References and Bibliography

Aggarwal, S. L. (1970). Block Copolymers. Plenum Press, New York. Allport, D. C. & Janes, W. 1. (1973). Block Copolymers. Applied Science Publishers,

London. Ashida, K. & Frisch, K. C. (ed.) (1956-91). International Progress in Polyurethanes,

Vol. 1-6. Tcchnomic Publications, Basel. Barikani, M. (1986). Thermally stable polyurethane elastomers: Their synthesis and

properties. PhD thesis, Loughborough University of Technology, England. Barikani, M. & Hepburn, C. (1987). The relative thermal stability of polyurethane

elastomers. 3: Influence of chain extender system. 1. Cell. Polym., 6(3), 47-66. Becker, W. E. (1972). Reaction Injection Moulding. Van Nostrand, Reinhold

Company, New York. Blow, C. M. & Hepburn, C. (1982). Rubber Technology and Manuf'acture.

Butterworth, London. Bruins, P. F. (ed.) (1969). Polyurethane Technology. Interscience, New York. Buist, 1. M. (ed.) (1978). Developments in Polyurethane-i. Applied Science, London. Buist,1. M. & Gudgeon, H. (1968). Advances in Polyurethane Technology. Maclaren

and Sons, London. Burke, 1. J. & Weiss, V. (eds) (1983). Block and Graf't Copolymers. Syracuse

University, Syracuse. Ceresa, R. 1. (1962). Block and Graft Copolymers. Butterworths, London. David, D. 1. & Staley, H. B. (1969). Analytical Chemistry of' Polyurethanes. Wiley-

Interscience, New York. Dunlop, K. L., Sandridge, R. L. & Keller, J. (1976). Analyt. Chern., 48, 497. Faxa, F. G. (1980). Plastics and Rubber International, 5(3), 105. Goodman, 1. (1985). Heterochain Block Copolymers. Elsevier Applied Science. Hertschel, W. (1884). Ber., 17, 1284. Hepburn, C. (1987). Polyurethane elastomers as hydraulic seal materials. 1. Cell.

Polym., 6(8), 51-66. Hunter, D. (1985). Diseases of' Occupations, 6th edn. Hodder and Stoughton,

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of' Polymer Materials. Chapman and Hall, London. Lee, L. 1. (1980). Rubber Cheln. & Teclmol., 153(3) JUly-August, 2118. Leiah, M. D. & Cooper, S. L. (1986). Polyurethanes in Medicine. CRC Press, New

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428 POLYURETHANE ELASTOMERS

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73, New York, USA. Minoura, Y. et al. (1978). Crosslinking and mechanical properties ofliquid rubber.

Part I: Curative effect of aliphatic diols. J. Appl. Polym. Sci., 22, 1817; Part II: Curative effect of aromatic diols. J. Appl. Polym. Sci., 22, 3101; Minoura, Y. et al. (1979). Part III: Curative effect of aralkyl and alicyclic diols. J. Appl. Polym. Sci., 23, 1137.

Moacanin, 1., Holden, G. & Tschoegl, N. W. (eds) (1969). Block Copolymers. Interscience, New York.

Molau, G. E. (ed.) (1971). Colloidal and Morphological Behaviour of Block and Graft Copolymers. Plenum Press, New York.

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Verlag, Munich. Polyurethanes World Congress, 1987, Aachen. SPI proceedings, Technomic, Basel,

Switzerland. Saunders, 1. H. & Frisch, K. C. (1962). Polyurethanes: Chemistry and Technology,

Vols. I and II. Interscience, New York. Saunders, K. 1. (1973). Organic Polymer Chemistry. Chapman and Hall, London. Schiller, A. M. (ed.) (a) (1973). Soviet Progress in Polyurethane series: (a) Soviet

Urethane Technology, Vol. I. Technomic Publications, Westport, Conn. (b)(1975). Svnthesis and Phrsical Chemistrv of Urethanes, Vol. II. Technomic Publications, Westport, Conn." " .

Siefken, W. (1949). Annalen, 562, 75. Sweeney, F. M. (1979). Introduction to Reaction Injection Moulding. Technomic

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Coventry, UK. Twitchett, H. J. (1974). Chem. Soc. Reviews, 3(2), 209. Vieweg, R. & Hoechtlen, A., In Kunstoff Handbuch, Vol. VII: Polyurethane. Carl

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Technology. Polyurethanes Vol. II. Wiley-Interscience, New York. Urethane Abstracts, Technomic Publications, Westport. Conn. (1987). European Marketfor Polyurethanes. Frost and Sullivan, London. (1986). Polyurethanes: Exploring Nell' Horizons. SPI proceedings, Technomic, Basel,

Switzerland.

Index

ABS, blends with thermoplastic PU, 263

Acrylates hydroxy-ether, 353, 354 polyester urethane, 353, 354 properties, 366-67 PU-based, 352--4

Acylurea, synthesis, 4 Adhesives, 221--43

aminimides, 237-9 blocked di- or poly isocyanate,

235-9 components, 221 Desmocolls, 234 Desmodur RF, 234 diisocyanates-based, 223-7 elastomer gum types, 234 film and tape, 241 hazards, 420 isocyanate

methods of use, 227-33 polarity, 225 reactivity, 224 self-polymerization, 224-5 surface welling, 225 unreactive surfaces, 226

polar-non-polar bonding, 226 poly isocyanate, added, 231-3 polyols used, 221

Adhesives-('ontd. polyurethanes

aqueous dispersions, 239--41 polymerization, 229-31 powdered polyurethanes, 241-2 thermoplastic types, 233--4

stabilization, 242-3 Adiprene

formulation, 160 prepolymers, properties, 126 properties, vs density, 162

Adiprene CM millable polyurethane, 201 processing, temperature, 202

Ageing periods, polyurethane, 106 Aliphatic diisocyanates

property-structure relationships, 59-61

us aromatic, 59 'zig-zagging' of properties, 72

Allophane, synthesis, 4 Allophonates, dissociation,

temperature effect, 112 Amide, synthesis, 3 Amine equivalent, defined, 43 Amines

429

as catalysts, 115-16 curatives, 132--4

see a/so Caytur 7: MOCA

430 INDEX

Aminimides, adhesives, 237-9 Apocure

properties of polyurethanes prepared from, 148

structures and properties, 138 Aromatic diisocyanates, us aliphatic,

59 Automotives, body panels, 398

Bay tee 1604, structure and properties, 167

BD, see polybutadienes BDO, see l,4-butane diol Benzoin, butyl ether, 353, 354 Benzophenone, hydrogen abstraction,

354 Benzyl dimethyl ketal, structures, 353 Bisphenol A

structure, 75 temperature maximum, 80, 81

Biurets acyl/alkyl substituted, dissociation,

temperature effect, 112 synthesis, 4

Butadiene, properties, 362-3 l,4-butane diol, 62-5, 74

alternatives, 167 structure, 62 thermoplastic PU formulation, 247 in Vulkollan, 155

Butyl rubbers, properties, 362-3

Calendering, TPUs, 253-5 Cap a, see polycaprolactone diol Caprolactone polyester, see

polycaprolactone Carbon black

effect on polyurethanes, 212 millable polyurethanes, 207, 210

Cast elastomers, compression moulding 161-3

Castor oil, reaction rates with MDI, 111

Catalysts, 27-8, 113-20 bases, 115-17 combinations, 120 methane reaction rates, 114 organotins, 114-16, 118-20 prepolymer stability

and acid catalysis, 113 shelf life, 113

residues, odours, 118 tertiary amines, 115-16, 117-18

Catechol maximum stability T, 78 structure, 73

Caytur 4, vulcanization, 202 Caytur 7

substituent for MOCA, 128 TDI polyether prepolymers, effects

on, 133 Cellular polyurethanes, 158-61

solvents, 160 stable prepolymers, 159-60 see also Vulkollan

Chain extenders 1,4-BDO, structure, 62 diamines, 'zig-zagging' of properties,

72 equivalent weights, 38

CHDI, see trans-l,4-cycIohexane diisocyanates

Chlorine diisocyanates

content, 295 hydrolyzable, 296-7

Chloro-sulphonyl polyethylene, properties, 366-7

Chloroprene, properties, 364-5 Chromatography

gas-liquid, 323-5 thin layer, 325-8

Cold-cast polyurethanes, 404 Compression moulding, cast

elastomers, 161-3

INDEX 431

Conathane polyester and polyether urethanes, 137

Crosslinking isocyanate and isocyanurate, 90 routes, 33~6 and thermal stability, 89~90

Curatives, see Caytur 7: MOCA Cure-A

22, 24, 154, 160, properties of polyurethanes prepared from, 141,142, 145, 146, 149, 150

structures and properties, 138~9 Cyanaprene polymers, properties, 151 trans-l,4-cyc1ohexane diisocyanates,

62~5, 74 -based polyurethanes

chain extension, 268 DMT A spectra, 273, 275 mixed aliphatic diols as chain

extenders, 277 hardness vs diisocyanate content, 173 hazards, 411 ~ 3 prepolymer synthesis and chain

extension, 169~ 70 properties, 168 structure, 74 temperature effects, 172

1,4-cyc1ohexane dimethanol, structure, 269

DABCO, see triethylene diamine (1,4-diazo[2,2,2J-bicyc10-octane)

DD-1604, properties of polyurethanes prepared from, 147

Desdomur R adhesives, 234 structure, 222

Desdomur TT, properties, 214~15 Desmocolls, adhesives, 234 Desmophen, in Vulkollan, 155 di(4-hydroxyphenyl) sulphone (DHS)

maximum stability T, 78, 80, 81 structure, 75

Diamines alternatives to MOCA, 165 chain extenders, 68~9

'zig-zagging' of properties, 72 chain-extenders, control, toluene

diisocyanate-based elastomers, 66

curing agents, structures and properties, 138

Dianisidine diisocyanates, structure, 14

Dianol 22 and 33, structure, 167, 269 Differential scanning calorimetry

(DSC) 84~9, 105~6 chain extender-based, polyurethane

elastomers, 85~6 as means of predicting relative

thermal stability of diamine, 87~9

and molar ratio 1:2'6:1, 85~7 polyurethanes, transitions, groups,

105~6

thermal stability prediction, 87 Differential thermal analysis, 328~9 Diisocyanates

activity, 297 analysis and characterization,

292~302

acidity, 295 chlorine content, 295~ 7 isomer ratio, 297 NCO content, 293~5

in atmosphere, 298~302 chain extenders, 1,4-BDO, 62~5,

74 health hazards, 102~3, 407~26

handling problems, 413~ 14 skin irritation, 412~17 threshold limit values (TL V), 408 toxicity data, 409~ 12

IPDI, isomers, 60. 62 lower-viscosity, applications, 397 reaction rates, I 07~ 10 spillage. 416

432 INDEX

Diisocyanates-contd. structure

effect on thermal stability, 61-5 thermal stability, 61-5

structure-thermal stability, storage modulus, 63

symmetrical, chain extenders with diols,73

thermal stability, effects on polyethane elastomers, 61-5 uneven molar ratio effects, 80-2 unsymmetrical, chain extenders,

65-7 see also CHDI: hexamethylene:

naphthalene: phenylene: PPDI: toluene; trans-l,4-cyclohexane diisocyanates; isocyanates; NCO groups

Dimethyl diphenylmethane diisocyanates, preparation, 9

Dimethylcyclohexylamine (DMCHA), catalyst, 115-16, 118

Dimethylethanolamine (DMEA), catalyst, 115-6

Diols abbreviations, 342 aliphatic, 'zig-zagging' of properties,

72 aralkyl and acyclic, crosslinking

polyurethane elastomers, 72 chain extenders, 70 as chain extenders, 167-8

Diphenylmethane diisocyanate, 10-13, 62-5

configuration structure, 66 effect of polyester side chains, 54 glycol-modified, 397 HUI2uMDI, isomers, 60, 62 health hazards, 409-10, 409-11 reaction rate

determination, 107-9 polyol molecular structure effects,

III structure, 12

Diphenylmethane diisocyanate-contd. synthesis, 10 thermoplastic PU formulation, 247 toxicity, 10-11 use in RIM, 180 variants, product descriptions and

applications, 12 DMT A, see Dynamic Mechanical

Thermal Analyzer DSC, see differential scanning

calorimetry DT A, see differential thermal analysis Dutrex, properties, 340 Dynamic Mechanical Thermal

Analyzer, 97, 99-101, 105 spectra, 273-5

Enerflux 72, properties, 340 Epichlorhydrin, properties, 368-9 Equivalent weights, 36-8 Ethacure,300

compared with MaCA, 166 structure, 165-7

Ethylene-propylene properties, 364-5 rubber (EPDM), comparative

properties, 195

Fibre reinforcement, RRIM, 196-8 Filler reinforcement, mill able

polyurethanes, 207 Film lamination, TPUs, 255 First aid, 416 Flame lamination, thermoplastic

polyurethanes, 255 Flexible segments

flexible to rigid segment, 50 property-structure relationships,

52-55 Fluorinated elastomers, properties,

366-7 Formrez materials, properties, lSI

INDEX 433

Fungal attack, 381

Glass transition temperature, low temperature stiffening, 101-2

Glycols in adhesives, structure, 222 chain extenders, 67-72 health hazards, 425

Health hazards of polyurethane elastomers, 407-26

diamines, 425 diisocyanates, atmospheric, 298-302 diphenylmethane diisocyanate,

409-11 glycol,425 handling problems, 413-14 isocyanate, monitoring and

detection, 420-5 manufacturing hazards, 417-20 naphthalene diisocyanate, 411 polyols, 425 skin irritation, 412-17 toluene diisocyanate, 409 toxicity data, 411-12 waste disposal, 426

Hexamethylene reaction rates, 108 temperature effects on diisocyanate

reaction rates, 110 see also diisocyanates

Hexamethylene diisocyanate, 13 hazards, 411

Hexane diol diacrylate (HDDA), structure, 352

Hydraulic seals, TPU, 264-7 Hydrogen abstraction, benzophenone,

354

Infra red spectroscopy A TR, 330, 332

Infra red spectroscopy-contd. FMIR, 330, 332 NCO groups

rapid method, 321-3 (unreacted), detection, 320

NH bond assignments, 316 polymers, differentiation, 330--3 PU absorption wavelengths, 312 TDI isomer ratio, 318-20 techniques, 311-23 useful IR band assignments, 314-15

Ionic dispersions, reagent for preparation, 287

Ionomers, 2-phase systems, 284-6 Isocyanates, 7-19

as adhesives, see adhesives, isocyanates

analysis alternative method, 423--4 diazotization method, 421-3

aromatic, 8 blocked, 17

adhesives, 235-9 branched, 18 crosslinks, in situ, 92 equivalent, defined, 43 equivalent weight, 40 hazards, 407-26 identification by colour reactions,

334--6 index, defined, 42-3 isocyanate-cured urethane rubber,

millable polyurethanes, 207-17 low volatility adducts, 17-18 reactions forming isocyanate

dimers, 15-19 spillage, neutralization, 416 storage life, 15-17 synthesis, 7-15

Curtius, Hoffman, and Lossen routes, 8

uretidiones, 19 see also diisocyanates; NCO groups

Isocyanurate, crosslinks, in situ, 92

434 INDEX

Isocyanurate rings, 18 Isonate 123P, blocked isocyanates, 236 Isoprenes, properties, 362-3

Ketoxime-blocked tetra isocyanates, 237

Latex emulsified latex, 282-3 self-emulsifying latex, 281-2

LIM (liquid injection moulding), see reaction injection moulding

LIM process, see also tyres Linear polyurethanes, see

thermoplastic polyurethanes Liquid polyurethane systems, 122-73

stable prepolymers, 124-52 chain extenders, 127-8 processing variables, 131-4 reaction temperature, 134-5 simple handcasting, 125-7 other systems, 135-52 TDI processing, 129-30

unstable prepolyumers, see Vulkollan

Low temperature stiffening,glass transition temperature, 101-2

MBTS effects, 205-6 properties, 205

MDA substituent for MOCA, 128 TDI polyether prepolymers, effects

on, 133 MDCA

alternative chain extenders, 165-9 urethanes, physical properties, 136

MDI, see diphenylmethane diisocyanatc

Medicine, polyurethanes, applications, 400-3

Melt dispersion technique, water dispersions of PU, 290

Methyl benzoate, structure, 353 Microcellular polyurethane RIM

formulation, 179-82 Microporous thermoplastic PU, 260-3 Millable polyurethanes, 199-220

applications 403-5 carbon-black loading, 207, 210 filler reinforcement, 207 isocyanate-cured urethane rubber,

207-17 combined, 220

peroxide-cured polyurethanes, 217-20

combined, 220 plasticization, 206-7 polyether series, 201-6 process route, 123 sulphur concentration effects, 204 sulphur vulcanized grades, 200-1 synthesis, 30-4

Millathane, millable polyurethane, 201 MOCA

chain extender, substitutes, 127-8 properties of polyurethanes

prepared from, 140 structures and properties, 138 TDI polyether prepolymers, effects

on, 133, 135 Molecular weights, calculations, 37-8 Mondur SH, blocked isocyanates,

236 MPD, TDI polyether prepolymers,

effects on, 133 M uItrathane F66 polymers,

properties, 153

Naphthalene reaction rates, 108 temperature effects on diisocyanate

reaction rates, 110 see also diisocyanates

INDEX 435

Naphthalene diisocyanate, 13 effect of polyester blends, 54 health hazards, 411 1,5- and 2,3-naphthalene diols,

maximum stability T, 78 structure, 14, 74, 75

Naphthalene diol/polyester, see Vulkollan

NCO groups content, diisocyanates, 293-5 influence on polyurethanes, 97-8 percentage free, 39, 49, 97-8 strength, elevated temperature, 99 water dispersions of PU, 281-91 see also diisocyanates; isocyanate

Number-average molecular weight, defined, 43-4

Odours, catalyst residues, 118 Organotins, catalysts, 114-16, 118-20 Oxetones, nucleophilic ring opening,

288

Paints, health hazards, 418-19 Paraphenylene diisocyanate

OMTA properties, 171 hardness vs diisocyanate content, 173 hazards, 411-13 prepolymer synthesis and chain

extension, 171-3 properties, 168-9 temperature effects, 172

Paraphenylene diisocyanate-based polyurethanes

chain extension, 268 OTMA spectra, 273, 275 mixed aliphatic diols as chain

extenders, 277 Peroxides

curing of PU, 205-7 dicamyl peroxide, 218-19 polyols, 310

Phenylene reaction rates, 108 temperature effects on diisocyanate

reaction rates, 110 see also diisocyanates

Photoinitiators, reaction sequence, 353, 354

Plasticizers compatibility, 405 effects on polyurethane

ageing, 209 properties, 208

millable polyurethanes, 206-7 Plastics

abrasion resistance, 374 properties, 370-1

Polacure comparisons, 82, 83 properties of polyurethanes

prepared from, 144 structure, 75 structures and properties, 138

Polacure-240M, structure, 166 Polybutadienes

electrical properties, 328 low-temperature resistance, 339 NCOjOH ratio, 339 process oils, plasticizers, 339 structure, 337 transparent polyurethanes, 339-50

Polycaprolactone CHOI polyurethanes, thermal

stability, 278 hydrolytic stability, 380-2 PPOI polyurethanes, thermal

stability, 278 property-structure relationships,

56-7,62,74 structure, 247 synthesis, 23-4 TDI, physical properties, 136 sec a/so polyols

Polycarbonate, comparative properties, 195

436

Polyesters general structures, 21 glass reinforced, comparative

properties, 195 hydrolysis, 331-3 hydrolytic stability, 380-2 identification of components, 329 properties, 368-9 series, elastomer route, 122 shoe solings, 395-7 synthesis, 21-4 TD!, properties, 151 TPUs,268-76

Polyethers CHDI polyurethanes, thermal

stability, 279 elastomer route, 122 electrical properties, 389 general structures, 23 hydrolysis, 331 hydrolytic stability, 380-2 identification of components,

329-30 millable polyurethanes, 201-6 PPDI polyurethanes, thermal

stability, 278 property-structure relationships,

55-6 shoe solings, 395-7 synthesis, 24-7

Polyethylene adipate elastomers, 53 reaction rates with MD!, 111

Polyols acid number, 307 amine-terminated, 350-4 analysis and characterization,

303-11 blends, 46-8 curatives, 134 fluorinated, 351 hydrolytic stability, 308 hydroxyl groups, 305-6 hydroxyl number, 303-5

INDEX

Polyols-contd. linear PU, 19-21 peroxide content, 310 pH measurement, 307 quantitization, chemical analysis,

40-2 reaction rates, 110-12 spray drying, 165 unsaturation, 308-10 water content, 164,306-7 see also polycaprolactone

Polypropylene, comparative properties, 195

Polypropylene ether, one shot foam catalysis, 117

Polypropylene glycol, reaction rates with MD!, 111

Polysulphide, properties, 364-5 Polyurethane elastomers

adhesives, see adhesives analysis and characterization,

292-336 ageing, 376-82 chromatography techniques,

323-8 differentiation of polymers

present, 330-3 diisocyanates, 292-302 dynamic mechanical thermal

analysis (DMTA), 99-101 energy absorption properties, 372 identification of components,

329-30 infra red spectroscopy techniques,

311-23 miscellaneous elements, 333-6 polar groups, 51 polyols, 303-11 thermal analysis, 328

applications, 390-406 automotive body panels, 398 cold-cast polyurethanes, 404 current types, 390-9

INDEX 437

Polyurethane elastomers-contd. applications-contd.

medicine, 400-3 millable polyurethane elastomers,

403-4 rain-erosion protection, 398 rollers, 397 shoe solings, 395-7 tyres, 392-5 tyres and low speed tyre-filling

compositions, 398 water vapour permeable, 399-400

aqueous, see water dispersions of PU

carbon black fillers, 207, 210, 212 catalysts, 27-8, 113-20 chain extenders

composition, 77-80 diamine cures, 128 diamine vs diols, 82-5 polyol cures, 128 synthesis, 73-6

chemical resistance, 383-4, 386-7 chemistry

basic intermediates, 2-28 structure, 4-7

cohesion energies, 52 cold-curing, 398 compositions

1 :2:1 molar ratio, 92-7 mixed chain extenders, 92-7 of series, 90-7

concept of complete urethane chemical system, 38-40

concept of equivalent weights, 36-8 continued crystal growth, 106 crosslinking

block ratio effects, 349 contribution to properties, 87-9 diol/triol ratio, 350 isocyanate and isocyanurate, 90 levels, 72 raction rates, 107

Polyurethane elastomers-contd. crosslinking-contd.

structure, 103 and thermal stability, 89-90, 103

differential scanning calorimetry, 84-9, 105-6

even molar ratio effects, 76-7 fluid and chemical resistance, 382 health hazards, 102-3, 417-20 high energy radiation, effects, 383-7 hydrolysis, resistance, 380-2, 385 identification, 334-6 infra red spectroscopy, 311-23 liquid elastomers

liquid processing routes, 29-30 see also liquid polyurethane

systems loss tangent values, 77-80 medical applications, 400-3 non-black fillers, 213 one shot reaction sequence, 32

processing, 391 paints, hazards, 418 plasticization, 106 PPDI-based, see PPDI prepolymer reaction sequences, 31 printing inks, 419-20 properties, 355-90

% free NCO influence, 97-8 ageing periods, 106 colour reactions, 334-6 comparison with rubbers and

plastics, 372-90 effect of diisocyanates, 58 electrical properties, 387-90 elevated temperatures, 99 environmental properties, 376-82 flexible to rigid segment, 50 friction properties, 375-6 increasing size of rigid block, 71 light resistance, 383 load deflection, 359-71 low temperature stiffening, 101-2

438 INDEX

Polyurethane elastomers-contd. Polyurethane elastomers-contd. properties-contd.

optical properties, 59-61 radiation resistance, 388 tensile properties, 357-9 thermal equilibrium, 101 wear resistance, 373-5

property-structure relationships, 2, 51-106

aliphatic diisocyanates, 59-61 aliphatic vs aromatic

diisocyanates, 59 diisocyanate structure, effect on

thermal stability, 61-5 flexible segments, 52-5 polycaprolactone elastomers,

56-7,62,74 polyethers, 55-6 rigid segments, 57-9 symmetrical diisocyanates, chain

extenders with diols, 73 unsymmetrical diisocyanates,

chain extenders, 65-7 RIM catalysis, 117

surfactants, 120-1 segmented, medical applications,

403 spray application, 163-4 stress relaxation, 379 stress-strain curves, 357, 358

hardness vs Young's modulus, 357,358

load deflection, 359, 371 structure

basic urethane building blocks, isocyanates, 7-19

diisocyanate effect on thermal stability, 61-5

flexible and rigid segments, 5 hydroxy-terminated

polybutadienes, 337-50 intermediate combinations,

polyether/polyester series, 122

structure-contd. summary, 103-6 two-phase, 103 see also crosslinking; property­

structure relationships synthesis

IX, f3 and r transition temperatures, different diol chain extenders, 79

alternative routes, 123 calculations, 45-6 from liquid reactants,

temperature ranges, 112 handcasting proced ure, 125-7 liquid processing routes, 29-30 machining, 406 materials used, 74-5 millable elastomer synthesis,

30-4, 123 mould lubricant, 405-6 moulding, 405 one shot sequence processing, 32 one-shot system, 391 shrinkage, 405 technique, 90-2

materials used, 91 thermoplastic route, 123

temperature effects, 376-80 thermal stability

IX and f3 transition T, 65 crosslinked structure, 103 diol structure influence, 76-7 effects, 61-5, 82-5 maxima, 76 storage modulus, maximum T, 63

thermoplastic linear urethane elastomers, 34-6

torsional stiffness, 379 transparent polyurethanes, 59-61,

339-50 use (1989), 392 water absorption effects, 389

INDEX 439

Polyurethane elastomers-contd. water blow-foam system, isocyanate

proportions, 48-50 water dispersions, see water

dispersions of PU Polyurethanes, linear, 20 Porous PU

processing, 261 properties, 262-3

P,P biphenol maximum stability T, 78, 80, 81 structure, 74

PPOI, see paraphenylene diisocyanate Prepolymers

applications, 391 ionomers, 284-6 reaction seq uences, 31 synthesis and chain extension,

171-3 Propylene oxide, properties, 368-9 Protective clothing, 416 PVc, properties, 368-9

Quinol maximum stability T, 78, 80, 81 structure, 74

Reaction injection moulding, 174-94 elastomer products

amine-terminated polyols, 350-4 UV light-curable PU systems,

352-4 energy requirements, 186-7 formulation, 179-82 high modulus system, 184 impingement mixing, 187 low modulus system, 183 machine design, 182-6 mould design, 187-94

mould sealing, 193 moulding, 191

Reaction injection moulding-contd. mould design-contd.

moulding pressures, 177 ribs and radius, 191-2 runners, 192-3 transition zone, 189-91

processing, 178-9 economics, 194

properties, reinforced, us unreinforced, 194

quasi-prepolymer systems, 176 reinforced (RRIM), 194-8 two-component systems, 175 unit operations, 185 us thermoplastic injection moulding,

186 water use, 181

Rigid segments, property-structure relationships, 57-9

RIM, see reaction injection moulding Rollers, PU, 397 RRIM, see reaction injection

moulding, reinforced Rubber

abrasion resistance, 374 friction properties, 376 rubber seals, TPU, 264-7 and rubber-like polymers, properties

compared with PU, 362-9 urethane

PPDI and CHDI, 267 specific hazards, 417

Shoe solings, polyethers and polyesters, 395-7

Silicones properties, 364-5, 370-1 surfactants, 121

Skin, hazards, see health hazards Spray application, polyurethanes,

163-4 Styrene, properties, 362-3, 368-9

440 INDEX

Sulphur curing of PU, 204-7 Sulphur vulcanized grades, millable

polyurethanes, 200-1 Surfactants, 120-1

T220, structure, 75 TDI, see toluene diisocyanate Tertiary amines, catalysts, 115-16,

117-18 Tetramethylbutanediamine (TMBDA),

catalyst, 115-16 Tetramethylethylenediamine

(TMEDA), catalyst, 118 TGA, see thermogravimetric analysis Thermal analysis, 328 Thermogravimetric analysis, 328-9 Thermoplastic injection moulding, vs

RIM,186 Thermoplastic linear urethane

elastomers, 34-6 Thermoplastic polyurethanes, 244-80

100%-solids reactive system, 257 ABS blends, 263 blends, 263-4, 397 calendering, 253-4 catalysts, 249 CHDI-based polyurethanes, 267-77 coatings, types, 256-7 commercially available, 257-9 DMTA spectra, 273-5 energy absorption (tan b), 279 extrusion, 250 film lamination, 255-6 flame lamination, 255 formulation, typical, 246 heat-melt calendering, 254-5 hydraulic seal materials, 264-7 injection-moulding processing-

temperature profiles, 251-3 microporous, 260-3 mixed aliphatic diols as chain

extenders, 277

Polyurethane elastomers-contd. NCO/OH ratios, 245 partially crosslinked, 245

post cure effects, 246 permeability, introduction, 261 polyester series, properties, 268-77 polyether series, properties, 272, 277 PPD I -based polyurethanes, 268-77 processing, 123,249-56, 391 properties, moisture effects, 252 reactive coatings, 256-7 set properties, 260 solution applications, 256 synthesis, 245-9

large scale, 249 melt-processing problems, 250 small-scale apparatus, 248

thermal stability, 278-9 transparent, processing, 264

Tin compounds, catalysis, see organotins

TMAB, see Polacure-740M TMP, see trimethylol propane TMPT A, see trimethylol propane

triacrylate TODI, see tolidene diisocyanate Tolidene diisocyanate, preparation, 9 Toluene diisocyanate, 9-13, 62-5

chain extenders, 2,4-TDI, configuration structure, 66

determination, atmosphere, 424-5 elastomers, diamine chain-extenders

control,66 health hazards, 10-11, 409

effects of exposure, 410 hydrolysis resistance, 385 polyether prepolymers

amines, different, effects, 133 chain extender concentration, 131 handcasting procedure, 125-7 processing and batch casting, 129 processing and cured properties,

130

INDEX 441

Toluene diisocyanate~contd. polyether prepolymers~contd.

processing and machine casting, 129

reaction rates, 108 structure, 222 synthesis, 9 temperature effects on diisocyanate

reaction rates, 110 toxicity, 10-11 see also diisocyanates

TPUs, see thermoplastic polyurethanes

Transparent polyurethanes, 59-61, 339-50

block ratios and ageing, 344-5 DSC thermo grams, 347 hard segment content, 346 medical applications, 403 polybutadienes, 339-50 processing, 264 trifunctional chain extender, 348-50

Triethylamine (TEA), catalyst, 115-16 Triethylene diamine (l,4-diazo[2,2,2]­

bicycIo-octane) (DABCO) catalysis, 115, 118 structure, 27

Trimethylol propane triacrylate (TMPT A), structure, 352

Tyres low speed tyre-filling compositions,

398 performance comparisons, 394 PU pneumatic, 392-5 see also reaction injection moulding

Urea, synthesis, 3 Urepan

compounding with Desdomur TT, 215-17

isocyanate cured rubber, 207, 217

U repan~con t d. millable polyurethane, 201 properties, 215

Urethane block unit, structure, 5 Urethane groups, thermal stability,

61-5 Uretidiones, 18, 19 Uretoneimines, 397 UV light-curable PU systems,

elastomer products, RIM, 352-4

Vi bra thane cast elastomers, properties, 154 millable polyurethane, 201

Vulkollan formulation, 155 manufacture, route, 136, 152-8 properties, 157 water crosslinked millable, 158

Vulkollen elastomer system, 123, 156-9

Water dispersions of PU, 281-91 blow-foam system, isocyanate

proportions, 48-50 emulsified latex, 282-3 melt dispersion technique, 290 PU isonomers, 284-6 reaction sequence, 282 self-emulsifying latex, 281-2 special features, 286-90

anionic dispersions, 287-8 cationic dispersions, 288-90

Water vapour permeable polyurethanes, 399-400

Weight-average molecular weight, defined, 44-5

Xylylene diisocyanate, structure, 14