PREPARATION AND EVALUATION OF LUBRICATING OIL ADDITIVES

388 Pages·18.428 MB·English

by  KOCH, EDWARD FRANK

The Pennsylvania State College
The Graduate School
Department of Chemistry
PREPARATION AND EVALUATION
OF LUBRICATING OIL ADDITIVES
A Thesis
by
Edward Frank Koch
Submitted in Partial Fulfillment of the
Requirements for the Degree of
Doctor of Philosophy in
Chemistry
August 1*?52
Approved:
Director, Petroleum Refining Laboratory
Head, Department/of Chemistry
PREPARATION AND EVALUATION
OF LUBRICATING OIL ADDITIVES
87503:1
ACKNOWLEDGMENT
The author is indebted to all of the members of the Petroleum
Refining Laboratory, past or present, for their cooperation in col­
lecting the data presented in this thesis. The financial assistance of
the Pennsylvania Grade Crude Oil Association is gratefully acknowledged.
The intelligent direction and suggestions of Dr. M. R. Fenske, Director
of the Petroleum Refining Laboratory, are deeply appreciated. The
indebtedness of the author to the ideas and wise suggestions of
R„ E. Hersh is thankfully acknowledged.
TABLE OF CONTENTS
gagf.
Summary i
I. Introduction 1
II. Survey of Literature 3
A. Characteristics of Oxidation 3
1. Mechanism 3
2. Types of Products 4
3. Characteristics ofH ydrocarbon Types 4
4. Effect of Temperature 7
5. Effect of Catalysts 7
B. Effect of Structure of Addition Agents on Lubricating
Oil Performance 9
1. Oxidation Inhibitors 9
(a) Sulfur Compounds 9
(b) Selenium Compounds 12
(c) Compounds of Phosphorus 15
(d) Phenolic Type Compounds 18
(e) Nitrogen Compounds 19
(f) Esters and Ester Derivatives 20
(g) Organometallic Compounds 21
(h) Miscellaneous Compounds 21
2. Detergents 22
(a) Metallic Derivatives of Carboxylic Acids 22
(b) Metallic Derivatives of PhenolicT ype
Compounds 22
(c) Metallic Derivatives of Sulfonic Acids 23
(d) Metallic Derivatives of Materials
Reacted With Phosphorus Sulfides 23
TABLE OF CONTENTS (Continued)
Page
(e) Miscellaneous Compounds 25
III. Experimental Methods and Procedures 26
A. Lubricating Oil Oxidation Stability Test 27
B. The Underwood Oxidation Test 30
C. Lauson Engine Tests 38
D. Physical Properties of Base Oils Used in Oxidation
and Detergency Tests 45
IV. Antioxidant Properties of Sulfurized Petroleum Derivatives 48
A. Sulfurized Petroleum Resins 48
1. Preparation of Sulfurized Resins 48
2. Testing of Sulfurized Resins 52
B. Sulfurized Non-Viscous Neutral 56
1. Preparations of Sulfurized Derivatives 56
»
2. Testing of Sulfurized Non-Viscous Neutral 56
C. Oil Oxidation Products and Sulfur Derivatives 56
1. Preparation of Sulfur Derivatives of Oil
Oxidation Products 57
2. Testing of Oil Oxidation Derivatives 59
V. Antioxidant Properties of Soybean Phosphatides and Sulfurized
Derivatives 61
A. Preparation of Sulfurized Soybean Phosphatides 61
B. Testing of Soybean Phosphatides and Sulfurized
Derivatives 64
VI. Antioxidant Properties of Amines and Related Compounds 70
A. Preparation of Sulfur and Selenium Derivatives of
Amines 70
B. Oxidation Tests on Amines and Derivatives 72
VII. Antioxidant Properties of Derivatives of Phenothiazine 79
A. Preparation of Derivatives of Phenothiazine
TABLE OF CONTENTS (Continued)
Page
B. Testing of Derivatives of Phenothiazine 85
Fill. Antioxidant Properties of Mercaptans, Sulfides, Disulfides,
and Selenium Analogs 92
A. Oxidation Tests on Mercaptans 92
B. Oxidation Tests on Sulfides 95
1. Preparation of a Cyclic Sulfide 95
2. Testing of Sulfides 96
Co Oxidation Tests on Disulfides 97
rx. Antioxidant Properties of Organic Trithiocarbonates 100
A. Reaction Products of Halogenated Hydrocarbons With
Sodium Trithiocarbonate 100
1. Preparation of Products 1G0
2» Testing of Products 104
B. Reaction Products of Halogenated Esters With Sodium
Trithio carb onat e 108
1. Preparation of Products 108
2. Testing of Products 114
Antioxidant Properties of Sulfur and Selenium Derivatives
of Phosphorus Acids 116
A. Sulfur and Selenium Derivatives of Tributyl Phosphite 116
1. Preparation of Derivatives 116
2. Examination of Sulfur and Selenium Derivatives
of Tributyl Phosphite 120
B. Sulfur and Selenium Derivatives of Triphenyl
Phosphite 136
1. Preparation of Derivatives 136
2. Antioxidant Properties of Sulfur and Selenium
Derivatives of Aryl Phosphites
C. Reaction Products of Alcohols With Phosphorus Sulfides
TABLE OF CONTENTS (Continued)
Page
1. Preparation of Products 147
2. Testing of Products 149
XI. Antioxidant and Dispersant Properties of Esters and Ester
Derivatives 150
A. Esters and Derivatives of Palmitic, Stearic, Oleic,
and Ricinoleic Acids 150
1. Preparation of Two Phosphorus Pentasulfide
Reaction Products With Oleic AcidE sters 150
2, Testing of Palmitic, Stearic, Oleic, and
Ricinoleic Acid Esters and Derivatives 153
B. Esters and Derivatives of Acetic, Acrylic, Anthranilic,
Abietic, and Naphthenic Acids 160
1. Preparation of Naphthenic Acid Esters and Sulfur
Derivatives of Acetic Acid and Acrylic Acid
Esters 160
2. Tests Conducted on Esters and Derivatives of
Acetic, Acrylic, Anthranilic, and Naphthenic
Acids 166
C. Esters of Oxalic, Succinic, Sebacic, and Phthalic
Acids 174
1. Esterification of Phthalic Anhydride With
n-Lauryl Alcohol and Ethylene Glycol 174
2. Oxidation Characteristics of Dibasic Acid
Esters 174
D. Maleic Acid Esters and Their Sulfur Derivatives 179
1. Preparation of Esters of Maleic Acid and
Sulfur Derivatives 180
2. Oxidation Tests on Sulfur and Ester Derivatives
of Maleic Acid 186
E. Phosphorus and Sulfur Derivatives of MaleicA cid
Esters 189
1. Preparation of Phosphorus and Sulfur Derivatives
of Maleic Acid Esters 189
2. Oxidation and Detergency Characteristics of
Sulfur and Phosphorus Derivatives of Maleic Acid
Esters 194
TABLE OF CONTENTS (Continued)
Page
F. Metallic Derivatives of Lauiyl Maleates Treated
With Phosphorus Pentasulfide. 208
1. Preparation of Metallic Derivatives 208
2. Testing of Metallic Derivatives 215
G. Salts of Monolauryl Maleate 226
1. Preparation of Salts of Monolauryl Maleate 226
2. Oxidation and Detergency Tests on Salts of
Monolauryl Maleate 228
H. Metallic Derivatives of the Reaction Product of
Sodium Lauryl Mercaptide With Monolauryl Chloro-
maleate 232
1. Preparation of Derivatives 232
2. Antioxidant and Detergent Properties of
Metallic Derivatives 243
I. Derivatives of Esters Prepared From Chloroma'leic
Anhydride 263
1. Preparation of Derivatives 263
2. Testing of Derivatives 272
XII. Antioxidant and Detergent Properties of Sulfonic Acid
Derivatives 280
A. Derivatives of Miscellaneous Sulfonic Acids 280
1. Preparation of Derivatives 280
2. Antioxidant and Detergent Properties of
Miscellaneous Sulfonic Acid Derivatives 282
B. Metallic Salts of Petroleum Sulfonic Acids 286
1. Preparation of Petroleum Sulfonic Acid Salts 286
2. Testing of Metallic Petroleum Sulfonates 294
XIII. Metallic Derivatives of Naphthenic Acids 319
A. Preparation of Barium and Cadmium Derivatives of
Petroleum Naphthenic Acids 319
TABLE OF CONTENTS (Concluded)
Page
B. Detergent and Anti oxidant Properties of Metallic
Naphthenates 320
XIV. Concluding Discussion 335
XV. Appendix 337
A. Physical Properties of Addition Agents 337
Bibliography 343
LIST OF FIGURES
Figure Page
Is The Effect of Various Metallic Derivatives on
Piston Demerits in the Lauson Engine Detergency
Test xviii
1 Antioxidant Action of Various Sulfur Compounds on
Two Desulfurized Oils at 171°C. 11
2 Relative Antioxidant Effect of Sulfides and
Selenides 13
3 Underwood Test Results After 10 Hours Run on a
Conventional Pennsylvania Neutral (0-195) Containing
Tributyl Thionophosphate (S-24A) 129
4 Improvement of the Detergency Properties of a
Blended Lubricating Oil by Increasing the Content
of Calcium Sulfonate in the Presence of an
Oxidation Inhibitor 306