Fluoroelastomers Handbook – The Definitive User’s Guide and Databook

Fluoroelastomers Handbook – The Definitive User’s Guide and Databook
Albert L. Moore, Sc.D.
Wilmington, Delaware
Contents
Series Editor’s Preface . ix
Preface . xi
Acknowledgments xiii
Part I. Fluoroelastomers Overview

1. Fundamentals . 3
   1.1 Introduction . 3
   1.2 Scope: Fluorocarbon Elastomers 4
   1.3 Nature of Fluoroelastomers . 5
   1.4 Fundamental Properties 6
   1.4.1 VDF Copolymers 6
   1.4.2 TFE/Olefin Copolymers 6
   1.4.3 Perfluoroelastomers . 6
   1.4.4 Other Compositions . 6
   1.5 Developmental History: Compositions, Cure Technology . 7
   1.6 Major Uses of Fluoroelastomers . 9
   1.7 Producers of Fluoroelastomers . 11
   References 12
2. Fluoroelastomer Composition and Properties . 13
   2.1 Major Families of Fluorocarbon Elastomers 13
   2.2 VDF/HFP/(TFE) Elastomers 15
   2.3 VDF/PMVE/TFE Elastomers . 17
   2.4 TFE/PMVE Perfluoroelastomers . 17
   2.5 TFE/P Elastomers . 19
   2.6 E/TFE/PMVE Elastomers 20
   References 22
   Part II. Fluoroelastomers Technology
3. Fluoroelastomer Monomers 25
   3.1 Introduction . 25
   3.2 Vinylidene Fluoride (VDF) . 25
   3.2.1 VDF Properties 25
   3.2.2 VDF Synthesis . 26iv Contents
   3.3 Tetrafluoroethylene (TFE) . 26
   3.3.1 TFE Properties . 27
   3.3.2 TFE Synthesis 27
   3.4 Hexafluoropropylene (HFP) 29
   3.4.1 HFP Properties 29
   3.4.2 HFP Synthesis . 29
   3.5 Perfluoro(Methyl Vinyl Ether) (PMVE) . 31
   3.5.1 PMVE Properties . 31
   3.5.2 PMVE Synthesis 31
   3.6 Olefins: Ethylene and Propylene . 32
   3.7 Cure-site Monomers 32
   3.7.1 Types of Cure-site Monomers 32
   3.7.2 Halogenated Vinyl Monomers 32
   3.7.3 Functional Vinyl Ethers 33
   3.8 Safety Aspects of Monomer Handling . 33
   3.8.1 Toxicity Considerations 33
   3.8.2 Flammability . 34
   3.8.3 Explosivity 34
   References 35
4. Production of Fluoroelastomers 37
   4.1 Introduction . 37
   4.2 General Process Description 37
   4.3 Free Radical Copolymerization . 38
   4.3.1 General Reaction Scheme . 38
   4.3.2 Copolymer Composition Relationships 39
   4.3.3 Monomer Reactivity Ratios 40
   4.4 Emulsion Polymerization . 41
   4.4.1 Emulsion Polymerization Kinetics 42
   4.4.2 Continuous Emulsion Polymerization 49
   4.4.3 Semibatch Emulsion Polymerization 53
   4.5 Suspension Polymerization . 59
   4.5.1 Polymer Compositions . 61
   4.5.2 Polymerization Mechanism and Kinetics . 61
   4.5.3 Reactor Design and Operation 63
   4.5.4 Polymerization Control . 63
   4.6 Process Conditions and Polymer Characteristics . 65
   4.6.1 Molecular Weight Distribution 65
   4.6.2 End Groups 68
   4.6.3 Composition and Monomer Sequence Distributions 68
   4.7 Monomer Recovery . 71
   4.8 Isolation . 71Contents v
   4.9 Process Safety 73
   4.10 Commercial Process Descriptions 74
   References 75
5. Cure Systems for Fluoroelastomers . 77
   5.1 Introduction . 77
   5.2 VDF/HFP/(TFE) Copolymers: Diamine, Bisphenol, Peroxide . 77
   5.2.1 Diamine Cure . 77
   5.2.2 Bisphenol Cure 78
   5.2.3 Peroxide Cure 83
   5.3 VDF/PMVE/TFE Elastomers: Peroxide (Bisphenol) 89
   5.4 Perfluoroelastomers – Various Systems . 93
   5.5 TFE/Propylene Elastomers: Peroxide, Bisphenol . 95
   5.6 Ethylene/TFE/PMVE Elastomers: Peroxide, Bisphenol 99
   References 101
6. Processing of Fluoroelastomers . 103
   6.1 Introduction . 103
   6.2 Mixing 103
   6.2.1 Compounding Ingredients 103
   6.2.2 Mill Mixing 103
   6.2.3 Internal Mixers . 105
   6.3 Extrusion . 106
   6.4 Molding 110
   6.4.1 General Considerations . 110
   6.4.2 Compression Molding 111
   6.4.3 Transfer Molding 112
   6.4.4 Injection Molding 113
   6.5 Calendering . 117
   6.6 Other Processing Methods 119
   6.6.1 Latex 119
   6.6.2 Thermoplastic Elastomers . 119
   References 122
   Part III. Environmental Resistance and Applications of Fluoroelastomers
7. Fluid Resistance of VDF-containing Fluoroelastomers . 125
   7.1 Introduction . 125
   7.2 Fluid Resistance Data . 125
   7.3 Discussion of Results 125
   7.4 Fluid Service Recommendations 126
   Table 7.1 Chemical Resistance – FKM, VDF/CTFE, FKM/TFE
   Fluoroelastomers . 127
   Acetaldehyde to Butyl Cellosolve . 127vi Contents
   Butyl Ether to Ethylene Trichloride . 138
   Ethylenediamine to Lime Sulfur . 150
   Lindol to Ramjet Fuel . 165
   Rapeseed Oil to Zinc Sulfate . 178
   Table 7.2 Fluid Resistance of Fluoroelastomer Families . 192
   References 193
8. Fluid and Heat Resistance of Perfluoroelastomers . 195
   8.1 Introduction . 195
   8.2 Fluid Resistance Data . 195
   8.3 Heat Resistance Data . 195
   8.4 Resistance to Special Environments . 196
   8.5 Major Applications . 196
   Table 8.1 Chemical Resistance: FFKM Fluoroelastomer . 198
   Abietic Acid to Lithium Hypochlorite . 198
   Lithium Nitrate to Zirconium Nitrate 212
   Table 8.2 Chemical Resistance . 223
   Table 8.3 Upper Continuous Service Temperatures for Perfluoroelastomer
   Compounds 223
   Table 8.4 Tecnoflon PFR: Heat Aging . 224
   Table 8.5 Perfluoroelastomer Black Compounds for Chemical Processing
   Industry 224
   Table 8.6 Perfluoroelastomer Compounds for Semiconductor Applications 225
   References 226
9. Fluid Resistance of TFE-olefin Fluoroelastomers . 227
   9.1 Introduction . 227
   9.2 Fluid Resistance of TFE/Propylene Elastomers 227
   9.2.1 TFE/P Dipolymer 227
   9.2.2 TFE/P/VDF Terpolymers 233
   9.2.3 TFE/P/TFP Terpolymers 234
   9.2.4 Service Recommendations 236
   9.3 Fluid Resistance of Ethylene/TFE/PMVE Elastomer 236
   9.3.1 Fluid Resistance Data 237
   9.3.2 Resistance to Oil Field Environments 237
   9.3.3 Cure System Effects 237
   9.3.4 Service Recommendations 237
   References 239
10. Fluoroelastomer Applications 241
    10.1 Introduction . 241
    10.2 Major End Uses . 241
    10.3 Fabrication Methods 241Contents vii
11. Compounds for O-rings and Molded Goods . 243
    11.1 O-rings 243
    11.1.1 Specifications . 243
    11.1.2 Compression Set Measurement 243
    11.1.3 VDF/HFP Dipolymer Compounds 245
    11.2 VDF/HFP/TFE Compounds . 253
    11.3 VDF/PMVE/TFE Compounds 259
    11.4 Seal Design Considerations 260
    11.5 Additional Fluoroelastomer Molding Compounds . 260
    References 277
12. Compounds for Auto Fuel Systems 279
    12.1 Introduction . 279
    12.2 Fuel Line Veneer . 280
    12.3 Fuel Tank Components . 287
    12.4 Fuel Injector Seals 288
    12.5 Development Trends . 289
    References 290
13. Compounds for Auto Power Train Service 291
    13.1 Introduction . 291
    13.2 Oil Seal Requirements 291
    13.3 Compounds for Oil Seals 294
    13.3.1 FKM Elastomers 294
    13.3.2 FEPM Elastomers 295
    13.4 Compounds for Transmission Seals . 296
    References 298
14. Compounds for Power Plant Service 299
    14.1 Introduction . 299
    14.2 Flue Duct Expansion Joints . 299
    14.3 High-fluorine Terpolymers . 299
    References 302
15. Other Fluoroelastomer Applications and Processing 303
    15.1 Introduction . 303
    15.2 Latex and Coatings . 303
    15.3 Thermoplastic Processing . 303
    15.4 Fluoroelastomer Caulks 304
    15.5 Processing Aids for Hydrocarbon Plastics 304
    References 305
16. Fluoroelastomer Safety and Disposal . 307
    16.1 Introduction . 307
    16.2 Safety in Production 307viii Contents
    16.3 Safety in Applications 308
    16.4 Disposal 308
    References 309
    Appendix: PDL Ratings 311
    Glossary 313
    Trademarks . 347
    Index 349
    Index
    Index terms Links Index terms Links
    A
    Accelerators 78 83 253
    phosphonium 8
    quaternary phosphonium salt 103
    Accumulator 55 57
    Acetone 111
    Acids
    organic and inorganic 196
    Acrylic elastomers
    seals 291
    Acrylic rubbers
    oil seals 293
    Addition reactions
    tetrafluoroethylene 27
    Additives 305
    engine oils 292
    Adhesion
    to metal inserts 292
    Adhesive systems 292
    Adiabatic reactor 52
    Aeration
    effect on oil seals 293
    Aeronautical applications 196 197
    Air entrapment 117
    Aliphatic peroxides 85
    Alkylphenol amines
    engine oil additives 292
    Amine-free radical inhibitors 87
    Amines
    engine oil additives 292
    oil-soluble 237
    water-soluble 237
    Amino phosphinic derivatives 83
    Aminosilane-coated wollastonite 90
    Amorphous elastomer compounds 280
    Analysis methods 15
    Applications
    aeronautical 197
    automotive 3
    automotive power train 291
    automotive transmission 296
    chemical processing 197
    of fluoroelastomers 9 11 308
    oil fields 197
    of perfluoroelastomers 6 19 196
    pharmaceutical industry 197
    seals 3
    semiconductor fabrication industry 197
    Aqueous brine 237
    Aqueous oligomeric radical growth 47
    Aqueous phase oligomerization rates 50
    Aqueous phase termination 46
    Aromatic dihydroxy compounds 78
    ASTM classification 3
    Autoclave curing 283
    Automotive
    fluids service 126
    fuel system requirements 279
    fuel tanks 287
    lubricants 78
    shaft seals 241
    Automotive seals 291
    Automotive shaft seals 295
    B
    Backbone
    perfluoroelastomer 8
    Backrinding 112
    Banbury mixer 105
    Barwell Precision Preformer 110
    Base-resistant fluoroelastomers 32350
    Index terms Links Index terms Links
    Base-resistant product 96
    Bases
    organic and inorganic 196
    Benzyltriphenylphosphonium
    chloride 250
    Bifluoride 79
    Bimodal blends 105
    Bimodal polymers 287
    Biocides 119
    2,2’-Bis(t-butylperoxy)diisopropylbenzene 227
    Bis(triarylphosphin)iminium salts 83
    Bisphenol 77
    bulk systems 82
    commercial 82
    curing 16 32 61
    78 79 110
    111 195 227
    precompounds 253 283
    vulcanizates 82
    Bisphenol AF 8 250 282
    Bisphenol curing 293
    Bisphenol precompounds 294
    Bisphenol-containing precompounds 295
    Bisphenol-curable
    dipolymers 287
    gums 299
    polymers 125
    precompounds 282
    terpolymers 287 288
    VDF/HFP 110
    Bisphenol-curable gums 294
    Bisphenol-cured
    compounds 6
    fluoroelastomers 3 79
    Bisphenol-cured elastomers 291 292
    Bisphenol-cured terpolymers 294
    Black compounds 245
    Blisters 112
    Branching 254
    excessive 33
    Breaker plate 108
    Brittle point 17
    Bromine cure sites 18 110
    Bromine-containing cure-site
    monomers 90
    Bromine-containing fluoroelastomers 85
    Bromine-containing monomers 8 9
    Bromine-containing olefins 32
    BTFB monomer 33
    C
    Ca(OH)2/MgO ratio 249
    Calcium hydroxide level
    adhesion effect 292
    Calendering 117 299
    Carbon black levels 246
    Carbon dioxide environment 197
    Carbonyl fluoride
    for synthesis of PMVE 31
    Caulks 304
    Chain branching 59
    Chain-transfer agents 37 55 58
    Charging 57 59
    Chemical attack
    by additives 294
    Chemical processing
    applications 196 197
    Chemical resistance
    engine seals 295
    vulcanizates 195
    Chlorotrifluoroethylene 6
    copolymers 7
    Clamp unit 114
    Coagulants 38
    Coal-fired power plants 299
    Coatings
    latex 303
    Coefficient of linear expansion 196
    Cold feed extruder 108351
    Index terms Links Index terms Links
    Combustion products
    from fluoroelastomer compounds 308
    Commercial elastomeric products 16
    Commercial fluorocarbon elastomers 5
    Commercial fluoroelastomers 37
    Components
    addition of 57
    Composition
    determination of 15
    determines characteristics 13
    Compounding 99 241
    Compression 260
    Compression molding
    advantages 111
    disadvantages 111
    shaft seals 291
    Compression set 246 250
    resistance 254 288 289
    tests 243 245
    Compression stress relaxation
    measurements 245
    Computer-controlled mixing lines 105
    Conjugated diene structure 79
    Continuous emulsion polymerization
    process 40 43 44
    47 48 49
    50
    Continuous reactor
    control of 52
    design and operation 50
    operation 37 51
    Continuous stirred tank reactors
    (CSTR) 49 50
    Control systems 117
    Cooling jackets 51 54
    Copolymer composition relationship 39 41
    Copolymerization 39
    with ethylene 15
    with propylene 15
    Copolymers
    elastomeric 234
    TFE-propylene 227
    VDF/HFP 78
    vinylidene fluoride 7
    Counter-rotating rolls 104
    Cracking products
    tetrafluoroethylene 29
    Creaming 119 303
    Creep 304
    Critical length 45
    Critical micelle concentration (cmc) 45
    Cross linking agent
    radical trap 196
    Cross-head die 108 280
    Crosslinker 250
    Bisphenol AF 103
    Crosslinking 288
    reactions 86
    temperatures 77
    Crosslinks 243
    Crystalline aluminosilicates 90
    Crystalline plastics 304
    Crystallinity
    affected by monomers 13
    CSTR 54
    monomer feeds 51
    polymerization systems 52
    shutdown 51
    startup procedures 51
    steady states polymerization systems 52
    CTFE-based plastics 7
    Curative masterbatches 250
    Curatives 106
    dispersion of 103
    Cure characteristics 295
    Cure kinetics 77
    Cure rates 253
    Cure-site monomers 32 37 59
    61352
    Index terms Links Index terms Links
    Cure sites 6 8 17
    monomers 32
    perfluorophenyl 18
    Cure systems
    bisphenol 195
    characteristics 77
    peroxide 195
    Cure times 250
    Cured stock 111
    Curing 14
    characteristics 260
    ETP 20
    fluoroelastomers 32
    by irradiation 304
    peroxide systems 14
    systems 8
    Cyano FVE 33
    Cyclic amidine base 82
    D
    Dai-el® G-101 304
    Dai-el® LT-303 260
    Decomposition rate
    first order 52
    Dehydrofluorination 79 234 254
    Demolding 254
    Detergents
    engine oil additives 292
    Deuterated tetrahydrofuran solution 98
    Dewatering 106
    Diamine 119
    Diamine cure system 77 78
    Die coating 304
    Die entrance 305
    Die-cut gaskets 245
    Diels-Alder adducts 29
    Dienic phenyl ether crosslinks 82
    Dienone 82
    Differential scanning calorimetry
    (DSC) 15
    Difluoroacetamides 27
    Diiodide transfer 119
    Dimethylacetamide 79
    Dipolymer compositions 14 15
    Dipolymers
    commercial 82
    curing of 250
    gums 250 282
    heat-treated TFE/P 96
    TFE/P 227
    VDF/HFP 77 104 106
    303
    Dispersants
    engine oil additives 292
    Dispersion
    stability 51 53
    stabilizer 44
    volume 56
    Disposal of fluoroelastomers 308
    Divinylperfluoroalkane
    crosslinks 196
    DLVO model of colloid science 46
    Drying extruder 106
    DuPont Dow Vertex™ seal 304
    Dust lips 291
    Dynamar™ Polymer Processing
    Additives 304
    Dyneon® FC 2210X 304
    Dyneon® Fluoroelastomer FX 10180 303
    Dyneon® precompounds
    properties of 282
    Dyneon® THV fluorothermoplastic 304
    E
    E/TFE/PMVE elastomers 20
    Elastomeric behavior 5
    Elastomeric seals 260
    Elastomers
    cure systems 77
    definition 15353
    Index terms Links Index terms Links
    Elastomers (Continued)
    ethylene acrylic 304
    ETP 100
    extrusion 114
    fluorinated thermoplastic 303
    pellets 106
    synthetic 103
    VDF/HFP/TFE 253 254
    Elastoplastics 16
    Elongation at break 250
    Embrittlement 78 288
    Emissions 288 289
    Emulsion polymerization 41 42 44
    free-radical 37
    soapless 47
    End groups
    iodine 59
    ionic 52 53 78
    sulfonate 43
    Engine oil
    additives 292
    Engineering controls 307
    Environmental conditions
    for engine seals 295
    Environments
    aggressive 197
    in deep wells 197
    fluid 260
    harsh 196
    temperature 260
    Epichlorohydrin 282
    Epoxysilane 90
    Ethylene
    copolymerization 15
    flammability 34
    properties 32
    tetrapolymer 6
    Ethylene/TFE/PMVE 99 227 236
    ETP 237
    curing 20
    elastomers 100 236 237
    fluid resistance 236
    fluoroelastomers 237
    vulcanizates 100
    Exothermic decomposition 308
    Expansion joints 299
    elastomeric 299
    flue duct 241
    Explosion hazards 307
    tetrafluoroethylene 27
    Explosion potential 34
    Explosive decompression 197
    Exposure to severe environments 237
    Extruder barrels 108
    Extrusion 241 283
    Extrusion characteristics 287
    F
    Fabrication 241
    Feed section 108
    Feed zone 108
    FEPM elastomers 295
    Fick’s Laws 280
    Filler neck hose 288
    Filler system 279
    Fillers 245
    Fires during post curing 308
    Fissures 89
    FKM elastomers
    seals 291
    FKM shaft seals 293
    Flammability
    ethylene and propylene 32
    hazards 34
    Flash 111
    Flexible fuels 289
    Flexural modulus 304
    Flow characteristics 254
    Flue duct expansion joints 241354
    Index terms Links Index terms Links
    Flue duct system 299
    Flue gases 299
    Fluid resistance 6 8 9
    100
    HK classification 3
    vulcanizates 195
    Fluorinated matrix 77
    Fluorinated monomers 25
    Fluorinated vinyl ethers 33
    Fluorine content 14 15 16
    253
    affects chemical resistance 294
    TFE/P elastomers 19
    varying 14
    Fluoroalkoxyphosphazene 7
    Fluorocarbon elastomers 13
    Fluorocarbons 41
    Fluoroelastomers 13
    applications 9
    base-resistant thermoplastic 120
    bisphenol-curable 282
    characteristics 77
    components 279
    compounding 103
    copolymerization 15
    gums 303
    high-fluorine 260
    incorporated iodine units 59
    latex 119
    low-viscosity 303 304
    o-rings 279
    operating conditions 114
    peroxide-curable 243 254
    PMVE-containing 289
    polymerization 42
    processing methods used 103
    producers 11
    sales 13
    for seals 291
    setting and controlling 48
    TFE-olefin 227
    thermoplastic 119
    VDF-based FKM 227
    VDF/HFP 77
    VDF/HFP/TFE 243 254
    VDF/PMVE/TFE 289
    veneer stock 283
    without ionic end groups 60
    worldwide production 3
    Fluoromonomers
    toxicity 33
    Fluoroplastics
    production volumes 25
    Fluoropolymers
    melt-processible 107
    processing 305
    Fluorosilicone 7
    Fouling 87
    Fourier Transform Infrared (FTIR) 15
    Free radicals 83 288
    curing 6 8 14
    32
    polymerization 9 37 38
    Fuel
    compositions 279
    emission limits 287
    methanol-containing 282
    oxygenated 279
    partially oxidized 280
    Fuel hose 279 280
    additional layers of 282
    estimation of M15 fuel loss 282
    veneer 287
    Fuel injector
    o-rings 288
    Fuel permeability 281
    Fuel pump 279
    seals 288
    Fuel sender module 287
    Fuel swell measurements 289
    Fuel tank components 279355
    Index terms Links Index terms Links
    Full (black) compounds 245
    Furnace blacks 246
    FVE
    cyano 33
    FVMQ o-rings 288
    G
    Gas deposition processes 197
    Gaskets 10
    cured-in-place 304
    Gates 116
    Gelation 82
    Glass transition temperature 5 6 9
    E/TFE/PMVE 20
    fluoroelastomers 10
    Green strength 250
    Grit-blasting 292
    Grooves
    in seals 19
    Gum fluoroelastomers 104
    Gum polymer 38
    VDF/HFP/TFE 253
    H
    Halogen cure site 6
    Halogenated vinyl monomers 32
    Handling precautions
    fluoroelastomers 307
    Handling procedures
    fluoromonomers 34
    Hard chrome plating 111
    Hazardous monomer mixtures 34
    Hazards
    explosion 54 56
    safety 52
    Heat
    exchange limits 56
    of polymerization 50 52 56
    removal of 51
    Heat of reaction
    TFE deflagration 29
    Heat resistance 195
    HK classification 3
    Heats of fusion 15
    Helix angle 108
    Hexafluoropropylene 13
    in fluoroelastomers 25
    properties 29
    synthesis 29 30
    Hexamethylene diamine 77
    HFP-based fluoroelastomers 7
    HFP-containing fluoroelastomers
    adequate seal performance 289
    HFP-containing polymers 293
    High-fluorine elastomers 289
    High-fluorine product 260
    High-VDF elastomers
    chemical resistance 296
    HK classification
    properties 3
    HNBR
    o-rings 288
    oil seals 293
    seals 291
    Homogeneous nucleation 45 46
    Hoses 241
    automobile fuel 60
    Hydraulic clamp 114
    Hydrocarbon fuel mixtures 279 287
    Hydrocarbon swell 227
    Hydrocarbon thermoplastics 304
    Hydrocarbons
    resistance to 13 20
    Hydrogen sulfide
    environment 197
    Hydropentafluoropropylene 90
    Hydroperoxides 288
    Hydroxides 103356
    Index terms Links Index terms Links
    I
    Ignition sources 34
    Immersion testing 293
    Initiation 43 45
    by thermal decomposition 49
    constant rate 58
    Initiator 37 55 57
    decomposition 86
    molar feed rate of 53
    Injection molding 78 113
    machinery 114
    shaft seals 291
    troubleshooting 117
    Injection unit 114
    Inorganic acids 196
    Inorganic backbones 7
    Inorganic bases 196
    Intermeshing rotors 105
    Intrinsic viscosity 48
    Iodine cure sites 18
    Iodine end groups 8 9 59
    294
    Iodine groups 196
    Iodine-containing transfer agents 33
    Ionic end-group level. See end groups
    optimizing 58
    Irradiation curing
    FTPE 304
    Isobutene 111
    ITFB monomers 33
    J
    Jamak stress relaxation jigs 288
    Jigs 243 245
    Shawbury-Wallace 245
    K
    Kinetic analysis 38
    Kinetic models 47 48 53
    L
    Latex processing 303
    Lips
    seals 291
    Liquid feeds 51
    “Living radical” polymerization 93
    Loading fixtures 112
    Low-fluorine polymers 294
    Low-pressure extrusion 304
    Low-temperature characteristics 14 17
    Low-temperature flexibility 6 19 20
    Lube oils
    amine additives 125
    M
    M15 fuel 281
    loss estimation 282
    Magnesium oxide level
    adhesion effect 292
    Maintenance procedures 307
    Mandrel 280
    Masterbatches 250
    Material Safety Data Sheets 307
    Melt fracture 305
    Melt-processible fluoropolymers 107
    Melting endotherm 303
    Melting points
    of elastomers 15
    Melting temperature
    THV 304
    Metal oxides 90 103
    Metering zone 108
    Methyl bromide 86 111
    Methyl radicals 86
    Methyltributylammonium Bisphenol
    AF salt 96
    Micellar entry 45
    mechanism 46
    Microemulsion process 59
    Mineral fillers 100 249357
    Index terms Links Index terms Links
    Mixed stock 107
    Modulus 250
    Mold
    cavities 110
    closing 117
    designs 117
    flash 117
    fouling 111
    opening 117
    platens 111
    precision extruded shapes 241
    release 110
    sticking 87
    Molded composite parts 249
    Molding
    compression 241
    injection 241
    of shaft seals 291
    temperatures 77
    transfer 241
    Molecular sieve zeolites 90
    Molecular weights
    controlling 44
    Monitoring systems 307
    Monomer 37
    affect on characteristics 13
    charge 59
    combinations 5
    compositions 50 57
    concentration 47
    CSTR feeds 51
    fugacity 48
    gaseous 51
    recovery and recycle 49
    MT black 77
    N
    Nitrile rubber 13 281
    hydrogenated 281
    Nitrogen leakage 289
    Nonionic radical 43
    Nozzle flash 117
    Nuclear magnetic resonance (NMR) 15 79
    Nucleophiles 90
    Nucleophilic attack 234
    Nucleophilic diamine 77
    Nylon 12 282
    O
    O-ring compounds 243
    O-ring seals 3 10 241
    288
    O-rings 287 289
    specifications 243
    Octafluorocyclobutane
    cracking product 29
    Octafluoroisobutylene
    cracking product 29
    ODR modulus 85
    Oil fields
    applications 196 197
    Oil resistance 295
    Oil seals 291
    testing 293
    Olefin monomers 32 34
    Operating procedures 307
    Organic acids and bases 196
    Oscillating disk rheometry 78
    Oxidizing agents
    resistance to 196
    P
    Particles
    by secondary nucleation 47
    determining number 48
    determining number of 44
    entry into 45
    formation 47 55
    formation and growth 44358
    Index terms Links Index terms Links
    Particles (Continued)
    formation by homogeneous
    nucleation 45
    micellar entry mechanism 46
    polymerization rate 47
    precursor 45
    PDL Ratings 125 195 311
    Pendant vinyl groups 196
    2H-Pentafluoropropylene 100
    Perfluorinated polymer backbone 8
    Perfluoro(alkyl vinyl ethers) 25
    Perfluoro(methyl vinyl ether)
    (PMVE) 14 25 31
    Perfluorocarbon diiodides 58
    Perfluoroelastomers 6 14 40
    51 77 236
    applications 19
    FFKM 237
    Perfluoroisobutylene 28
    Perfluorophenyl cure sites 18
    Permeation rate 280
    Permeation test method
    Thwing Albert cup 281
    Peroxide curing 6 14 86
    93 95 195
    227 254
    fluoroelastomers 86
    study 85
    vulcanizate properties of 86
    Peroxide level 86
    Peroxide systems 110
    Peroxide-curable fluoroelastomers 8 32 87
    Peroxide-curable gums 294 299
    Peroxide-curable perfluoroelastomers 94
    Peroxide-curable products 294
    Peroxide-curable VDF/HFP/TFE
    fluoroelastomers 294
    Peroxide-curable VDF/PMVE/TFE
    elastomers 90
    Peroxide-cured terpolymer 96
    Peroxide-cured vulcanizates 90
    Peroxide-initiated curing 6
    Peroxides 77 83
    Persulfate-sulfite redox initiation
    systems 93
    Pharmaceutical
    applications 196 197
    Phenolates
    engine oil additives 292
    Phosphatizing 292
    Phosphonium accelerators 83
    Phosphonium salts 83
    Piston injection unit 113
    Plant tests 307
    Plasma processes 197
    Plasticization 289
    Plastics
    high-fluorine 304
    Polar fluids 196
    resistance 20
    Polyamine curative 119
    Polycaprolactone 305
    Polyethylene
    high density 304
    linear low density 304
    Polymer
    composition 54
    degradation 95
    desired composition 57
    dispersion 37
    estimates of composition 53
    formed in the reactor 37
    isolation 38
    optimizing viscosity 58
    pellets 106
    radical propagation of particles 46
    radicals 86
    scale-up 56
    VDF/HFP/TFE 259
    VDF/PMVE/TFE 243 259359
    Index terms Links Index terms Links
    Polymer (Continued)
    viscosity control 53
    Polymeric peroxide 27
    Polymerization 42 55
    commercial production 39
    conditions 49
    emulsion 37
    heat of 50 52 56
    inhibitors 29
    living radical 58
    process safety 307
    rate in a CSTR 52
    removal of heat 51
    shutdown 55
    Polymerization rate 44 47 53
    54 56 59
    second stage 61
    semibatch reactors 56
    Polymerization systems 39 42
    Polytetrafluoroethylene
    thermoplastics 93
    Post cure temperatures
    adhesion systems 292
    Post curing 118
    Pot 112
    Power generation facilities 299
    Power systems 117
    Power train systems 241
    Precompounds
    Dai-el® 253
    VDF/HFP 245 249 250
    VDF/HFP/TFE 253
    Premature crosslinking (scorch) 78
    Premature curing 87
    Press heating system 112
    Primer curing 292
    Production
    worldwide 3
    Propagation rate coefficient 41 44
    Propagation reactions 39
    Properties
    by varying composition 13
    Propylene
    copolymerization 15
    copolymers 9
    flammability 34
    properties 32
    Pyrolysis
    products 28
    tetrafluoroethylene 30
    Q
    Quaternary ammonium salts 83
    Quaternary phosphonium accelerator 250
    Quick-connect seals 287
    R
    Radial squeeze 289
    Radical adducts 86
    Radical growth
    aqueous oligomeric 47
    Radical trap 83 195 196
    237
    Radical-generation rate 48 52 57
    Radicals
    determining number of 44
    entry efficiency 53 57
    estimating cumulative 58
    flux 43
    lost by recombination 43
    nonionic 43
    propagation 46
    rate of conversion 39
    ratio of 39
    summation of generated 58
    Ram injection units 113
    Random copolymerization 41
    Rate
    of aqueous-phase oligomerization 50
    of constant initiation 58360
    Index terms Links Index terms Links
    Rate (Continued)
    conversion 39
    of decomposition 42 52
    determining 48
    goals for monomer feed 53
    of incorporation of monomers 39
    of polymerization 44 56
    See also Polymerization
    of radical-generation 57
    of transfer 49
    Ratio of radical types 39
    Reaction temperature
    vinylidene chloride 26
    Reactions
    chain transfer-to-polymer 59
    kinetics relationships 39
    Reactive fluids 126
    Reactivity ratios 40 41
    estimating 40
    Reactor
    dynamics 53
    jacket cooling of temperature 51
    jacketed cylindrical 55
    volume 56
    Reciprocating screw injection unit 114
    Recovery
    from strain 5
    Redox initiation 95
    persulfate-sulfite 18
    Redox initiator 42
    Redox rate 43
    Relationships
    dependence 48
    Relative viscosity 48
    Relaxation
    from strain 5
    Reversion 288
    Rubber
    cure characteristics 110
    injection mold 113
    mill 104
    Runners 116
    S
    Safe handling
    of monomers 307
    Safety
    fluoroelastomer life cycle 307
    handling of monomers 33
    tetrafluoroethylene 27
    Salt removal 38
    Scorch 112
    Screen pack 108
    Seals
    for aggressive fluids 197
    application 260
    automotive 295
    automotive transmission 296
    FTPE 304
    groove geometry 19
    for high-temperature 196
    o-rings 3 10
    oil retention 291
    performance at low temperature 17
    shaft 10
    Secondary nucleation 47
    Semibatch emulsion polymerization 42 43 47
    50 53 55
    control of 57
    Semibatch reactors 54
    charging 57
    design and operation 55
    design considerations 56
    limitations 54
    operation 37
    scale-up 56
    Semiconductor
    applications 196 197
    Service temperatures
    in chemical processes 197361
    Index terms Links Index terms Links
    Set resistance
    o-ring 196
    Shaft seals 3 10 291
    294 295
    automotive 295
    Shaw Intermix 105
    Shawbury-Wallace
    jigs 245
    load cell 245
    load stand 288
    Silane primers 292
    Silicone
    oil seals 293
    seals 291
    Single-screw extruder 107
    Soap 37 44
    concentration 46
    Sodium alginate 119
    Solubility equilibria 280
    Solubility limit 53
    Solution coating 303
    Solvent
    ozone-depleting 61
    Sour fuel 288
    effect of 288
    Sprue 112 116
    Static seals 243
    performance 260
    Steady state permeability 280
    Sterilization
    steam 197
    Stock
    to rolls 104
    temperature 106
    Straight head extruder 108
    Stress
    recovery from 5
    relax 118
    Strip feeding 118
    Succinimides
    engine oil additives 292
    Sulfides
    engine oil additives 292
    Supernatant 119
    Suppliers
    fluoroelastomer 11
    Surfactants 46
    fluorinated anionic 44
    Suspension polymerization 39 60
    advantages 59
    Suspension products
    bisphenol-curable 60
    Sustained particle nucleation 50
    Swell
    varies with fluorine 14
    T
    TAIC radical trap 86
    Tangential rotors 105
    Tecnoflon FOR 4391 282
    Tecnoflon FOR 50HS 245
    Tecnoflon FOR 90HS 245
    Tecnoflon N 535 283
    Tecnoflon TN Latex 303
    Temperature
    control systems 52
    cycling 243
    jacket-coolant 57
    Temperature environment
    seals 291 296
    severe 293
    Temperature stability
    vulcanizate 196
    Tensile strength
    and heat resistance 195
    Termination reactions 43
    Terpenes
    polymerization inhibitors 29
    Terpolymers 96
    bisphenol-curable 254 287362
    Index terms Links Index terms Links
    Terpolymers (Continued)
    composition 15
    ethylene/TFE/PMVE 227
    TFE and PMVE 41
    TFE/P/VDF 234
    VDF/HFP/TFE 14 87 119
    243 253 282
    Terpolymers and tetrapolymers
    compositions of 39
    Test block 289
    Tetrabutylammonium hydrogen
    sulfate 83
    Tetrafluoroethers 27
    Tetrafluoroethylene 26
    copolymers 9
    cracking 29
    epoxide 27
    explosive hazards 27
    in fluoroelastomers 25
    properties 27
    synthesis 27
    Tetraphenyltin 93
    TFE
    explosion potential 33
    particle formation 45
    TFE/olefin elastomers 77
    TFE/olefin FEPM elastomers 293
    chemical resistance 293
    TFE/P 6 9 19
    dipolymer vulcanizates 96
    FEPMs 236
    fluid resistance 236
    peroxide-cured 234
    TFE/P dipolymer 295
    TFE/P fluoroelastomers 294
    chemical resistance 294
    TFE/P/TFP
    bisphenol-cured 234
    vulcanizates 234
    TFE/P/TFP elastomers
    chemical resistance 296
    TFE/P/VDF 96 227 233
    234
    TFE/P/VDF elastomers
    chemical resistance 296
    TFE/P/VDF terpolymers 295
    TFE/PMVE 17 93
    TFE/propylene 227
    Thermal black 245
    Thermal expansion 196
    Thermal resistance 8 9
    engine seals 295
    TFE/PMVE 94
    Thermal stability 254
    Thermoplastics 281
    THV fluorothermoplastics 304
    Thwing Albert cup 281
    Tie-coats 292
    Toggle clamp 114
    Toxicity
    fluoromonomers 33
    TR-10 test 14
    Transfer agents
    semibatch reactor 49
    Transfer coefficient 49
    Transfer mold
    three-plate multiple cavity 113
    Transfer molding process 112
    Transfer pad 112
    Transfer rate 49
    Transfer reactions 48
    Transition zone 108
    Triallyl cyanurate 85
    Triallyl isocyanurate (TAIC) 85 237 254
    radical trap 196
    Triazine crosslinks 18 93 94
    195
    Triethylenetetraamine 119
    Trifluoropropylene 100 227363
    Index terms Links Index terms Links
    Trifluorovinyethers 27
    Trimethallyl isocyanurate 85 237 254
    Triphenylphosphine oxide 82
    Tubing die 108
    Two-part liquid systems 304
    Two-roll mills 103
    V
    Variable speed DC drive 108
    VDF copolymers 6 44 49
    51
    commercial 48
    continuous emulsion polymerization 50
    particle formation 45
    with soap 48
    systems 44
    VDF homopolymer 59
    VDF production 26
    VDF-based fluoroelastomers 18
    VDF-containing fluoroelastomers 296
    effects of fluids 125
    VDF/HFP 13 118
    bisphenol-cured 111
    copolymerization 40
    copolymers 78 82 287
    dipolymers 77 304
    elastomers 96
    fluoroelastomers 77
    precompounds 104 245 249
    250
    VDF/HFP/(TFE) 60 77
    polymerization 49
    products 50
    VDF/HFP/PMVE/TFE 90
    VDF/HFP/TFE 77 78 82
    119 243 253
    259 299
    bimodal polymers 60
    bisphenol-cured 299
    gum 253
    high-fluorine 299
    iodine-containing 254
    latex 303
    peroxide-curable 254
    peroxide-curable fluoroelastomers 60
    precompounds 253
    terpolymers 15 243 253
    287
    vulcanizates 90
    VDF/HFP/TFE elastomers 291 292
    VDF/HFP/TFE terpolymers 293
    seals 291
    VDF/PMVE/TFE 31 243 259
    peroxide-curable 260
    products 50
    ternary diagram 17
    terpolymers 89
    vulcanizates 90
    VDF/PMVE/TFE elastomers 293
    chemical resistance 293
    VDF/PMVE/TFE fluoroelastomer 293
    VDF/TFE copolymers 41
    Veneer barrier layer 282
    Vent stacks 299
    Vented barrel design 108
    Ventilation 307
    Vertical ram machine 113
    Vinyl ethers 33
    Vinyl groups 196
    Vinyl monomers 33
    Vinylidene fluoride 13
    physical properties 25
    production volume 25
    Viscosity
    inherent 48
    intrinsic 48
    polymer 52
    relative 48
    stocks 246
    Viton® polymers
    high-fluorine 254364
    Index terms Links Index terms Links
    Viton® B-202 283
    Viton® Curative No. 50 250
    Viton® E-60C 104
    Viton® Extreme™ TBR-605CS 234
    Viton® F605C 282
    Viton® Fluoroelastomer 126
    Viton® FreeFlow™ additives 304
    Viton® GLT 260
    Viton® type nomenclature 16
    Volatile materials 86
    Volatile products
    measurement of 307
    Volume swell
    elastomers 282
    Vulcanizates
    chemical resistance 195
    ETP 100
    fluid resistance 195
    heat resistance 195
    peroxide-cured 227
    properties 86 250 254
    260
    temperature stability 196
    with varying fluorine 14
    VDF/HFP/(TFE) 96
    Z
    Z-mer 45 47

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