the synthesis of lubricant additives from waste commodity polymers gregory james hunt

220 Pages·2012·4.99 MB·English

by  Robert Hunt

T S O L
HE YNTHESIS F UBRICANT
A F W
DDITIVES ROM ASTE
C P
OMMODITY OLYMERS

B
Y
G J H
REGORY AMES UNT

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THE SYNTHESIS OF LUBRICANT ADDITIVES FROM WASTE
COMMODITY POLYMERS

Thesis submitted for the degree of:
“Doctor of Philosophy”, PhD

From work conducted in the Department of Chemistry at
the University of Durham and at the BP Technology
Centre, BP PLC.

The work was funded by the Engineering and Physical Sciences Research
Council, UK, and BP PLC, UK, by a CASE doctoral training award.

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Further financial support was generously provided by:

Collingwood College at the University of Durham

Royal Society of Chemistry

Macro Group UK

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STATEMENT OF COPYRIGHT
The copyright of this thesis rests with the author unless referenced within the
text where copyright rests with the original holder. No quotation from it should
be published without his written consent and information derived from it
should be acknowledged.

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DECLARATION
The work reported in this thesis was carried out in the Department of
Chemistry at the University of Durham, Durham, UK and the BP Technology
Centre, Pangbourne, UK between October 2006 and March 2010. All the work
was carried out by the author unless otherwise stated, and has not previously
been submitted for a degree at this or any other University.

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Acknowledgements

Firstly, I must express my deepest gratitude to Prof. Neil Cameron who has
always been on hand to guide, discuss and encourage with his expertise and for
allowing me to attend an array of meetings and conferences. Neil’s limitless
patience in the writing of this Thesis also requires acknowledgement.

Having benefited from working in CG169 and CG234 there are many to thank;
Dr. Matt Gibson (Gibbo) for setting me straight during my Masters project and
for his organic chemistry skill. Dr’s Fransico-Fernadez Trillo, Jon Fay and
Sebastian Spain for all their insights into organic and polymer chemistry. David
Ward Johnson (the Johnson) for many interesting conversations and being the
butt of so many jokes. Kimmins for his enthusiasm and many a good night out
in the New Inn or Spice Lounge. Paco, Gerledine and the Germans are thanked
for the multitude of language lessons by the fume cupboards. Dr. Alison Parry
for all her expertise and help, not to mention her impressive whistling skills. Dr.
Ross Carnachan is thanked for providing so many memories, most notably the
iPod/laptop incident and being the sole consistent member of the group during
my time in Durham. Caroline is thanked for spicing up the dynamics of the lab,
as is Lauren Cowie for her enthusiasm and wit.

Dr Lian Hutchings is thanked for all his discussions regarding SEC, and for not
getting too mad after running it dry. Dr. Richard Thompson for running the Ion
beam experiments. All the analytical staff, Alan, Ian, Mike, Jackie and Aileen.

Special mention should be made to Scott, Jon, Johnson and Lauren for
providing me with friendship and encouragement which made weekend
chemistry fun!

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Dr. Gordon Lamb is thanked for all this patience and encouragement of new
ideas and for making my time in Pangbourne so enjoyable. Dr. Andrew Smith
for all his insights into chemistry.

I must thank my parents Eileen and Robert for all their help and support.

Finally, I must thank my fiancée Rachel; I couldn’t have done it without you!

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Table of Contents
INTRODUCTION: ASPECTS OF POLYMER SCIENCE; SYNTHESIS, DEGRADATION
AND LUBRICATION. ....................................................................................... 1
AIMS AND OBJECTIVES ............................................................................................ 2
FUNDAMENTALS OF POLYMER SCIENCE ...................................................................... 2
What is a polymer? ....................................................................................... 2
How are polymers classified? ....................................................................... 3
What are the common features of a polymer? ............................................ 4
Classification according to method of manufacture .................................... 5
POLYMER DEGRADATION ....................................................................................... 13
Methods of degradation ............................................................................. 14
Thermal Degradation .................................................................................. 16
Chemical Degradation ................................................................................ 19
Catalytic Degradation ................................................................................. 19
Superacids ................................................................................................... 22
Biological Degradations .............................................................................. 23
Photodegradation[47] ................................................................................ 25
Microwave degradation ............................................................................. 26
Ultrasonic degradation[46, 48]................................................................... 26
Mechanical degradation[48] ...................................................................... 27
Use of Reactors ........................................................................................... 27
LUBRICANT FORMULATION..................................................................................... 29
Basics of Lubrication ................................................................................... 29
Lubricant Additives ..................................................................................... 37
The Final Lubricant ...................................................................................... 47
GENERATION OF FUNCTIONAL MATERIALS FROM WASTE PLASTIC ............... 48
INTRODUCTION .................................................................................................... 49
RESULTS AND DISCUSSION ..................................................................................... 50
Initial investigation: the use of microwave assisted pyrolysis with a CEM
Discover Microwave Reactor ...................................................................... 50

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Biotage Initiator 60 Microwave pyrolysis system ....................................... 59
Recycling of expanded polystyrene using Biotage Initiator 60 Microwave
pyrolysis system .......................................................................................... 72
CONCLUSIONS ..................................................................................................... 78
EXPERIMENTAL SECTION ........................................................................................ 79
General ........................................................................................................ 79
Methods ...................................................................................................... 80
LUBRICANT COMPONENTS FROM WASTE POLYSTYRENE AND CONVENTIONAL
SOURCES ..................................................................................................... 83
INTRODUCTION .................................................................................................... 84
Copolymerisation of maleic anhydride and styrene ................................... 85
RESULTS AND DISCUSSION ..................................................................................... 93
Effect of maleic anhydride on the fragmentation of cumyl dithiobenzoate.
.................................................................................................................... 99
Maleic anhydride addition to a Macro-RAFT agent. ................................ 104
Stearyl methacrylate copolymers ............................................................. 114
Polymerisation with N-maleimides ........................................................... 119
Coupling reactions .................................................................................... 122
Reactions with degraded polystyrene ...................................................... 126
Microwave assisted synthesis of maleimides. .......................................... 129
EXPERIMENTAL SECTION ...................................................................................... 131
General ...................................................................................................... 131
Monomer synthesis .................................................................................. 132
Macro-monomer synthesis. ...................................................................... 133
Chain Transfer agent synthesis. ................................................................ 133
Polymer Synthesis ..................................................................................... 136
Post synthetic functionalisations .............................................................. 139
CONCLUSIONS ................................................................................................... 142
TESTING OF LUBRICANT COMPONENTS FROM WASTE POLYSTYRENE AND
CONVENTIONAL SOURCES ......................................................................... 144

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INTRODUCTION .................................................................................................. 145
RESULTS AND DISCUSSION ................................................................................... 145
Solubility .................................................................................................... 147
Dispersancy ............................................................................................... 150
Viscosity characteristics ............................................................................ 162
Thermal and Oxidative stability ................................................................ 166
EXPERIMENTAL .................................................................................................. 169
Rheological Testing ................................................................................... 169
Kinematic Viscosity ................................................................................... 169
Oxidation and thermal stability ................................................................ 169
CONCLUSIONS ................................................................................................... 170
CONCLUSIONS AND FUTURE WORK ........................................................... 173
CONFERENCE PRESENTATIONS .............................................................................. 178
CONFERENCE ATTENDANCE (NON-PRESENTER) ........................................................ 178
AWARDS AND BURSARIES .................................................................................... 179
REFERENCES ...................................................................................................... 180

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