251

9

Sulfur Carriers

Thomas Rossrucker and Achim Fessenbecker

CONTENTS

9.1 Introduction ........................................................................................................................... 252
9.2 History ................................................................................................................................... 253
9.2.1 First Synthesis and Application (1890–1918) ............................................................ 253
9.2.2 First Application in Metalworking Oils (1920–1930) ............................................... 254
9.2.3 Sulfurized Compounds for Gear Oils and Other Lubricants (1930–1945) ............... 254
9.2.4 Scientifi c Research on Chemistry and Application (1930–1949) .............................. 255
9.2.5 Summary of the Past 50 Years .................................................................................. 256
9.3 Chemistry .............................................................................................................................. 257
9.3.1 Chemical Structure of Sulfur Carriers ...................................................................... 257
9.3.1.1 Sulfurized Isobutene ................................................................................... 258
9.3.1.2 Active-Type Sulfurized Olefi ns ................................................................... 258
9.3.1.3 Inactive Sulfurized α-Olefi ns ...................................................................... 258
9.3.1.4 Sulfurized Synthetic Esters (Light Color) .................................................. 258
9.3.1.5 Sulfurized Fatty Oil (Black Color) ............................................................. 259
9.3.1.6 Sulfurized Fatty Oil/Olefi n Mixture (Light Color) ..................................... 259
9.3.2 Current Commercial Production Processes .............................................................. 259
9.3.2.1 General Aspects .......................................................................................... 259
9.3.2.2 Black Sulfurization ..................................................................................... 260
9.3.2.3 High-Pressure H 2 S Reaction ....................................................................... 261
9.3.2.4 Mercaptan Route ......................................................................................... 262
9.3.3 Other Synthetic Routes .............................................................................................. 262
9.3.3.1 Sulfurchlorination Route ............................................................................. 262
9.3.3.2 Alkylhalogenide/NaSx ................................................................................ 263
9.3.4 Raw Materials ............................................................................................................264
9.4 Properties and Performance Characteristics ......................................................................... 264
9.4.1 Chemical Properties .................................................................................................. 264
9.4.1.1 Effect of Additive Structure on Performance ............................................. 264
9.4.2 Physical Properties .................................................................................................... 2 67
9.4.2.1 Effect of Additive Structure on Properties ................................................. 267
9.5 Comparative Performance Data in Pertinent Application Areas .......................................... 269
9.5.1 Metalworking ............................................................................................................ 269
9.5.1.1 Cutting/Forming ......................................................................................... 269
9.5.1.2 Contribution of Sulfur Carriers to Metalworking ....................................... 269
9.5.1.3 Replacement of Sulfur Flowers ................................................................... 269
9.5.1.4 Copper Corrosion ........................................................................................ 270
9.5.1.5 Substitutes for Chlorinated Paraffi ns .......................................................... 270
9.5.1.6 Substitute for Heavy Metals ........................................................................ 270
9.5.1.7 Carbon Residue Reducing in Rolling Oils .................................................. 270
9.5.1.8 Water Miscible Metalworking Products ..................................................... 270