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.
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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-
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427
428 POLYURETHANE ELASTOMERS
York, USA. A bimonthly trade and news publication by Crain Communications, London.
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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.
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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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Reinhold Company, New York. Woods, G. (1982). Flexible Polyurethane Foams. Applied Science Publishers,
London. Woods, G. (1990). The ICI Polyurethanes Book, 2nd edn. John Wiley, Chichester. Wright, P. & Cumming, A. P. C. (1969). Solid Polyurethane Elastomers. Maclaren
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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