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MONOMERS FOR POLYMERIZATION POLYMERS





Chapter 3. Olefin monomers…………………………………………………… 81

3.1. Lower olefins………………………………………………………………… 82

3.1.3. Basic material in the manufacture of lower olefins…………………. 83

3.1.4. Manufacture of ethylene…………………………………………….. 86

High-temperature dehydrogenation of ethane…………………… 87

Manufacture of ethylene from methane…………………………. 87

Manufacture of ethylene from methanol………………………… 88

Dehydration of ethanol………………………………………….. 89

3.1.3. Manufacture of propylene…………………………………………… 90

Isolation of propylene from refinery and cracking gases……….. 90

Isolation of propylene from the products

оf Fischer-Tropsch synthesis …………………………………… 90

Thermal dehydrogenation of propane…………………………… 92

Catalytic dehydrogenation of propane and other lower alkanes (Oleflex

process)………………………………………………………….. 92

3.1.4. Manufacture of 1-butene…………………………………………….. 95

Isolation of 1-butene from hydrocarbon fractions C…………… 95

Catalytic dimerization of ethylene………………………………. 96

3.1.5. Manufacture of isobutylene…………………………………………. 97

Isolation of isobutylene from hydrocarbon fractions С………… 97



Dehydrogenation of isobutene…………………………………... 98

Isomerization of 1-butene……………………………………….. 99

Synthesis of isobutylene from acetone………………………….. 99 3.2. Higher olefins………………………………………………………………… 99

3.2.1. Manufacture of higher olefins by dimerization and codimerization of ole-

fins……………………………………………………………… 99



Cationic dimerization of olefins……………………………… 100

Anionic dimerization of olefins………………………………… 101

Dimerization in the presence of organometallic catalysts……… 102

Coordination-catalytic dimerization and codimerization of olefins103

Dimerization of n-butenes……………………………………… 105

Codimerization of propylene and n-butenes…………………… 105 3.2.2. Disproportionation of olefins……………………………………… 108

3.2.3. Dimerization and disproportionation of olefins in a single technological

process……………………………………………………………… 110

Synthesis of isopentenes from ethylene………………………… 110

Manufacture of isopentenes from propylene…………………… 111

Manufacture of isopentenes and higher olefins from ethylene,

propylene, and their mixtures…………………………………… 112

3.2.4. Manufacture of higher olefins from synthesis gas………………….. 113

3.2.5. Manufacture of cycloolefins ……………………………………….. 113 Synthesis of cyclopenten……………………………………………. 115 Synthesis of cyclohexent……………………………………………. 116Synthesis of nonbornene…………………………………………… 117

Chapter 4. Diene monomers…………………………………………………… 118

4.1. 1,3-Butadiene……………………………………………………………….. 122

4.1.1. Lebedev’s method……………………………………………… 123

4.1.2. Ostromyslensky’s method………………………………………….. 123

4.1.3. Manufacture of butadiene from acetylene………………………….. 124



Synthesis of butadiene via aldol (the aldol method)…………… 124

Synthesis of butadiene via butynediol…………………………. 126

Synthesis of butadiene via dimerization of acetylene………….. 127

Pyrolysis of hydrocarbon raw material ………………………... 127

4.1.4. Industrial methods for the manufacture of butadiene

from butane or 1-butene………………………………………………… 127

Dehydrogenation of С-С hydrocarbons to olefins…………… 129

Oxidative dehydrogenation of butane and butanes……………. 129

One-step dehydrogenation of butane to butadiene…………….. 131



Isolation of butadiene………………………………………….. 133 4.2.Isoprene…………………………………………………………………………135 4.2.1Тwo-step manufacture of isoprene from isobutylene and formaldehyde136

Reaction mechanism…………………………………………… 137

Transformation of 1,3-glycols into dioxanes…………………... 139

Formation of isopentene alcohols……………………………… 139

Transformation of 4,4-dimethyl-1,3-dioxane into isoprene …… 140


4.2.2. Manufacture of isoprene from isobutylene and formaldehyde via 3-methyl-

1,3-butanediol (MBD)……………………………………... ………..143

4.2.3. Manufacture of isoprene from isobutylene and methylal………….. 145

4.2.4. Manufacture of isoprene by dehydrogenation of hydrocarbons С… 146

Two-step dehydrogenation of isopentane to isoprene………… 146

One-step dehydrogenation of isopentane to isoprene ………… 149

Two-step oxidative dehydrogenation of isopentane to isoprene.. 150

4.2.5. Manufacture of isoprene from propylene………………………….. 153

Dimerization of propylene……………………………………… 153

Isomerization of 2-methyl-1-pentene to 2-methyl-2-pentene …. 155

Cracking of 2-methyl-2-pentene ………………………………. 156

Synthesis of isoprene from ethylene and propylene…………… 159

4.2.6. Manufacture of isoprene from acetylene and acetone……………… 159

4.2.7. Manufacture of isoprene by liquid-phase oxidation of hydrocarbons 162

4.2.8. Manufacture of isoprene from 2-butenes and synthesis gas……….. 163 4.3. Diene monomers for the manufacture of ethylene-propylene-diene rubbers 165


4.3.1. Manufacture of nonconjugated dienes…………………………….. 166


Synthesis of dicyclopentadiene………………………………… 166

Synthesis of 1,4-hexadiene…………………………………….. 167

Synthesis of 1,5-cyclooctadiene……………………………….. 167

4.3.2. Manufacture of norbornene derivatives……………………………. 168



Synthesis of ethylidenenorbornene…………………………….. 168

Synthesis of methylenenorbornene…………………………….. 169

Synthesis of propenylnorbornene………………………………. 169

Synthesis of 5’-(buten-2-yl-4)-2’-norbornene…………………. 170

Synthesis of cyclopentadienyl-5-endo-norbornen-2-yl-5’-methan 170

 

Chapter 5. Halogen-containing monomers…………………………………… 171

5.1. Chlorine-containing monomers…………………………………………….. 171

5.1.3 . Theoretical backgrounds of hydrocarbon chlorination……………. 171



5.1.4 . Oxidative chlorination…………………………………………….. 173

5.1.5 Hydrochlorination………………………………………………….. 176

5.1.4. Dehydrochlorination ……………………………………………… 176

5.1.5. Manufacture of chloroorganic compounds………………………… 177

Gas-phase chlorination of hydrocarbons and chlorine derivatives 177

Liquid-phase chlorination of hydrocarbons……………………. 178

Gas-phase decomposition of chlorine derivatives …………….. 179

5.1.6. Manufacture of vinyl chloride……………………………………… 180

Balanced method of vinyl chloride synthesis from ethylene ….. 181

One-step of vinyl chloride synthesis from ethylene (Staffer proc.)185

Two-step synthesis of vinyl chloride from ethylene…………… 186

Synthesis of vinyl chloride from ethane……………………….. 187

Hydrochlorination of acetylene………………………………… 189

5.1.7. Manufacture of vinylidene chloride………………………………… 191

5.1.8. Manufacture of chloroprene………………………………………… 193

Preparative methods of obtaining chloroprene……………………193 Industrial methods for the synthesis of chloroprene……………………………. 194

5.1.9. Manufacture of epichlorohydrin…………………………………… 197 5.2. Fluorine-containing monomers……………………………………………… 199

5.2.1. Theoretical backgrounds of fluorination processes………………… 199

5.2.2. Mechanism of fluorination reactions……………………………….. 200

5.2.3. Methods of fluorination of alkanes ………………………………… 201

Metal fluoride process …………………………………………. 202

Cryogenic fluorination…………………………………………. 202

Electrochemical fluorination…………………………………… 203

5.2.4. Fluorinating agents…………………………………………………. 204

Molecular fluorine……………………………………………… 204

Hypofluorites…………………………………………………… 204

Hydrogen fluoride……………………………………………… 205

5.2.5. Manufacture of vinyl fluoride……………………………………… 206

5.2.6. Manufacture of vinylidene fluoride ……………………………….. 207

5.2.7. Manufacture of perfluoro-derivatives of hydrocarbons……………. 207

Synthesis of tetrafluoroethylene……………………………….. 207

Synthesis of hexafluorobutadiene……………………………… 208

Synthesis of perfluoroallenes………………………………….. 209

5.2.8. Manufacture of other fluoro-derivatives of hydrocarbons………… 209

Synthesis of trifluorochloroethylene…………………………… 209

Synthesis of sym-dichlorodifluoroethylene……………………. 209

Synthesis of 3,3,3-trifluoropropylene………………………….. 209

5.2.9. Manufacture ofchladones (freons)………………………………… 210



Chapter 6. Vinylic monomers with aromatic and heterocyclic substituents.. 212

6.1. Styrene and its derivatives…………………………………………………… 212

6.1.1. Manufacture of styrene ……………………………………………. 212

Preparative methods of obtaining styrene……………………… 213

Industrial methods for the manufacture of styrene ……………. 214

6.1.2. Manufacture of a-methylstyrene…………………………………… 218 6.2. Vinylpyridines………………………………………………………………. 219

6.2.1.General aspects of basic methods for the synthesis of vinylpyridines 221

6.2.2. Industrial methods for the manufacture of vinylpyridines ………… 221

Synthesis of2-methyl-5-vinylpyridine………………………… 220

Synthesis of 2- and 4-vinylpyridines and 2-vinyl-5-ethylpyridine 222

6.3. N-Vinylpyrrolidinone ………………………………………………... 223

6.3.1. Direct vinylation ofa-pyrrolidinone by acetylene…………………. 224

6.3.2. Indirect vinylation of a-pyrrolidinone ……………………………... 226 6.4. N-vinylcarbazole ……………………………………………………………. 228

6.4.1. Manufacture of N-vinylcarbazole through vinylation by acetylene… 229

6.4.2. Manufacture of N-vinylcarbazole by the vinyl exchange reaction… 230

6.4.3. Manufacture of N-vinylcarbazoles by multi-step processes………. 231

Decomposition of N-(2-hydroxyethyl)carbazole ……………… 231

Decomposition of 1-substituted N-ethylcarbazoles……………. 233 6.5. Other vinylic monomers…………………………………………………….. 234

6.5.1. Manufacture of ethylidenenorbornene……………………………… 234

6.5.2. Manufacture of vinyl toluene………………………………………. 235

6.5.3. Manufacture of vinyl ketones……………………………………… 236

Synthesis of vinyl methyl ketone……………………………… 236

Synthesis of isopropenyl methyl ketone………………………. 238

Synthesis of vinyl phenyl ketone……………………………… 239

Synthesis of vinylene carbonate………………………………. 239

Chapter 7. Acrylic monomers…………………………………………………. 241

7.1. Acrylonitrile………………………………………………………………… 242

7.1.1Synthesis of acrylonitrile via ethylene oxide and ethylene cyanohydrin243

7.1.2. Oxidative ammonolysis of propylene……………………………… 246

7.1.3. Synthesis of acrylonitrile from acetylene and prussic acid ……….. 249

7.1.4. Synthesis of acrylonitrile via acetaldehyde and hydroxynitryl……. 251



7.1.5. Synthesis of acrylonitrile from propylene and nitrogen oxides…… 252

7.1.6. Synthesis of acrylonitrile by direct interaction of ethylene, prussic acid, and

oxygen………………………………………………………… 252

7.1.7. Oxidative ammonolysis of propane……………………………….. 252 7.2. Acrylamide…………………………………………………………………. 252

7.2.1. Preparative methods of obtaining acrylamide……………………... 253

7.2.2. Industrial methods for the manufacture of acrylamide …………… 254 7.3. Acrylic acid ………………………………………………………………... 255

7.3.1. Hydrolysis of acrylonitrile………………………………………… 255

7.3.2. Hydrocarboxylation of acetylene…………………………………. 257

7.3.3. Vapor-phase oxidation of propylene……………………………… 257

7.3.4. Hydrolysis of ethylene cyanohydrin……………………………… 260

7.3.5. Hydrolysis of b-propiolactone …………………………………… 260

7.3.6. Oxidative carbonylation of ethylene……………………………… 261 7.4. Methacrylic acid ………………………………………………………….. 261

7.4.1. Gas-phase oxidation of isobutylene………………………………. 262

7.4.2. Oxidation of methacrolein ……………………………………….. 262

7.4.3. Gas-phase oxidation of methacrolein…………………………….. 263 7.5. Acrylates…………………………………………………………………... 263

7.5.1. Manufacture of acrylates by esterification of acrylic

and methacrylic acids ………………………………………………….. 263

Esterification by alcohols in the presence of sulfuric acid…… 263

Esterification by alcohols in the presence of ion-exchange resins 264

Esterification by olefins……………………………………… 265

7.5.2. Manufacture of acrylates via transesterification…………………. 265

Transesterification in the presence of acidic catalysts……….. 265

Transesterification in the presence of ion-exchange resins….. 266

Transesterification in the presence other transesterification

catalysts……………………………………………………….. 266

7.5.3. Manufacture of acrylates from ethylene cyanohydrin…………….. 266

7.5.4. Manufacture of acrylates from acetylene by the Reppe reaction….. 267

BASF process…………………………………………………. 267

Rom and Haas process………………………………………… 267

7.5.5. Manufacture of acrylates from ketene and formal………………… 268

7.5.6. Manufacture of acrylates from acrylonitrile………………………. 268 7.6. Methacrylates………………………………………………………………. 269

7.6.1. Manufacture of methacrylate from acetone and cyanohydrin…….. 269

Synthesis of cyanohydrin (prussic acid)………………………. 269

Condensation of acetone and prussic acid ……………………. 270

Synthesis of methacrylamide sulfate………………………….. 270



Hydrolysis or esterification of methacrylamide sulfate ………. 271

Commercial realization of the process………………………… 272

7.6.2. Manufacture of methyl methacrylate from tert-butyl alcohol……… 273

Oxidation of tert-butyl alcohol to methacrolein ………………. 273

Oxidation of methacrolein to methacroleinic acid…………….. 273

Esterification of methacrylic acid to methyl methacrylate…….. 274

7.6.4. Manufacture of methyl methacrylate from isobutylene…………… 274

7.6.5. New methods for the synthesis of methyl methacrylate…………… 277

Synthesis of methyl methacrylate via isobutyraldehyde………. 277

Carbomethoxylation of propylene……………………………... 278

Carbomethoxylation of methylacetylene……………………… 279

Methoxycarbonylation of allene and methylacetylene-allene

Fraction………………………………………………………… 280

7.6.5. Manufacture of other alkyl methacrylates…………………………. 281

Synthesis of methacrylamide………………………………….. 281

Synthesis of hydroxyethyl methacrylate………………………. 281 7.7. Oligoetheracrylates…………………………………………………………. 282

Chapter 8. Alcohols and vinyl ethers…………………………………………. 283

8.1. Polyvinyl and polyallyl alcohols…………………………………………… 284 8.2. Backgrounds of vinylation processes ……………………………………… 286 8.3. Vinyl ethers………………………………………………………………… 289

8.3.1. Manufacture of vinyl ethers by vinylation of alcohols……………. 290

Vinylation of alcohols under atmospheric pressure…………… 290

Vinylation of alcohols under elevated pressure ………………. 292

Other methods for the synthesis of vinyl ethers…………….… 293 8.4. Vinyl esters. Vinyl acetate…………………………………………………. 294

Synthesis ofvinyl acetate from acetylene and acetic acid…….. 296

Synthesis ofvinyl acetate from acetaldehyde

and acetic anhydride…………………………………………… 298

Synthesis ofvinyl acetate from ethylene and acetic acid……… 300

Synthesis ofvinyl acetate from alternative sources…………… 304 8.5 Derivatives of polyvinyl alcohol – polyvinylacetals………………………… 311

Chapter 9.Monomers for polyethers…………………………………………. 313

9.1. Formaldehyde………………………………………………………………. 316

9.1.1 Mechanism and catalysts of oxidative dehydrogenation of methanol 316

Mechanism of oxidative dehydrogenation of methanol……….. 316



Catalysts of oxidative dehydrogenation of methanol………….. 321

General aspects of the technology of oxidative

dehydrogenation of methanol………………………………….. 322

9.1.2. Manufacture offormaldehyde……………………………………… 323

Synthesis offormaldehyde with oxide catalysts………………. 323

Oxidation of natural gas and lower alkanes…………………… 324 9.2. Ethylene oxide …………………………………………………………….. 327

9.2.1. Manufacture of ethylene oxide via ethylene chlorohydrin………. 327

9.2.2. Direct oxidation of ethylene……………………………………… 329 9.3. Propylene oxide …………………………………………………………… 331

9.3.1 Manufacture of propylene oxide by direct oxidation with oxygen.. 333

Oxidation of propane………………………………………….. 333

Noncatalytic liquid-phase oxidation of propylene…………….. 333

Catalytic liquid-phase oxidation of propylene………………… 334

Liquid-phase oxidation of propylene by peroxides……………. 334

Epoxidation of propylene……………………………………… 336

9.3.2. Manufacture of propylene oxide by oxidation

of propylene via propylenechlorohydrin……………………………… 337 9.4. Phenylene oxide…………………………………………………………….. 338 9.5. Allyl glycidyl ………………………………………………………………. 339 9.6. Epichlorohydrin ……………………………………………………………. 340

Manufacture of epichlorohydrin from glycerol……………….. 341

Manufacture ofepichlorohydrin from allyl chloride………….. 342 9.7. Sulfones……………………………………………………………………. 343

Part III

 








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