MONOMERS FOR POLYCONDENSATION POLYMERS

Chapter 10. Monomers for polyesters………………………………………… 346 10.1. Terephthalic acid and dimethyl terephthalate…………………………….. 347

10.1.1. Du Pont process………………………………………………….. 349

10.1.2. Witten process…………………………………………………… 350

10.1.3. Amoco process…………………………………………………... 351

Mechanism of p-xylene oxidation…………………………….. 351

Intermediate and side products in oxidation of p-xylene

to terephthalic acid ……………………………………………. 358

Technology of manufacture of terephthalic acid ……………… 360

10.1.4. One-step VNIPIM process……………………………………….. 361

10.1.5. Manufacture of aromatic and heterocyclic carboxylic

acids by thermal transformation of their alkali salts……………………... 361

Transformations of alkali salts…………………………………. 362

Synthesis of terephthalic acid from toluene and xylenes………. 363

10.1.6. Mitsubishi process………………………………………………… 366

10.1.7. Manufacture of terephthalic acid from coal………………………. 367 10.2. Maleic anhydride…………………………………………………………... 368

10.2.1. Manufacture of maleic anhydride by gas-phase oxidation

of benzene………………………………………………………… 368

10.2.3. Manufacture of maleic anhydride by oxidation of butane……….. 370

10.2.3. Manufacture of maleic anhydride by oxidation of n-butenes……. 371

10.2.4. Isolation of maleic anhydride as a side product in

the manufacture of phthalic anhydride…………………………………… 372 10.3. Phthalic anhydride…………………………………………………………. 372

10.3.1. Vapor-phase oxidation of o-xylene or naphthalene………………. 374

10.3.3. Liqid-phase oxidation of o-xylene or naphthalene……………….. 375

10.3.3. VNIIOS process………………………………………………….. 375 10.4. Fumaric acid………………………………………………………………. 378 10.5. Dichloromaleic and dichlorofumaric acids and their derivatives…………. 379

10.5.1. Manufacture of dichloromaleic acid and its anhydride…………… 379

10.5.2. Manufacture of dichlorofumaric acid and its anhydride………….. 380 10.6. 2,6-Naphthalenedicarboxylic acid…………………………………………. 380 10.7. Thiophene-2,5-dicarboxylic acid………………………………………….. 381 10.8. Azelaic acid……………………………………………………………….. 382 10.9. Diols………………………………………………………………………. 383

10.9.1. Manufacture ethylene glycol…………………………………….. 383

Hydration of ethylene oxide…………………………………… 383

Other methods for the synthesis of ethylene glycol …………… 384

10.9.2. Manufacture of 1,2-propanediol………………………………….. 386

Hydration of propylene oxide…………………………………. 386

Other methods for the synthesis of 1,2-propanediol ………….. 388

10.9.3 Manufacture of 1,4-butanediol……………………………………. 389

Synthesis of 1,4-butanediol from acetylene and formaldehyde.. 390

Synthesis of 1,4-butanediol from propylene………………….. 391

Synthesis of 1,4-butanediol from renewable raw material

(Cvaker Oatz process)……………………………………….. 393

Propylene of 1,4-butanediol by acetoxylation

of butadiene (Mitsubishi process)……………………………. 393

Synthesis of 1,4-butanediol through chlorination

of butadiene(Тоуо Soda process)…………………………….. 394

Synthesis of 1,4-butanediol through hydroformylation

of allyl alcohol (Кurare process)……………………………… 395

10.9.4. Manufacture of 1,4-dimethylcyclohexane……………………….. 398

Chapter 11. Monomers for polyamides……………………………………… 399

11.1. Monomers for polymerization polyamides …………………………….… 400

11.1.1. Manufacture of caprolactam……………………………………... 401

Methods for the synthesis of caprolactam…………………….. 401

Main stages in thesynthesis of caprolactam …………………. 405

Synthesis of caprolactam from toluene……………………….. 422

Photochemical synthesis of caprolactam……………………… 426

11.1.2. Manufacture of valerolactam…………………………………….. 427

11.1.3. Manufacture of 7-aminoheptanoic acid………………………….. 427

11.1.4. Manufacture of caprilolactam……………………………………. 429

11.1.5. Manufacture of 9-aminopelargonic acid ………………………… 429

11.1.6. Manufacture of 11-aminoundecanoic acid……………………….. 429

11.1.7. Manufacture of laurolactam………………………………………. 432

Trimerization of butadiene…………………………………….. 432

Heamisher Huls process……………………………………….. 433

Uber process…………………………………………………… 433

11.1.8. Manufacture of a-pyrrolidinone………………………………….. 434

Amination of g-butyrolactone………………………………….. 435

Noncatalytic synthesis of a-pyrrolidinone…………………….. 435

Reductive amination of maleic anhydride……………………... 436

Other methods for the synthesis of a-pyrrolidinone…………… 437 11.2. Monomers for polycondensation polyamides derived from dicarboxylic

acids and diamines…………………………………………………………. 439

11.2.1 Manufacture of adipic acid………………………………………… 440

Synthesis of adipic acid from cyclohexane…………………….. 441

Synthesis of adipic acid from tetrahydrofurane……………… 442

Synthesis of adipic acid from phenol………………………….. 442

Other industrial methods for the synthesis of adipic acid……… 442

11.2.2. Manufacture of adiponitrile………………………………………… 443

Synthesis of adiponitrile from adipic acid……………………… 443

Synthesis of adiponitrile from butadiene………………………. 444

Synthesis of adiponitrile from acrylonitrile

by electrochemical method…………………………………….. 445

Catalytic dimerization of acrylonitrile…………………………. 446

11.2.3. Manufacture of hexamethylenediamine……………………………. 447

Synthesis of hеxamethylenediamine from adipic acid…………. 447

Synthesis of hеxamethylenediamine via 1,6-hexanediol………. 449

Synthesis of hеxamethylenediamine from butadiene………….. 449

Dimerizationof acrylonitrile…………………………………... 450

11.2.4 Manufacture of other monomers for the synthesis of polyamides .. 450

11.2.5. Manufacture of m-xylylenediamine……………………………… 457

Bromination of xylene…………………………………………. 457

Oxidative ammonolysis………………………………………… 458 11.3. Monomers for other fiber-forming polyamides …………………………… 458

11.3.1. Manufacture of fiber-forming polyamides based on suberic

acid and 1,4-diaminomethylcyclohexane………………………….. 458

Synthesis of suberic acid ………………………………………. 459

Synthesis of 1,4-diaminomethylcyclohexane………………….. 459

11.3.2. Manufacture of fiber-forming polyamides based on

decanedicarboxylic acid and 4,4¢-diaminodicyclohexylmethane…. 459

Synthesis of decanedicarboxylic acid………………………….. 460

Synthesis of 4,4¢-diaminodicyclohexylmethane……………….. 460 11.4. Monomers for fully aromatic polyamides…………………………………. 461

11.4.1. Manufacture of aromatic acid chlorides………………………….. 461

Synthesis of acid chlorides from xylenes……………………… 461

Thionyl method………………………………………………... 462

11.4.2. Manufacture of monomers for fiber-forming polyamides by polycondensa-

tion of 4,4¢-diaminodiphenyl sulfone………………. …………….. 463

11.4.3. Manufacture of 2,5-bis-(p-aminophenyl)-1,3,4-oxadiazole………. 464

11.4.4.Manufacture of 5,5¢-bis(m-aminophenyl)-2,2¢-bis(1,3,4-oxadiazolyl)465

11.4.5. Manufacture of 4,4¢-bis-(p-aminophenyl)-2,2-dithiazole………… 465

11.4.6. Manufacture of bis-(m-aminophenyl)-thiazolo(5,4-d)thiazole…… 466

11.4.7. Manufacture of monomers for polyamides based on

piperazine and diacids……………………………………………. 466

Synthesis of piperazine…………………………………………… 466

Synthesis of 4,4¢-diphenyldicarboxylic acid………………………. 467

Chapter 12. Monomers for polyimides……………………………………….. 470

12.1. Pyromellitic dianhydride………………………………………………….. 472

12.1.1. Manufacture of durene…………………………………………… 473

12.1.2. Manufacture ofpyromellitic dianhydride………………………... 475 12.2. Diphenyltetracarboxylic dianhydrides…………………………………….. 481

12.2.1. Manufacture of 2,2¢,3,3¢-diphenyltetracarboxylic dianhydride…… 481

12.2.2. Manufacture of 2,3,5,6-diphenyltetracarboxylic dianhydride…….. 482

12.2.3. Manufacture of 2,2¢,6,6¢-diphenyltetracarboxylic dianhydride …… 483

12.2.4. Manufacture of 3,3¢,4,4¢-diphenyltetracarboxylic dianhydride ….. 484 12.3. Naphthalenetetracarboxylic dianhydrides…………………………………. 485

12.3.1. Manufacture of 1,4,5,8-naphthalenetetracarboxylic dianhydride … 485

12.3.2. Manufacture of 2,3,6,7-naphthalenetetracarboxylic dianhydride … 486 12.4. Benzophenone- and perylenetetracarboxylic dianhydrides………………... 486

12.4.1. Manufacture of 3,3¢,4,4¢-benzophenonetetracarboxylic dianhydride 486

12.4.2. Manufacture of 3,4,9,10-perylenetetracarboxylic dianhydride …… 487 12.5. Aromatic diamines…………………………………………………………. 488

12.5.1. Manufacture of o- and m-phenylenediamines…………………….. 488

12.5.2. Manufacture of p-phenylenediamine……………………………… 489

12.5.3. Manufacture of benzidine…………………………………………. 493

12.5.4. Manufacture of 4,4’-diaminodiphenylmethane…………………… 493

12.5.5. Manufacture of 4,4¢-diaminodiphenyl oxide……………………… 493 12.6. Aniline derivatives…………………………………………………………. 494

12.6.1. Manufacture of anilinophthalein…………………………………... 494

12.6.2. Manufacture of anilinofluorene…………………………………… 495

12.6.3. Manufacture of anilinoanthrone…………………………………… 495

Chapter 13. Monomers for polyurethanes……………………………………. 496

13.1 Diamines……………………………………………………………………. 500 13.1.1 Manufacture of diamines by reduction of dinitriles…………………….. 500

13.1.2 Manufacture of diamines by reduction of aromatic

dinitro compounds………………………………………………… 501

Reduction of dinitro compounds by metals in acidic medium… 502

Reduction of dinitro compounds by metals in alkaline medium.. 503

Reduction of nitro compounds by sulfides …………………….. 504

Catalytic reduction of dinitro compounds……………………… 504 13.2 Diisocyanates and isocyanates……………………………………………… 505

13.2.1 Phosgenftion of amines……………………………………………. 506

13.2.2 Curtius, Hofmann and Lossen rearrangements……………………. 506

13.2.3 Manufacture of tolylene diisocyanates……………………………. 508

Reduction of dinitrotoluenes to tolylenediamine………………. 509

Phosgenation of tolylenediamine ……………………………… 509

Synthesis of phosgene…………………………………………. 509

Other industrial methods for the manufacture of

tolylene diisocyanates………………………………………….. 510

13.2.4 Manufacture of 4,4¢-diphenylmethane diisocyanate ……………… 511

Condensation of aniline with formaldehyde…………………… 512

Synthesis of aniline…………………………………………….. 513

13.2.5. Manufacture of other diisocyanates……………………………….. 516

13.2.6 Synthesis of isocyanates using organosilicon compounds ………… 519

Phosgenation of N-silylamines…………………………………. 519

Thermolysis of N-silylurethanes……………………………..... 522 Thermolysis of О-silylurethanes ………………………………. 522 13.3 Polyols and polyethers……………………………………………………… 524

13.3.1 Manufacture of b-diols…………………………………………….. 525

13.3.2. Manufacture of glycerol…………………………………………... 526

13.3.3. Manufacture of arylaliphatic diols ……………………………….. 528

13.3.4. Manufacture of monomers for poly(ether polyols)……………….. 528

Chapter 14. Monomers for polycarbonates………………………………….. 531

14.1 Bisphenols…………………………………………………………………. 535

14.1.1 Manufacture of bisphenol A………………………………………. 537

Condensation of phenol with acetone…………………………. 537

Condensation of phenol with acetone in the presence

of ion-exchange resins………………………………………… 544

Synthesis of bisphenol A from phenol and methylacetylene

or allene……………………………………………………….. 546

Synthesis of bisphenol A from phenol and

p-isopropenylphenol…………………………………………… 548

Synthesis of bisphenol A from phenol and 2-chloropropene-1… 549

Methods of purification of bisphenol A ………………………. 550

14.1.2 Manufacture of halogen-substituted bisphenols…………………... 550

Synthesis of tetrachlorobisphenol A…………………………... 551

Synthesis of tetrabromobisphenol A………………………….. 552 14.2 Diphenyl carbonate………………………………………………………… 552

14.2.1 Manufacture of diphenyl carbonate by phosgenation of phenols…. 553

14.2.2. Manufacture of diphenyl carbonate by

interaction of phenol with carbon tetrachloride…………………….. 555 14.3 Bisphenol S…………………………………………………………………. 556 14.4 Resorcinol…………………………………………………………………... 558 14.5 Cyclocarbonates…………………………………………………………….. 559

14.5.1. Manufacture of cyclocarbonates from a-oxides…………………... 564

14.5.2. Manufacture of cyclocarbonates from chlorohydrin ethers ………. 565

14.5.3. Manufacture of cyclocarbonates from diols………………………. 566

14.5.4. Manufacture of multifunctional cyclocarbonates…………………. 567 Chapter 15. Monomers for phenol- and amino-aldehyde polymers………… 569

15.1. Monomers for phenol-aldehyde polymers…………………………………. 569

15.1.1. Manufacture of phenols…………………………………………… 569

Isolation of phenols from the products of coal processing…….. 570

Isolation of phenols from the products of oil refining…………. 573

Synthesis of phenols via sulfonation of benzene………………. 573

Alkaline hydrolysis of chlorobenzene (Dow Chemical method).. 574

Rachig modified method (Hooker Chem process)……………… 574

Cumene method………………………………………………… 575

Oxidation of benzene ………………………………………….. 584

15.1.2. Manufacture of bromophenols and their derivatives – antipyrenes.. 588 15.2. Monomers for carbamido-aldehyde polymers……………………………. 590

15.2.1. Manufacture of carbamide……………………………………….. 591

15.2.2. Manufacture of melamine………………………………………... 593

Chapter 16. Organosilicon monomers………………………………………… 596

16.1. Methods of obtaining organosilicon monomers…………………………… 598

16.1.1. Organomagnesium synthesis …………………………………….. 598

16.1.2. Direct synthesis…………………………………………………... 598

16.1.3. Dehydrocondensation of silicon hydrides with hydrocarbons…… 599

16.1.4. Condensation of silicon hydrides with halogen-derivatives……... 599

16.1.5. Hydrosilylation…………………………………………………… 599 16.2. Organochlorosilanes………………………………………………………. 601

16.2.1. Manufacture of methyl- and ethylchlorosilanes by direct synthesis 602

Synthesis of silicon-copper contact mass……………………… 603

Synthesis of methylchlorosilanes………………………………. 605

Synthesis of ethylchlorosilane ……………………………….. 607

Synthesis of ethyldichlorosilane ………………………………. 608

Synthesis of diethyldichlorosilane……………………………... 609

Synthesis of phenylchlorosilanes………………………………. 610

16.2.2. Manufacture of organochlorosilanes by thermocatalytic silylation 610

Synthesis of methylphenyldichlorosilane……………………… 611

Hydrosilylation of unsaturated compounds……………………. 611

High-temperature condensation method……………………….. 612

16.2.3.Manufacture of organochlorosilanes by disproportionation reactions 612

16.2.4. Pyrolytic methods for the synthesis of organochlorosilanes ……… 613

16.2.5. Manufacture of organosilicon monomers by chemical

transformations of organochlorosilanes…………………………………… 614

16.2.6. Manufacture of tetrachlorosilane………………………………….. 615

16.2.7. Purification of diorganodichlorosilanes ………………………….. 616 16.3.Monomers for siloxanerubbers……………………………………………. 617

16.3.1. Manufacture of siloxane rubbers ……………………………….… 617

16.3.2. Manufacture of siloxane monomers by hydrolysis of

diorganodichlorosilanes……………………………………….………….. 619

General aspects of hydrolysis of diorganodichlorosilanes ……. 620

Industrial methods for the hydrolysis of

diorganodichlorosilanes……………………………………….. 621

16.3.3. Other methods of obtaining siloxane monomers …………………. 623

Thermal rearrangement of linear polysiloxanes………………... 623

Catalytic rearrangement of linear polysiloxanes……………….. 624 16.4. Monomers for modified siloxane rubbers…………………………………. 626

16.4.1. Manufacture of hexaorganocyclotrisiloxanes…………………….. 628

16.4.2. Manufacture of organosilicon urethanes………………………….. 629

Synthesis of O-silylurethanes………………………………….. 629

Synthesis of N-silylurethanes………………………………….. 630

Synthesis of urethanes from glycoxysilanes……….…………... 631

Synthesis of carbofunctional organosilicon diols……………… 632

Synthesis of products of condensation of organosilicon

isocyanates with hydroxyl-containing compounds……………. 634

Synthesis of monomers for organosilicon polyurethanes

prepared by hydrosilylation reaction…………………………… 635

Synthesis of monomers for organosilicon polyurethanes

prepared from organosilicon bis(chloroformates)……………… 636 16.5. Monomers for polysilicohydrocarbons – permselective polymers………… 637

Chapter 17. Other organoelement monomers………………………………… 642

17.1.Monomers for sulfur-containing polymers ……………………………….. 642

17.1.1.Manufacture of sodium sulfide and polysulfides…………………. 642

17.1.2.Manufacture of 1,2-dichloroethane ……………………………… 643

17.1.3.Manufacture of p-dichlorobenzene………………………………. 643 17.2. Phosphazenes (phosphonitriles)…………………………………………… 646 17.3.Boron-containing monomers……………………………………………… 649 17.4.Nitrogen-containing monomers …………………………………………… 653

17.4.1.Manufacture of monomers with azole cycles ……………………. 654

Synthesis of 2,5-bis(p-aminopheny)-1,3,4-oxadiazole………… 655

Synthesis of 4,4¢-bis(p-aminophenyl)-2,2¢-dithiazole…………. 656

Synthesis of 5,5¢-di(m-aminophenyl)-2,2¢-bis(1,3,4-oxadiazolyl) 656

Synthesis of 5,5-di(p-aminophenyl)-2,2¢-bis(1,3,4-oxadiazolyl).. 657

17.4.2. Manufacture of di- and tetracarboxylic acids…………………….. 657

17.4.3. Manufacture of benzimidazoles………………………………….. 659

17.4.4. Manufacture ofbenzoxazoles…………………………………….. 659

17.4.5. Manufacture of bis(maleimides)………………………………….. 660 17.5. Metal-containing monomers and the related polymers …………………… 661

17.5.1. Manufacture of monomers containing covalently bound metals…. 663

Synthesis of unsaturated nontransition-metal

organometallic monomers……………… …………………… 664

Synthesis of unsaturated nontransition-metal

organometallic monomers……………………………………… 664 17.5.2. Manufacture of ionic metal-containing monomers……………… 665 17.5.3. Manufacture of мetal-containing monomers containing

coordinatively bound metals…………………………………………….. 666 17.5.4 Manufacture of π-tipe metal-containing monomers ……………… 666 Subject index…………………………………………………………………… 670

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