John S. Dick
Raw Materials Supply Chain for Rubber Products
Overview of the Global Use of Raw Materials, Polymers, Compounding Ingredients, and Chemical Intermediates
Preface
6
Contents
8
Acknowledgments
7
1 Introduction
18
1.1 Rubber Industry’s Place in the World Economy
19
1.2 The Structure of the Tire Industry
19
1.3 The Structure of the Nontire Industry
22
1.4 Sectors of the Nontire Rubber Industry
24
1.5 Market Forces
27
2 Basic Raw Materials from Earth Extractions and Agriculture
30
2.1 Vital Basic Raw Materials for Rubber
31
2.1.1 Crude Petroleum Oil
31
2.1.2 Natural Gas
37
2.1.3 Natural Rubber
40
2.1.4 Sulfur
42
2.1.5 Zinc Ore
43
2.1.6 Copper Ore
44
2.1.7 Iron Ore
45
2.1.8 Silica
46
2.1.9 Brine and Sea Salt
47
2.1.10 Fluorspar
47
2.2 Important Basic Raw Materials for Rubber
48
2.2.1 Antimony Ore
48
2.2.2 Aluminum Ore
48
2.2.3 Clay
49
2.2.4 Coal
50
2.2.5 Cobalt Ore
51
2.2.6 Limestone
52
2.2.7 Phosphate Rock
52
2.2.8 Pine Trees
53
2.2.9 Tallow (from Cattle)
54
2.2.10 Titanium Ore
55
2.2.11 Vegetable Oils
55
2.3 Summary
57
3 General-Purpose Elastomers
58
3.1 Natural Rubber
58
3.2 Synthetic Natural Rubber
60
3.3 Styrene Butadiene Rubber (SBR)
62
3.4 Butadiene Rubber (BR)
70
3.5 Ethylene Propylene Diene Rubber (EPDM)
75
3.6 Summary
79
4 Specialty Elastomers
82
4.1 Butyl Rubber
83
4.2 Halobutyl Rubber
86
4.3 Brominated Copolymer of Isobutylene and para-Methylstyrene (BIMSM)
90
4.4 Nitrile Rubber
92
4.5 Hydrogenated Nitrile Rubber (HNBR)
96
4.6 Curable PVC/NBR Polyblends
99
4.7 Acrylic Rubber
103
4.8 Polychloroprene (CR)
105
4.9 Chlorinated Polyethylene Rubber
109
4.10 Chlorosulfonated Polyethylene (CSM)
111
4.11 Epichlorohydrin Rubber
113
4.12 Ethylene Acrylic Elastomer (AEM)
116
4.13 Ethylene Vinyl Acetate (EVA)
118
4.14 Fluoroelastomers
121
4.15 Perfluoroelastomers (FFKM)
126
4.16 Silicone Rubber
127
4.17 Summary
130
5 Textile Reinforcing Materials and Their Adhesive Systems Used in Rubber
132
5.1 Textile Reinforcing Materials
132
5.1.1 Aramid
132
5.1.2 Carbon Fibers
135
5.1.3 Glass Fibers
137
5.1.4 Nylon
139
5.1.5 Polyester Fiber
144
5.1.6 Rayon
147
5.1.7 Steel Cord and Cable
151
5.2 Adhesive Systems Used in Rubber
153
5.2.1 Dips for Rubber-to-Cord Adhesion
153
5.2.1.1 Resorcinol Formaldehyde Resin (Liquid)
154
5.2.1.2 Styrene Butadiene Vinylpyridine Latex
156
5.2.1.3 Isocyanate and/or Epoxy Treatment
159
5.2.2 Rubber Compounding Additives for Cord Adhesion
160
5.2.2.1 Hydrated Precipitated Silica
161
5.2.2.2 Resorcinol Formaldehyde Resin (Solid)
163
5.2.2.3 Hexamethoxymethylmelamine (HMMM)
165
5.2.2.4 Hexamethylene Tetramine (HMT)
168
5.2.2.5 Cobalt Stearate
169
5.3 Summary
171
6 Thermoplastic Elastomers
172
6.1 Styrenic Block Copolymers (SBC)
173
6.2 Thermoplastic Olefins (TPO)
177
6.3 Thermoplastic Vulcanizate (TPV) Based on PP/EPDM
180
6.4 Thermoplastic Vulcanizate (TPV) Based on NBR/PP
184
6.5 Thermoplastic Vulcanizate (TPV) Based on IIR/PP
186
6.6 Thermoplastic Vulcanizate (TPV) Based on ACM/Nylon
189
6.7 Thermoplastic Vulcanizate (TPV) Based on BIMS/Nylon
191
6.8 Thermoplastic Polyurethanes (TPUs)
192
6.9 Copolyester and Polyamide Block Copolymers
194
6.10 Summary
195
7 Polyurethane
196
7.1 Polyols
198
7.2 Adipic Acid-Ethylene Glycol Polyester Polyol
198
7.3 Polypropylene Glycol Polyol
200
7.4 Isocyanates
201
7.4.1 4,4'-Diphenylmethane Diisocyanate (MDI)
202
7.4.2 Toluene Diisocyanate (TDI)
205
7.5 Chain Extenders
206
7.5.1 1,4-Butanediol (1,4-BD)
207
7.5.2 Bis(beta-hydroxyethyl) Ether of Resorcinol (HER)
209
7.5.3 Hydroquinone Di-(2-hydroxyethyl) Ether (HQEE)
211
7.5.4 Trimethylolpropane (TMP)
213
7.6 Methylene-Bis-o-chloroaniline (MBCA)
214
7.7 Summary
216
8 Carbon Black, Fillers, Reinforcing Agents, and Coupling Agents
218
8.1 Furnace Carbon Blacks
218
8.2 Thermal Carbon Black
223
8.3 Acetylene Carbon Black
225
8.4 Hydrated Precipitated Silica
227
8.5 Fumed Silica
230
8.6 TESPT Organosilane Coupling Agent
232
8.7 Kaolin Clay
234
8.8 Calcium Carbonate
237
8.9 Talc
239
8.10 Titanium Dioxide
241
8.11 Ground Coal
243
8.12 Iron Oxide
244
8.13 Summary
246
9 Process Oils, Synthetic Ester Plasticizers, and Processing Aids
248
9.1 Aromatic Process Oil
248
9.2 Naphthenic Process Oil
251
9.3 Paraffinic Oil
253
9.4 Rosin Oil
256
9.5 Dioctyl Phthalate (DOP)
257
9.6 Diisodecyl Phthalate (DIDP)
261
9.7 Dioctyl Adipate (DOA)
263
9.8 Dioctyl Sebacate (DOS)
265
9.9 Butyl Oleate
267
9.10 Dibutoxyethoxyethyl Adipate (DBEEA)
270
9.11 Vulcanized Vegetable Oil (VVO)
272
9.12 Summary
273
10 Curatives
274
10.1 Activators
275
10.1.1 Zinc Oxide
275
10.1.2 Stearic Acid
278
10.2 Vulcanizing Agents (Sulfur Based)
280
10.2.1 Rubber Maker’s Sulfur
280
10.2.2 Insoluble Sulfur
283
10.2.3 Dithiodimorpholine (DTDM)
285
10.2.4 Tetramethylthiuram Disulfide (TMTD)
288
10.3 Primary Accelerators
291
10.3.1 N-t-butyl-2-benzothiazole Sulfenamide (TBBS)
291
10.3.2 N-Cyclohexyl-2-benzothiazole Sulfenamide (CBS)
294
10.3.3 2-(4-Morpholinothio)-benzothiazole Sulfenamide (MBS)
297
10.3.4 N,N'-Dicyclohexyl-2-benzothiazole Sulfenamide (DCBS)
300
10.3.5 4-Morpholinyl-2-benzothiazole Disulfide (MBSS)
302
10.3.6 Alkyl Phenol Disulfide
305
10.3.7 Ethylene Thiourea (ETU)
306
10.4 Secondary Accelerators
308
10.4.1 2-Mercaptobenzothiazole (MBT)
308
10.4.2 Benzothiazole Disulfide (MBTS)
311
10.4.3 Tetramethyl Thiuram Monosulfide (TMTM)
314
10.4.4 Zinc Dibutyldithiocarbamate (ZnDBC)
317
10.4.5 Zinc Dimethyldithiocarbamate (ZnDMC)
319
10.4.6 Tellurium Diethyldithiocarbamate (TeDEC)
321
10.4.7 Diphenyl Guanidine (DPG)
323
10.4.8 Di-o-Tolylguanidine (DOTG)
326
10.5 Inhibitors and Retarders
328
10.5.1 Cyclohexylthiophthalimide (CTP)
328
10.5.2 Benzoic Acid
331
10.5.3 Phthalic Anhydride
333
10.5.4 Salicylic Acid
334
10.5.5 Magnesium Oxide (MgO)
336
10.6 Nonsulfur Vulcanizing Agents
337
10.6.1 Dicumyl Peroxide (DCP)
338
10.6.2 Di(2-t-butylperoxyisopropyl)benzene (BBPIB)
340
10.6.3 Methylol-Terminated p-Alkyl-Substituted Phenol Formaldehyde Curing Resin
341
10.6.4 Zinc Oxide
343
10.7 Summary
344
11 Antioxidants, Antiozonants, Tackifiers, Flame Retardants, and Blowing Agents
346
11.1 Antioxidants
346
11.1.1 2,2,4-Trimethyl-1,2-dihydroquinoline (TMQ)
346
11.1.2 Acetone Diphenylamine Condensation Product (ADPA)
349
11.1.3 Phenyl-alpha-naphthylamine (PAN)
351
11.1.4 Octylated Diphenylamine (8DPA)
354
11.1.5 Methylene-bis-methylbutyl phenol (o-MBp14)
356
11.1.6 N,N'-Di-beta-naphthyl-p-phenylene Diamine (DNPD)
358
11.2 Antiozonants
360
11.2.1 N-1,3-Dimethylbutyl-N'-phenyl-p-phenylene Diamine (6PPD)
360
11.2.2 N-N'-bis (1-methylheptyl)-p-phenylene Diamine (i88PD)
365
11.2.3 N,N'-Diphenyl-p-phenylene Diamine (DPPD)
367
11.2.4 Protective Waxes
369
11.3 Tackifiers
371
11.3.1 Phenol Formaldehyde Resins
371
11.3.2 Phenol Acetylene Tackifying Resin
373
11.3.3 Petroleum Aliphatic Hydrocarbon Resins
375
11.3.4 Polyterpene Resins
376
11.4 Blowing Agents (for Sponge Rubber)
378
11.4.1 Azodicarbonamide (ADC)
378
11.4.2 p,p'-Oxybis(benzenesulfonyl) Hydrazide (OBSH)
379
11.5 Flame Retardants
382
11.5.1 Antimony Oxide (Antimony Trioxide)
382
11.5.2 Chlorinated Paraffin (CP)
384
11.5.3 Alumina Trihydrate (ATH)
386
11.5.4 Zinc Borate Hydrate
387
11.5.5 Triaryl Phosphate (TAP)
389
11.6 Summary
390
12 Intermediate Feedstocks
392
12.1 Acetaldehyde
394
12.2 Acetic Acid
395
12.3 Acetone
396
12.4 Acetylene
397
12.5 Acrylonitrile (ACN)
398
12.6 Acrylonitrile Butadiene Rubber (NBR)
399
12.7 Adipic Acid
400
12.8 p-Alkylphenol (para-Alkylphenol)
401
12.9 4-Aminodiphenylamine (4-ADPA)
401
12.10 Ammonia
402
12.11 Ammonium Thiocyanate
404
12.12 t-Amylene
405
12.13 Aniline
405
12.14 Aniline Hydrochloride
407
12.15 Antimony
408
12.16 Antimony Trichloride
408
12.17 Benzene
409
12.18 Benzothiazyl Disulfide (MBTS)
411
12.19 Borates (Borax)
411
12.20 Boric Acid
412
12.21 Bromine
413
12.22 Butadiene (BD)
414
12.23 Butane
416
12.24 1,4-Butanediol (BDO)
417
12.25 Butanol (Butyl Alcohol)
418
12.26 n-Butyl Acrylate
419
12.27 t-Butylamine
420
12.28 n-Butyl Chloride
421
12.29 t-Butylphenol
421
12.30 n-Butyraldehyde
422
12.31 Calcium Carbide
423
12.32 Calcium Hydroxide
424
12.33 Calcium Oxide
425
12.34 Caprolactam
425
12.35 Carbon Disulfide
427
12.36 Chlorine
428
12.37 Chlorobenzene (Monochlorobenzene)
429
12.38 Chlorodifluoromethane
430
12.39 Chlorohydrin
430
12.40 Coal Tar
431
12.41 Crotonaldehyde
431
12.42 Cumene
432
12.43 Cyclohexane
433
12.44 Cyclohexanone
435
12.45 Cyclohexylamine
436
12.46 Cyclohexyl Mercaptan
436
12.47 Cyclopentadiene
437
12.48 p,p'-Diaminodiphenylmethane
438
12.49 Diaminotoluene
438
12.50 Dibutylamine
439
12.51 Dichlorodimethylsilane
440
12.52 Dicyclohexylamine
441
12.53 Dicyclopentadiene
441
12.54 Diethylamine
442
12.55 Diisobutylene
443
12.56 Dimethylamine
443
12.57 Dimethyl Terephthalate
444
12.58 p-Dinitrobenzene (para-Dinitrobenzene)
445
12.59 2,4-Dinitrotoluene
446
12.60 Diphenylamine
446
12.61 Diphenylmethane-4,4'-Diisocyanate (MDI)
447
12.62 Epichlorohydrin
449
12.63 Ethane
450
12.64 Ethyl Acrylate
450
12.65 Ethyl Alcohol (Ethanol)
451
12.66 Ethylbenzene
452
12.67 Ethylene
453
12.68 Ethylene Carbonate
455
12.69 Ethylene Chlorohydrin
455
12.70 Ethylenediamine
456
12.71 Ethylene Dichloride
457
12.72 Ethylene Glycol (EG)
458
12.73 Ethylene Oxide (EO)
458
12.74 2-Ethylhexanol (2EH)
460
12.75 5-Ethylidenenorbornene (ENB)
461
12.76 Formaldehyde
462
12.77 1,4-Hexadiene
464
12.78 Hexamethylenediamine
464
12.79 Hexamethylenetetramine (HMT)
465
12.80 Hydrazine
466
12.81 Hydrochloric Acid
467
12.82 Hypochlorous Acid
468
12.83 Hydrogen
468
12.84 Hydrogen Fluoride
469
12.85 Hydrogen Peroxide
470
12.86 Hydroquinone
471
12.87 Iron
472
12.88 Isobutylene
472
12.89 Isobutylene-Isoprene Rubber (IIR, Butyl Rubber)
474
12.90 Isocyanate-Terminated Prepolymer
475
12.91 Isoprene
475
12.92 Isopropyl Alcohol
476
12.93 p-Isopropylphenol
477
12.94 Melamine
478
12.95 Mercaptobenzothiazole (MBT)
479
12.96 Mesityl Oxide
479
12.97 Methane
480
12.98 Methanol
481
12.99 Methyl Acrylate
482
12.100 Methyl Chloride
483
12.101 Methylethyl Ketone (MEK)
484
12.102 Methyl Isobutyl Ketone (MIBK)
485
12.103 p-Methylphenol
486
12.104 p-Methylstyrene
486
12.105 Morpholine
487
12.106 Naphthalene
488
12.107 ß.-Naphthol
489
12.108 a-Naphthylamine
489
12.109 Nitric Acid
490
12.110 p-Nitroaniline
491
12.111 Nitrobenzene
492
12.112 a-Nitronaphthalene
492
12.113 n-Octanol (octyl alcohol)
493
12.114 p-t-Octylphenol (p-tert-Octylphenol)
494
12.115 Oleic Acid
495
12.116 Phenol
496
12.117 p-Phenylenediamine (PPDA)
498
12.118 Phosgene
499
12.119 Phosphorus
500
12.120 Phosphorus Oxychloride
500
12.121 Phosphorus Pentoxide
501
12.122 Phosphorus Trichloride
502
12.123 Phthalic Anhydride
503
12.124 Phthalimide
504
12.125 a-Picoline
505
12.126 Polyacrylonitrile
506
12.127 Polypropylene (PP)
506
12.128 Polypropylene Glycol
507
12.129 Polyvinyl Chloride (PVC)
508
12.130 Potassium Bromide
509
12.131 Propane
510
12.132 Propylene
511
12.133 Propylene Glycol (PG)
512
12.134 Propylene Oxide
513
12.135 Quinone (1,4-Benzoquinone)
514
12.136 Resorcinol
515
12.137 Sebacic Acid
516
12.138 Silicon Metal
517
12.139 Silicon Tetrachloride
518
12.140 Sodium Bromide
519
12.141 Sodium Carbonate
519
12.142 Sodium Dimethyldithiocarbamate (NaDMC)
520
12.143 Sodium Hydroxide (Caustic Soda)
521
12.144 Sodium Hypochlorite
522
12.145 Sodium Mercaptobenzothiazole (NaMBT or Sodium MBT)
523
12.146 Sodium Nitrate
524
12.147 Sodium Phenate
524
12.148 Sodium Silicate
525
12.149 Sodium Sulfate
525
12.150 Sodium Sulfite
526
12.151 Stannous Chloride
527
12.152 Stearic Acid
528
12.153 Styrene
529
12.154 Sulfur
530
12.155 Sulfur Dioxide
531
12.156 Sulfuric Acid
532
12.157 Sulfur Monochloride
533
12.158 Terephthalic Acid
534
12.159 Tetrafluoroethylene
535
12.160 Tin
536
12.161 Titanium Tetrachloride
536
12.162 Toluene
537
12.163 Toluene Diisocyanate (TDI)
538
12.164 o-Toluidine (ortho-Toluidine)
539
12.165 1,1,1-Trichloroethane
540
12.166 Trichlorosilane
541
12.167 1,1,1-Trimethylolpropane (TMP)
541
12.168 Urea
542
12.169 Vinyl Acetate
543
12.170 Vinyl Chloride Monomer
544
12.171 Vinyl Fluoride
545
12.172 Vinyl Pyridine
546
12.173 Wax
547
12.174 Xylene
547
12.175 Zinc Metal
548
12.176 Zinc Carbonate
549
12.177 Zinc Stearate
550
12.178 Zinc Sulfate
550
Glossary of Acronyms
552
Index
560
About the Authors
600
© 2009-2024 ciando GmbH