, the termsbulk plastics or standard plastics. Engineeringplastics possess improved mechanical propert-ies and improved dimensional stability as com-pared to commodity plastics. Such improvedproperties may be higher moduli of elasticity,higher heat distortion temperature, smaller coldflows, higher impact strengths, etc. Engineeringplastics are also often defined as those thermo-plastics that maintain dimensional stability and

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