Hans R. Kricheldorf, Oskar Nuyken, Graham Swift9780824754730, 0-8247-5473-5
Table of contents :
HANDBOOK OF POLYMER SYNTHESIS……Page 1
PLASTICS ENGINEERING……Page 2
Preface……Page 7
Contents……Page 8
List of Contributors……Page 10
Contents……Page 0
I. INTRODUCTION……Page 12
A. Radical Polymerization……Page 14
B. Coordination Catalysts……Page 17
1. Titanium Chloride-Based Catalysts……Page 20
3. Supported Catalysts……Page 21
4. Phillips Catalyst……Page 22
5. Homogeneous (Single Site) Catalysts……Page 23
6. Aluminoxane as Cocatalysts……Page 26
7. Late Transition Metal Catalyst……Page 29
C. Copolymers of Ethene……Page 31
1. Radical Copolymerization……Page 32
2. Linear Low-Density Polyethene (LLDPE)……Page 33
3. Ethene-Propene Copolymers……Page 35
4. Ethene-Cycloolefin Copolymers……Page 36
5. Ethene-Copolymerization by Styrene or Polar Monomers……Page 38
A. Homopolymerization……Page 39
B. Isotactic Polypropene……Page 41
2. Active Sites……Page 43
3. Mechanism……Page 45
5. Role of Lewis Base Esters……Page 46
6. Homogeneous Catalysts……Page 49
C. Syndiotactic Polypropylene……Page 55
1. Elastomeric Polypropene……Page 56
D. Atactic Polypropene……Page 57
1. Supported Metallocene Catalysts……Page 58
E. Copolymers……Page 59
1. Polymer Characterization and Compounding……Page 60
B. Polymers of Other a-olefins……Page 61
C. Polycycloolefins……Page 62
D. Polyisobutene……Page 64
2. Block Copolymers and Graft Polymers……Page 66
3. Polymers of 1,1- and 1,2-Disubstituted Olefins……Page 67
REFERENCES……Page 68
A. Synthesis [5,7]……Page 84
B. Homopolymerization……Page 85
1. Radical Polymerization……Page 86
2. Controlled Radical Polymerization……Page 88
3. Anionic Polymerization……Page 91
4. Cationic Polymerization……Page 95
5. Coordination Polymerization……Page 96
2. Poly(styrene-co-maleic anhydride) (PSMA)……Page 97
6. Copolymerization with Divinylbenzene……Page 98
D. Block Copolymers……Page 99
1. Polystyrene Backbone……Page 101
2. Polystyrene Sidearm……Page 103
3. Branched and Hyperbranched Polystyrene……Page 104
1. Cationic Polymerization……Page 105
3. Anionic Polymerization……Page 107
B. cis- and trans-b-Methylstyrene……Page 108
1. Radical Polymerization……Page 109
2. Cationic Polymerization……Page 110
3. Coordinative Polymerization……Page 111
D. ar-Methoxystyrene……Page 112
2. Cationic Polymerization……Page 113
4. Anionic Polymerization……Page 114
1. Radical Polymerization……Page 115
3. Coordination Polymerization……Page 116
2. Cationic Polymerization……Page 117
3. Anionic Polymerization……Page 118
1. Cationic Polymerization……Page 119
III. VINYL ARENES……Page 120
A. Cationic Polymerization……Page 122
B. Anionic Polymerization……Page 123
D. Free-Radical Polymerization……Page 124
IV. N-VINYLCARBAZOLE……Page 125
A. Monomer Synthesis……Page 126
B. Radical Polymerization……Page 127
2. Organic Cation Salts……Page 128
D. Charge Transfer Polymerization……Page 129
E. Solid- State Polymerization……Page 131
A. Monomer Synthesis……Page 132
2. Aqueous Solution Polymerization……Page 133
3. Solution Polymerization in Organic Solvents……Page 135
D. Radiation and Solid- State Polymerization……Page 136
1. Properties of Poly(N-Vinylpyrrolidone)……Page 137
A. Monomers……Page 138
1. Radical Polymerization……Page 139
2. Anionic Polymerization……Page 140
3. Block and Graft Copolymers……Page 141
REFERENCES……Page 143
1. Definition and Historical Background……Page 161
2. Synthesis of Vinyl Ether Monomers……Page 162
1. Bronsted and Lewis Acids……Page 164
2. Hydrogen Iodide-Iodine (Living/Controlled Cationic Polymerization)……Page 170
3. Polymerization of Vinyl Ethers with Iodine……Page 171
4. Initiation by Stable Carbenium and Carbenium Ion-Radical Salts……Page 172
7. Metal Sulfates……Page 174
9. Photochemical Initiation……Page 175
10. Radiation Techniques……Page 176
11. Electrochemical Initiation……Page 177
D. Free-Radical Polymerizations……Page 178
1. Cationic Copolymerization……Page 180
2. Free-Radical Copolymerization……Page 181
2. Synthesis of Vinyl Ester Monomers……Page 182
1. General Reactivity Considerations……Page 184
2. Structure of Poly(vinyl acetate)……Page 185
1. Emulsion Polymerization……Page 186
4. Solution Polymerization……Page 187
D. Controlled Radical Polymerization Methods……Page 188
E. Modification of Poly(vinyl acetate)……Page 189
A. Introduction……Page 190
B. Radical Polymerization: General Aspects……Page 192
1. Polymerization in Bulk……Page 194
3. Polymerization in Emulsion……Page 197
5. Other Methods of Polymerization……Page 199
A. Introduction……Page 201
2. Solution Polymerization……Page 203
3. Suspension Polymerization……Page 204
5. Polymerizations Initiated by Organometallic Compounds……Page 205
C. Radiation-Induced Polymerization……Page 207
1. Effects of Polymerization Variables……Page 208
2. Properties of PVF……Page 209
4. Application……Page 210
A. Introduction……Page 211
1. Polymerization in Emulsion and Suspension……Page 212
3. Polymerization Initiated with Organometallic Compounds……Page 213
C. Radiation-Initiated Polymerization……Page 214
1. Copolymers……Page 215
2. Properties……Page 216
3. Applications……Page 217
E. Polymerization of Other Fluoroalkenes……Page 218
A. Introduction……Page 219
1. Polymerization in Emulsion and Suspension [686]……Page 221
3. Polymerization Initiated with Organometalic Compounds……Page 222
1. Photo-Initiated Polymerization……Page 223
2. Radiation-Initiated Polymerization……Page 224
3. Glow-Discharge and Plasma Polymerization……Page 226
D. Technical Production and Properties of PTFE……Page 227
REFERENCES……Page 229
1. Formula and History……Page 250
3. Reactions……Page 251
1. Bulk Polymerization……Page 252
2. Solution Polymerization……Page 253
4. Emulsion Polymerization……Page 254
5. Irradiation Polymerization……Page 255
6. Plasma Polymerization……Page 257
1. Free Radical Polymerization……Page 258
2. Anionic Polymerization……Page 263
3. Polymerization by Complex Initiators……Page 268
4. Metal-free Polymerizations……Page 270
5. Group Transfer Polymerization……Page 271
7. Living Radical Polymerization……Page 274
8. Stable Free Radical Polymerization (SFRP)……Page 275
9. Atom Transfer Radical Polymerization (ATRP)……Page 277
A. Introduction……Page 281
C. General Aspects of Polymerization……Page 282
D. Radical Polymerization……Page 283
E. Anionic Polymerization……Page 284
F. Polymerization Processes……Page 285
G. Chemical Properties……Page 286
A. Introduction……Page 287
1. Manufacturing of Acrylic Acid [450]……Page 289
2. Manufacturing of Methacrylic Acid……Page 290
2. Radical Polymerization……Page 291
3. Radiation-induced Polymerization [525–527]……Page 293
F. Applications [548,549]……Page 294
A. Acryloyl Chloride and Methacryloyl Chloride……Page 295
B. Acrylic Anhydride and Methacrylic Anhydride……Page 297
A. Introduction……Page 299
B. Bulk Polymerization……Page 300
1. Radical-Induced Polymerization……Page 301
2. Anionic Polymerization……Page 303
4. Stereoregularity of Polyacrylonitrile……Page 304
3. Emulsion Polymerization of Acrylonitrile……Page 305
A. Introduction……Page 306
B. Reactivity and Homopolymerization of Maleic Anhydride……Page 307
C. Copolymerization with Vinyl Monomers……Page 308
D. Polymerizations of Monomers Derived from Maleic Acid……Page 310
REFERENCES……Page 311
I. INTRODUCTION……Page 342
A. Anionic Polymerization……Page 343
B. Coordination Catalysts……Page 344
C. cis-1,4-Polybutadiene……Page 346
1. Metallocene-catalysts……Page 348
D. trans-1,4-Polybutadiene……Page 349
III. POLYISOPRENE……Page 351
1. Anionic Polymerization……Page 352
2. Coordinative Catalysts……Page 354
D. Metallocene-catalysts……Page 355
IV. CHLOROPRENE……Page 356
A. Poly(2,3-dimethyl-1,3-butadiene)……Page 357
B. Poly(alkyl-1,3-butadienes)……Page 358
A. Poly-1,3-Pentadiene……Page 360
B. 1,4-Poly(1,3-Pentadiene)……Page 362
A. Poly(2,4-Hexadiene)……Page 364
B. Polyterpenes……Page 366
C. Polycyclodienes……Page 368
D. Nonconjugated Polydienes……Page 369
A. 1,3-Butadiene- Styrene-Copolymers……Page 371
C. Copolymers with Dienes and Olefins……Page 374
E. Copolymers of Other Dienes……Page 375
REFERENCES……Page 376
I. INTRODUCTION……Page 390
II. GENERAL MECHANISTIC ASPECTS……Page 391
A. General Aspects……Page 393
B. Titanium- Based Initiators……Page 394
D. Molybdenum-Based Initiators……Page 395
E. Tungsten-Based Initiators……Page 397
F. Ruthenium-Based Initiators……Page 399
IV. THERMODYNAMIC ASPECTS……Page 402
V. FORMATION OF CYCLIC BY-PRODUCTS……Page 404
VI. POLYMER MICROSTRUCTURE AND MECHANISTICAL CONSIDERATIONS……Page 405
B. Vestenamer……Page 410
E. Others……Page 411
2. Cyclopentene and Derivatives……Page 412
4. Cyclooctadiene and Derivatives……Page 413
2. Norbornene Derivatives……Page 414
REFERENCES……Page 422
I. INTRODUCTION……Page 436
A. Syntheses via Electrophilic Substitution……Page 437
B. Syntheses Via Nucleophilic Substitution……Page 438
C. Chemical Modification……Page 442
D. Various Synthetic Methods……Page 446
E. Ring-Opening Polymerization (ROP)……Page 450
A. Syntheses Via Electrophilic Substitution……Page 453
1. Mechanistic Studies……Page 456
C. Various Structures……Page 457
1. Liquid-crystalline PEKs?……Page 463
2. Telechelic oligomers (tOEKs), block-copolymers and networks……Page 464
1. Polycondensation Methods……Page 468
2. Ring-opening Polymerization……Page 470
E. Functionalized poly(ether ketone)s……Page 474
1. Polyphenyleneoxides……Page 478
2. Polyethers with heterocycles in the main chain……Page 480
G. Various Polyethers……Page 485
1. Various Structures and Synthetic Methods……Page 491
2. Liquid-Crystalline (LC) Polyethers……Page 493
I. Aromatic Polysulfides……Page 495
REFERENCES……Page 501
I. INTRODUCTION……Page 511
A. Basic Reactions of Isocyanates……Page 512
B. Other Isocyanate Reactions……Page 515
A. Isocyanates……Page 516
B. Polyols……Page 519
C. Catalysts [1,3–8,13,14]……Page 521
A. Analysis of Isocyanates……Page 522
C. Calculation of Equivalent Ratios……Page 523
D. Infrared Spectra of Polyurethanes……Page 524
V. POLYURETHANE FOAMS [2,6,8,13,20,21]……Page 525
A. The Mechanism of Foam Formation [21,22]……Page 526
B. The Role of Components in the Foam Mixture……Page 527
C. Technology of the Flexible Foam Preparation……Page 528
F. Rigid Foams……Page 529
G. Processing of Polyurethanes [7,23]……Page 530
H. Reaction Injection Molding (RIM) [24,25]……Page 531
VI. ELASTOMERS [4,8,14,26]……Page 532
3. Processing of Thermoplastic Polyurethane Elastomers [23]……Page 536
VII. ELASTOMERIC POLYURETHANE (‘SPANDEX’) FIBERS……Page 537
A. Two-Component Coatings……Page 538
B. One-Component Systems……Page 539
F. Polyurethane Dispersions……Page 540
IX. POLYURETHANE ADHESIVES [6,8,27]……Page 541
A. Thermal Stability of Polyurethanes [29–32]……Page 542
B. Resistance to UV-Light of Polyurethanes [36–38]……Page 544
XII. SAFETY CONSIDERATIONS WHEN WORKING WITH POLYURETHANE RAW MATERIALS [3,8]……Page 545
REFERENCES……Page 546
I. INTRODUCTION……Page 548
A. Polyimides via Poly(amic acid) from Dianhydrides and Diamines. Reaction Conditions and Monomers Reactivity……Page 549
B. One-step Polycondensation. Thermoplastic Polyimides……Page 561
C. Polyimides from Dianhydrides and Diisocyanates……Page 567
1. From Diimides……Page 569
2. From Silylated Diamines……Page 572
III. CONDENSATION COPOLYIMIDES……Page 573
2. From Imide Containing Monomers……Page 574
3. Poly(ester imide) Resins……Page 575
C. Poly(amide imide)s……Page 578
1. From Amide-containing Monomers……Page 579
2. From Imide-containing Monomers……Page 580
4. From Diisocyanates……Page 581
1. From Monomers Containing Ether Linkages……Page 582
E. Segmented Polyimides……Page 583
F. Polyimides Containing Other Heterocycles……Page 585
G. Polymers with Imide Pendant Groups……Page 586
H. Organic–Inorganic Hybrid Polyimides……Page 588
A. Linear Addition Polyimides……Page 589
B. Thermosetting Polyimides……Page 590
C. Diels–Alder Polymerization……Page 593
D. Bisnadimides……Page 595
E. Ethynyl Terminated Oligoimides……Page 597
F. Other End-Capping Groups……Page 600
REFERENCES……Page 601
A. Manufacture of the Monomer……Page 610
B. Radical Polymerization……Page 612
2. Precipitation Polymerization……Page 613
6. Solubilization of the Polymers……Page 614
1. Anionically……Page 615
3. Oxidative Copolymerization……Page 616
5. Block Copolymers……Page 617
1. Radically Polymerized Acrolein (Redox Poly(acrolein))……Page 618
2. Anionically Polymerized Acrolein……Page 619
1. Properties and Structure……Page 620
3. Anionic Polymerization……Page 621
5. Step-growth Polymerization……Page 623
1. Properties and Reactions……Page 624
2. Synthesis……Page 625
4. Anionic Polymerization……Page 626
8. Applications……Page 628
A. Monomer Synthesis……Page 629
B. Radical Polymerization……Page 630
1. Anionic Polymerization……Page 632
2. Cationic Polymerization……Page 634
3. Group Transfer Polymerization……Page 635
1. Radical Copolymerization……Page 636
E. Recent Developments……Page 637
F. Physical Properties……Page 638
IV. POLYMERS OF a,b-UNSATURATED KETONES……Page 639
A. Radical Polymerization……Page 640
B. Anionic Polymerization……Page 641
C. Coordinated and Cationic Polymerization……Page 644
E. Physical Properties of the Polymers……Page 646
A. 1-Alkenylphosphonic Acid……Page 647
B. Derivatives of Ethenylphosphonic Acid……Page 648
C. Diene-type Monomers……Page 649
D. Vinyl Esters and Divinyl Esters……Page 650
F. Acrylic Esters, Acrylic Amide, and Styrene-Containing Phosphorus……Page 652
REFERENCES……Page 653
A. Classification……Page 666
B. Kinetical, Thermodynamical, and Analytical Aspects of Macromolecular Metal Complex Formation……Page 668
A. Metal Complexes in Living Systems……Page 672
B. Metal Complexes at Natural Polymer……Page 673
1. General Considerations……Page 674
B. Binding of Metal Ions or Complexes at Organic Polymers……Page 678
1. Ethers……Page 679
2. Ketones, Carboxylic Acids and Nitriles……Page 680
3. Amines, Amido-Oximes and Hydroxamic Acids……Page 681
4. Schiff Bases……Page 682
5. Pyridyl, Bipyridyl and Other Heterocycles……Page 684
6. Porphyrins and Phthalocyanines……Page 685
C. Binding of Metal Complexes on the Surface of Macromolecular Carriers……Page 687
D. Polymerization of Metal Containing Monomers……Page 690
1. Covalent-type Monomers……Page 691
3. Coordinative- type Monomers……Page 692
5. Complex/Chelate-type Monomers……Page 694
IV. TYPE II: METAL COMPLEXES AS PART OF A LINEAR OR CROSSLINKED MACROMOLECULE VIA THE LIGAND……Page 698
B. Cyclic Organic Ligand Type……Page 699
A Homochain Polymers with Covalent Metal–Metal Bonds……Page 705
B. Heterochain Polymers with Covalent Bonds Between Metals and Another Element……Page 706
C. Heterochain Polymers with Coordinative Bonds Between Metals and Another Element……Page 707
1. Chain Forming Coordination Polymers……Page 708
1. Non-interpenetrating Coordination Polymers……Page 709
2. Interpenetrating Coordination Polymers……Page 716
E. Metallocenes as Part of a Polymer Chain……Page 719
1. Covalent/Covalent Bonds Between the Central Metal Ions……Page 721
4. Self-organization to Cofacial Arrangements……Page 722
G. Metallodendrimers……Page 723
VI. METALS INCORPORATED PHYSICALLY INTO MACROMOLECULES……Page 725
REFERENCES……Page 730
I. INTRODUCTION……Page 743
II. PRINCIPLES OF ELECTRICAL CONDUCTION……Page 745
V. TYPES OF ELECTRICALLY CONDUCTING ORGANIC MATERIALS……Page 746
VII. VARIOUS TYPES AND SYNTHESIS OF POLY(ACETYLENE)……Page 747
VIII. CONSEQUENCES: NEW TYPES AND METHODS……Page 748
1. Cycloaddition……Page 749
2. Modification of Polymerization Conditions……Page 750
X. ORIENTATION PROCESSES……Page 751
XI. WHAT ABOUT STABILITY?……Page 752
XII. THERMAL POLYMERIZATION OF ALKYNES TO (CH)X [45]……Page 753
XV. POLY(DIACETYLENE)S……Page 754
XVI. POLY(PYRROLE)—ANOTHER STEP FORWARD……Page 755
XVII. POLY(PYRROLE)-BATTERIES [54,60]……Page 757
XVIII. NEW MOLECULAR ARRANGEMENTS……Page 758
XIX. POLY(THIOPHENE)……Page 759
XX. SUBSTITUTED POLY(THIOPHENE)S……Page 760
XXIII. POLY(PHENYLENEVINYLENE) PPV……Page 762
XXVI. SYNTHESIS OF PPS……Page 764
XXVII. DOPING OF PPS [90]……Page 766
XXX. POLY(ANILINE): HISTORICAL BACKGROUND AND METHODS OF SYNTHESIS [20]……Page 767
A. Chemical Oxidation……Page 770
XXXV. POLY(PHENYLENE) [12,13]……Page 771
XXXVII. MISCELLANEOUS POLYMERS……Page 772
XXXVIII. PHENALENE-m-COMPLEXES [119]……Page 773
XIL. TWO DIMENSIONAL POLYMERS [24]……Page 777
XLII. APPLICATIONS AND GOALS FOR THE FUTURE [88,121]……Page 778
REFERENCES……Page 779
II. INTRODUCTION……Page 785
III. BASIC PRINCIPLES OF PHOTOCONDUCTIVITY……Page 787
D. Carrier Transport……Page 788
IV. EXPERIMENTAL TECHNIQUES……Page 789
A. Polymers with Pendant or in-Chain Electronically Isolated Photoactive Groups……Page 791
1. Carbazole-Containing Polymers……Page 792
2. Other Photoconductive Polymers with Non-Conjugated Main Chain……Page 800
B. Polymers with p-Conjugated Main Chain……Page 803
C. Polymers with o-Conjugated Main Chain……Page 809
REFERENCES……Page 811
I. INTRODUCTION……Page 817
1. Precursor Routes……Page 819
2. Polycondensation and C–C-Coupling Routes……Page 821
B. Heteroaromatic Systems……Page 824
C. Light Emitting Polymers (LEPs) Based on Polyfluorenes……Page 825
2. Polyfluorene Copolymers……Page 826
1. PPPs by Transition-Metal-Catalyzed Condensation Reactions……Page 827
2. Other Routes to Poly( p-phenylene)s……Page 830
III. CONDUCTING POLYMERS WITH ISOLATED CHROMOPHORES……Page 831
A. Nonconjugated Polymers with Side Chain Chromophores……Page 832
1. Conjugated Main-chain Polymers with Twisted Conformation……Page 837
2. Main Chain Polymers with Non-conjugated Interrupters……Page 838
IV. CONCLUSIONS……Page 841
REFERENCES……Page 842
II. DEFINITION OF POLYMER NETWORKS……Page 846
III. THEORETICAL CONSIDERATIONS……Page 848
IV. CROSSLINKING — CONCEPT……Page 853
V. PHENOL-FORMALDEHYDE RESINS……Page 854
A. Reaction of Phenol and Formaldehyde Under Basic Conditions……Page 855
C. Reaction of Phenol and Formaldehyde Under Acidic Conditions……Page 856
D. Curing of Novolac Prepolymers……Page 857
VI. UREA- AND MELAMIN-FORMALDEHYDE RESINS……Page 858
VII. EPOXY RESINS……Page 860
A. Aliphatic-Cycloaliphatic Epoxy Compounds and Prepolymers [48]……Page 863
B. Curing……Page 864
VIII. CROSSLINKING–POLYURETHANE NETWORKS……Page 865
A. Crosslinking……Page 866
IX. UNSATURATED POLYESTERS UPs……Page 867
C. Crosslinking Via Reactive Structoterminal Precursors……Page 868
XI. (METH)ACRYLIC NETWORKS……Page 871
1. Emulsion (co)polymerization of Monomers……Page 874
B. Solution Polymerization……Page 875
A. Unaccelerated Sulfur Vulcanization……Page 876
B. Accelerated Sulfur Vulcanization……Page 877
XIV. CONCLUDING REMARKS……Page 880
REFERENCES……Page 881
RECENT REVIEWS……Page 884
II. BIOMEDICAL POLYMERS……Page 886
A. Polyesters from Hydroxyacids……Page 887
C. Hydroxylated Polyesters……Page 889
D. Carboxylated Polyesters……Page 890
IV. POLY(AMIDE-ESTER)S……Page 891
V. POLYAMIDES AND POLYAMINOACIDS……Page 892
IX. SUTURES AND WOUND REPAIRS……Page 893
XII. SUMMARY……Page 894
REFERENCES……Page 895
I. CHEMISTRY OF CONTROLLED/LIVING RADICAL POLYMERIZATION (CRP)……Page 899
II. CONTROLLED/LIVING RADICAL POLYMERIZATION BASED ON REVERSIBLE THERMAL CLEAVAGE OF WEAK COVALENT BONDS……Page 902
III. TRANSITION METAL CATALYZED PROCESSES — ATOM TRANSFER RADICAL POLYMERIZATION……Page 905
IV. DEGENERATIVE TRANSFER……Page 909
V. COMPARISON OF VARIOUS METHODS OF CONTROLLING RADICAL POLYMERIZATION……Page 912
VII. COMPOSITIONS……Page 914
VIII. ARCHITECTURE……Page 920
IX. FUNCTIONALITY……Page 921
XI. CONCLUSIONS……Page 922
REFERENCES……Page 923
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