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MONOMERS FOR POLYMERIZATION POLYMERSChapter 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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