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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

13.2.6Synthesis of isocyanates using organosilicon compounds ………… 519 Phosgenation of N-silylamines…………………………………. 519 Thermolysis of N-silylurethanes……………………………..... 522 Thermolysis of О-silylurethanes ………………………………. 522

13.3Polyols and polyethers……………………………………………………… 524

13.3.1Manufacture of -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

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

14.1.1Manufacture 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

14.1.2Manufacture of halogen-substituted bisphenols…………………... 550 Synthesis of tetrachlorobisphenol A…………………………... 551 Synthesis of tetrabromobisphenol A………………………….. 552

14.2Diphenyl carbonate………………………………………………………… 552

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

14.2.2.Manufacture of diphenyl carbonate by

interaction of phenol with

carbon tetrachloride…………………….. 555

14.3Bisphenol S…………………………………………………………………. 556

14.4Resorcinol…………………………………………………………………... 558

14.5Cyclocarbonates…………………………………………………………….. 559

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

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

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

712

14.5.4.Manufacture of multifunctional cyclocarbonates…………………. 567

Chapter 15. Monomers for phenoland 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)……………… 574Cumene 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 methyland 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

713

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

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

16.2.7.Purification of diorganodichlorosilanes ………………………….. 616

16.3.Monomers for siloxane rubbers……………………………………………. 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

714

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 diand tetracarboxylic acids…………………….. 657

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

17.4.4.Manufacture of benzoxazoles…………………………………….. 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

Учебное издание

715

Платэ Николай Альфредович Сливинский Евгений Викторович

ОСНОВЫ ХИМИИ И ТЕХНОЛОГИИ МОНОМЕРОВ

Утверждено к печати Ученым советом

Института нефтехимического синтеза им. А.В. Топчиева

Российской академии наук

Редактор М.Л. Франк Художник А.С. Скороход Технический редактор В.В. Лебедева

Корректоры А.Б. Васильев, Р.В. Молоканова, Т.И. Шеповалова

Подписано к печати 05.11.2002 Тираж 1000 экз. Издательство “Наука”

МАИК “Наука/Интерпериодика”

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