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

il 13

II II II "

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

21

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-