SOURCEBOOK OF ADVANCED
POLYMER LABORATORY
PREPARATIONS
Stanley R. Sandler Elf Atochem North America
King of Prussia, Pennsylvania
Wolf Karo Consultant to the Chemical Industry
Huntingdon Valley, Pennsylvania
ACADEMIC PRESS
London Boston New York Sydney Tokyo Toronto
CONTENTS
Preface xv Introduction xvii
1 POLYMERIZATION OF STYRENE A N D OTHER OLEFINS
1. BULK POLYMERIZATION 3 1-1. Preparation of Polystyrene by the Bulk Thermal
Polymerization of Styrene 4 2. SUSPENSION POLYMERIZATION 5
1-2. Preparation of Polystyrene by Suspension Polymerization 6
3. EMULSION POLYMERIZATION 6 1-3. Emulsion Polymerization of Styrene 7
4. ANIONIC POLYMERIZATIONS 8 1-4. Preparation of Polystyrene by the Polymerization of Styrene
Using Sodium Naphthalene Catalyst 11 5. PREPARATION OF MONODISPERSED MICROSPHERES
OF POLYSTYRENE 12 1-5. Monodispersed Crosslinked Microspheres by Dispersion
Polymerization 13 6. POLYMERIZATION OF OTHER OLEFINS USING A
CATIONIC POLYMERIZATION PROCESS 14 1-6. Preparation of Butyl Rubber (Copolymerization of
Isobutylene with Isoprene Using BF3 Catalyst) 16 7. POLYMERIZATION OF OTHER OLEFINS BY AN
ANIONIC POLYMERIZATION PROCESS 17 1-7. Preparation of Polybutadiene by the Amylsodium-Catalyzed
Polymerization of Butadiene 17
v
VI CONTENTS
8. CATALYTIC BREAKTHROUGHS IN POLYMERIZING OLEFINS 17
References 19
2 POLYESTERS 2-1. Preparation of Poly(ethylene terephthalate) 27
References 29
3 POLYCARBONATES 3-1. Preparation of Poly(2,2-dimethyl-l,3-propanediol carbonate)
[poly(neopentylene carbonate)] 32 References 33
4 POLYAMIDES 4-1. Preparation of Poly(hexamethylenesebacamide) (Nylon
6-10) by the Interfacial Polymerization Technique 38 References 38
5 POLYMERIZATION OF ALDEHYDES 5-1. Preparation of Polyacetaldehyde by Cationic Polymerization
of Acetaldehyde Using BF3 Catalysis 42 5-2. Polymerization of Acetaldehyde Using Potassium
Triphenylmethoxide Catalysis 43 References 44
6 POLYMERIZATION OF EPOXIDES AND CYCLIC ETHERS
6-1. Preparation of Polyoxypropylene Glycol by the Room-Temperature Polymerization of Propylene Oxide Using KOH 47
6-2. Polymerization of /-Propylene Oxide with Solid KOH Catalyst 49
6-3. Polymerization of Ethylene Oxide Using SnCl4 (or BF3) Catalyst 49
References 52
7 POLYUREAS 1. REACTION OF DIAMINES WITH DIISOCYANATES 54
7-1. Preparation of a Polyurea from Bis(3-aminopropyl) Ether and 1,6-Hexamethylene Diisocyanate 54
CONTENTS vii
2. REACTION OF DIAMINES WITH UREA 55 7-2. Preparation of Poly(4-oxyhexamethyleneurea) 55
References 56
8 POLYURETHANES 8-1. Preparation of a Polyurethane Prepolymer 61 8-2. Preparation of Polyethylene methylene bis(4-
phenylcarbamate)] 62 References 62
9 THERMALLY STABLE POLYMERS 9-1. Preparation of Poly(2,6-dimethyl-l,4-phenylene oxide) by
Polymerization of Silver 4-Bromo-2,6-dimethylphenolate 66
9-2. Preparation of Poly(2,6-dimethyl-l,4-phenylene oxide) Using CuCl-Pyridine-02 68
References 69
10 POLYMERIZATION OF ACRYLIC MONOMERS 1. POLYMERIZATION OF ACRYLIC ACIDS AND
RELATED COMPOUNDS 73
10-1. Preparation of Isotactic Poly(acrylic acid) 73 10-2. Preparation of Poly(methacrylic acid) by Suspension
Polymerization with a Monomer-Soluble Initiator 75 10-3. Polymerization of Methacrylic Acid in an Aqueous
Solution 76 10-4. Charge-Transfer Complex Polymerization of Acrylic
Acid-Acrylamide 77 10-5. Bottle Polymerization of Itaconic Acid 79
2. POLYMERIZATION OF ACRYLAMIDE AND RELATED AMIDES 81
10-6. Suspension Copolymerization of Acrylamide and Acrylic Acid 85
10-7. Polymerization of Acrylamide in Aqueous Solution 86 10-8. Preparation of Poly(acrylamide) Gels 86 10-9. Polymerization of Methacrylamide in Toluene 87
10-10. Emulsion Copolymerization of Styrene and Acrylamide 89
10-11. Inverse Emulsion Polymerization of Aqueous Acrylamide in Toluene 90
II CONTENTS CONTENTS
10-12. Anionic Polymerization of JV,iV-Dimethylacrylamide 1 2
10-13. Hydrogen-Transfer Polymerization of Acrylamide in Pyridine 93 " •
3. POLYMERIZATION OF ACRYLONITRILE AND RELATED MONOMERS 94 10-14. Slurry Homopolymerization of Acrylonitrile 97 10-15. Solution Polymerization of Acrylonitrile in Zinc
Chloride Solution 99 10-16. Emulsion Polymerization of Acrylonitrile 100 10-17. Emulsion Polymerization of Methacrylonitrile 101 10-18. Monosodium Benzophenone-Initiated Polymerization of
Acrylonitrile 102 4. POLYMERIZATION OF ACRYLIC AND METHACRYLIC
ESTERS 103 10-19. Generalized Procedure for the Preparation of Polymer
Sheets 108 10-20. Suspension Polymerization of Methyl Methacrylate
110 10-21. Solution Copolymerization of Glycidyl Methacrylate and
Styrene 111 10-22. Preparation of a Crosslinked Polymer Gel 112 10-23. Emulsion Polymerization of Ethyl Acrylate (Thermal
Initiation) 114 10-24. Redox Emulsion Polymerization of Ethyl Acrylates
115 10-25. Preparation of Isotactic Poly(methyl methacrylate)
116 10-26. Group Transfer Polymerization of Methyl Methacrylate
118 References 119
11 AMINO RESINS 1. UREA-FORMALDEHYDE CONDENSATIONS 126
11-1. Preparation of Urea-Formaldehyde Textile Resins (F: U Ratio 2:1) 126
2. MELAMINE-ALDEHYDE CONDENSATIONS 127 11-2. Preparation of Hexamethylolmelamine Prepolymer 128
References 129
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Л ! il i l l
F
• 16 F
I J J
CONTENTS ix
12 PHENOL-ALDEHYDE CONDENSATIONS 12-1. Preparation of a Phenol-Formaldehyde Resole 131 12-2. Preparation of a Phenol-Formaldehyde Casting Resin
132 References 134
13 EPOXY RESINS 1. ANALYSIS OF EPOXY RESINS 136 2. CURING-POLYMERIZATION REACTIONS OF EPOXY
COMPOUNDS AND RESINS 137 13-1. Curing Reaction of Bisphenol A Diglycidyl Ether with
Poly(adipic acid anhydride) 137 References 139
14 ALKYD RESINS 14-1. Preparation of Poly(glyceryl phthalate) Alkyd Resin 144
References 147
15 POLYACETALS AND POLYVINYL ACETALS) 1. POLYACETALS FROM FORMALDEHYDE 151
15-1. Preparation of the Polyformal of Diethylene Glycol 151 2. POLYACETALS FROM SUBSTITUTED ALDEHYDES 151
15-2. Preparation of a Polyacetal by the Reaction of Benzaldehyde with Bis(2-hydroxyethyl) Sulfide 152
15-3. Preparation of a Polyacetal by the Reaction of Pentaerythritol with a Mixture of 1,3- and 1,4-Cyclohexane Dialdehydes 153
3. POLYVINYL ACETALS) 153 15-4. General Procedure for the Preparation of Poly(vinyl
acetals) 155 15-5. Preparation of Poly(vinyl butyral) 155
References 156
16 POLYVINYL ETHERS) 1. CATIONIC POLYMERIZATION 159
16-1. Preparation of a Polyvinyl «-butyl ether) Using Stannous Chloride Catalyst 160
16-2. Preparation of Polyvinyl л-butyl ether) Using Boron Trifluoride Etherate Catalyst 160
CONTENTS
2. FREE-RADICAL POLYMERIZATION 161 16-3. Preparation of Polyvinyl ethyl ether) Using Di-fert-butyl
Peroxide Initiator 162 16-4. Copolymerization of Maleic Anhydride with Ethyl Vinyl
Ether 162 References 163
17
18
19
20
POLY( JV-VINYLPYRROLIDONE) 1. BULK POLYMERIZATION PROCEDURES 167
17-1. Bulk Polymerization with AIBN 167 17-2. Bulk Polymerization of a PVP-Based Hydrogel 169
2. AQUEOUS SOLUTION PROCEDURES 170 17-3. Generalized Procedure for Polymerization with
Ammonia-Hydrogen Peroxide 170 3. CATIONIC POLYMERIZATION 172
17-4. Copolymerization iV-Vinylpyrrolidone and Methyl Methacrylate with Triethylboron 172
4. COMPLEX FORMATION 173 References 174
SILICONE RESINS (POLYORGANOSILOXANES) OR SILICONES
18-1. Silicone Resins from Phenyltrichlorosilane 177 18-2. Silicone Resins by Cyclohydrolysis of
Dimethyldichlorosilane and Methyltrichlorosilane 178 References 178
OLEFIN-SULFUR DIOXIDE COPOLYMERS 19-1. Preparation of Octene-Sulfur Dioxide Copolymers 181 19-2. Preparation of Propylene-Sulfur Dioxide Copolymers
182 References 183
SULFIDE POLYMERS 1. CONDENSATION REACTIONS 185 2. OXIDATION REACTIONS 187
20-1. Preparation of a Polydisulfide by the Oxidation of Hexamethylenedithiol with Bromine 187
CONTENTS
1 I
II II
I I J I 1 J I J
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22
3. POLYCARYLENE SULFIDES) 188 20-2. Preparation of Poly(phenylene sulfide) by the Reaction
of /7-Dichlorobenzene and Sodium Sulfide in 7V-Methyl-2-pyrrolidone 189
References 192
POLYMERIZATION OF MONO- AND DIISOCYANATES 1. HOMOPOLYMERIZATION OF MONOISOCYANATES
TO 1-NYLON 194
21-1. General Method for the Preparation of 1-Nylon 195
2. POLYMERIZATION OF DIISOCYANATES TO GIVE POLYCARBODIIMIDES 198
21-2. Polymerization of 2,4-Toluene Diisocyanate 199
3. POLYMERIZATION OF POLYISOCYANATES TO POLYISOCYANURATES 201
References 201
POLYOXYALKYLATION OF HYDROXY COMPOUNDS 1. CHEMISTRY 204
2. POLYOXYALKYLATION OF ALCOHOLS AND DIOLS 207
22-1. Preparation of Ethyleneglycol Monoethyl Ether 208
22-2. Polyoxypropylation and Polyoxyethylation of 2,6,8-
Trimethyl-8-nonanol 208
22-3. Preparation of Polyoxypropylated Stearyl Alcohol 209
22-4. Preparation of Polyoxypropylene Glycol 209 3. POLYOXYALKYLATION OF POLYHYDROXY
COMPOUNDS 210 22-5. Polyoxypropylation of Sucrose 210
22-6. Polyoxypropylation of Sorbitol 211
22-7. Preparation of Polyoxyethylated Pentaerythritol 212
4. POLYOXYALKYLATION OF PHENOLS 212
22-8. Preparation of Polyoxyethylated Nonylphenol 213
22-9. Polyoxypropylation of ^-terf-Butylphenol 213
References 214
CONTENTS
2 3 POLYMERIZATION OF VINYL ESTERS 1. MONOMER PURIFICATION 219 2. INITIATION, INHIBITION, AND RETARDATION OF
POLYMERIZATION 222 3. POLYMER STRUCTURE 223 4. REACTIVITY RATIOS OF VINYL ESTERS 227 5. CONFORMATION OF POLYVINYL ESTERS) 229 6. BULK POLYMERIZATION 230
23-1. Sealed-Tube, Bulk Polymerization of Vinyl Acetate 232
7. SOLUTION POLYMERIZATION 232 23-2. Polymerization of Vinyl Acetate in tert-Butyl Alcohol
233 8. SUSPENSION POLYMERIZATION 234
23-3. Suspension Polymerization of Vinyl Acetate (Control of Molecular Weight by Variation in Initiator Level) 236
9. EMULSION POLYMERIZATION 237 23-4. Emulsion Polymerization of Vinyl Acetate-Potassium
Persulfate-Sodium Lauryl Sulfate System 239 23-5. Emulsion Ter-polymerization of Vinyl Acetate, Butyl
Acrylate, and Vinyl Neodecanoate (Seeded Process with Gradual Monomer and Initiator Additions) 242
10. NONAQUEOUS DISPERSION POLYMERIZATION 243 23-6. Preparation of Polyvinyl acetate) in Nonaqueous
Dispersion 243 11. RADIATION-INITIATED POLYMERIZATION 244 References 245
2 4 POLYMERIZATION OF ALLYL ESTERS 1. POLYMERIZATION OF ALLYL ACRYLATE AND
METHACRYLATE 252 24-1. Solution Polymerization of Allyl Methacrylate 253
2. POLYMERIZATION OF DIALLYL CARBONATES 253 24-2. Solution Polymerization of Diethylene Glycol Bis(allyl
carbonate) 254 3. POLYMERIZATION OF DIALLYL ESTERS OF
PHTHALIC ACIDS 255 24-3. Bulk Polymerization of Diallyl o-Phthalate with High-
Temperature Initiator 256
I I
CONTENTS
II J
II II II i l II I 1 J J
J J
25
26
24-4. ' Referenz
POLYft 25-1. I
I Reference
INTRO] POLYM 1. INTRC 2. DEVE
RECIF 26-1. E 26-2. F
E F E E 2 E S E A С E Ii
Reference
26-3.
26-4.
26-5.
26-6.
26-7.
Subject Index :
CONTENTS
OF
229
Acetate
Alcohol
(Control of Level) 236
Potassium
, Butyl Process with
242 243
244
CONTENTS
24-4. "Suspension Polymerization" of Diallyl o-Phthalate 257 References 259
2 5 POLYVINYL ALCOHOL) 25-1. Preparation of Polyvinyl alcohol) by the Alcoholysis of
Polyvinyl acetate) 263 References 264
26 INTRODUCTORY NOTES ON EMULSION POLYMERIZATION TECHNIQUES 1. INTRODUCTION 266 2. DEVELOPING AN EMULSION POLYMERIZATION
RECIPE 268 26-1. Emulsion Polymerization of Styrene 273 26-2. Preparation of Butadiene-Styrene Copolymers by the
Emulsion Polymerization Technique 273 26-3. Preparation of Acrylonitrile-Butadiene Copolymers by
Emulsion Polymerization 274 26-4. Emulsion Copolymerization of Styrene and Acrylamide
274 26-5. Emulsion Polymerization of Vinyl Acetate without
Surfactant 275 26-6. Emulsion Ter-polymerization of Vinyl Acetate, Butyl
Acrylate, and Vinyl Neodecanoate (Seeded Process with Gradual Monomer and Initiator Additions) 275
26-7. Emulsion Polymerization of Ethyl Acrylate (Thermal Initiation) 276
References 277
Subject Index 279
253 253
Bis(allyl
High-