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Biobased Polyols for
Industrial Polymers
 Scrivener Publishing
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Biobased Polyols for
Industrial Polymers

Deny Kyriacos
This edition first published 2020 by John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA
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10 9 8 7 6 5 4 3 2 1
 Contents

Preface xi
1 Vegetable Oils, Animal Fats, Carbohydrates and Polyols 1
1.1 Introduction 1
1.2 Sustainability 3
1.3 Polyols from Vegetable Oils 5
1.3.1 Polyols from Triglycerides 5
1.3.2 Polyols from Glycerol 10
1.4 Polyols from Carbohydrates 12
1.4.1 Ligno-Cellulosics 12
1.4.2 Cellulose 12
1.4.2.1 Hydrolysis 13
1.4.2.2 Oxidative Degradation 13
1.4.2.3 Thermal Degradation 14
1.4.3 Hemicellulose 14
1.4.4 Lignin 15
1.4.5 Sucrose 16
1.4.6 Starch 19
1.4.6.1 Glucose 19
1.4.6.2 Sorbitol 20
References 22
2 Polyurethanes, Polyesters and Epoxies 25
2.1 Introduction 25
2.2 Polyurethanes 25
2.2.1 Rigid Foams 25
2.2.1.1 Isocyanates 26
2.2.1.2 Polyols 26
2.2.2 Flexible Foams 27
2.2.2.1 Isocyanates 28
2.2.2.2 Polyols 28

v
vi Contents

2.2.3 Microcellular Elastomers 28

2.2.3.1 Footwear 29
2.2.3.2 Integral Skin 31
2.2.4 Thermoplastic Polyurethane (TPU) Elastomers 32
2.2.4.1 Isocyanates 33
2.2.4.2 Polyols/Diols (Chain Extenders) 34
2.2.5 Casting Systems 34
2.2.5.1 Isocyanates 36
2.2.5.2 Polyols 36
2.2.5.3 Crosslinkers 36
2.2.5.4 Examples 36
2.2.6 Coatings 37
2.2.6.1 Urethane Oils/Uralkyds 37
2.2.6.2 Moisture Curable Coatings 38
2.2.6.3 Blocked Isocyanates 39
2.2.6.4 Two-Component Coatings 39
2.3 Polyesters 40
2.3.1 Unsaturated Polyesters 40
2.3.1.1 Alkyds 40
2.3.1.2 Drying Oils 42
2.3.2 Thermoplastic Polyesters 43
2.3.3 Polyester Polyols 45
2.4 Epoxies 46
References 48
3 Vegetable Oils and Fats 51
3.1 Introduction 51
3.2 Sources, Components and Extraction of Vegetable Oils 52
3.2.1 Soybean Oil 52
3.2.1.1 Source 52
3.2.1.2 Components of Soya Bean 54
3.2.1.3 Triglyceride (Oil) Extraction 67
3.2.2 Palm Oil 73
3.2.2.1 Source 74
3.2.2.2 Components 76
3.2.2.3 Extraction 79
3.2.3 Corn Oil 85
3.2.3.1 Source 85
3.2.3.2 Corn Kernel Components 87
3.2.3.3 Processing of Corn Kernels 88
3.2.3.4 Corn Oil Extraction and Refining 92
 Contents vii

3.2.4 Linseed Oil 93

3.2.4.1 Source 93
3.2.4.2 Components of Flaxseed 94
3.2.5 Castor Oil 94
3.2.5.1 Source 94
3.2.5.2 Oil Extraction 94
3.2.5.3 Castor Oil Components 100
3.2.6 Rapeseed Oil 100
3.2.6.1 Source 100
3.2.6.2 Oil Extraction 101
3.2.6.3 Components of Canola Seeds,
Rapeseeds and Canola Oil 105
3.2.7 Sunflower Oil 107
3.2.7.1 Source 107
3.2.7.2 Processing 109
3.2.7.3 Components of Sunflower Oil 110
3.2.7.4 Producers of Sunflower Oil 110
3.2.8 Vernonia Oil 110
3.2.9 Cashew Nut and Nutshell Oil 113
3.3 Comparative Data 117
3.3.1 Typical Oil Extraction from 100 kg of Oil Seeds 117
3.3.2 Fatty Acid Components of Vegetable Oil Triglycerides 118
3.3.3 Global Production 118
3.4 Fats 120
3.4.1 Fish Oil 120
3.4.2 Animal Fat 123
3.4.2.1 Lard 123
3.4.2.2 Beef Tallow 124
3.4.3 Comparative Data 124
References 126
4 Chemistry of Triglycerides and Fatty Acids 133
4.1 Introduction 133
4.2 Reactions of Double Bonds 133
4.2.1 Epoxidation 133
4.2.1.1 Chemical Epoxidation 134
4.2.1.2 Enzymatic Epoxidation 139
4.2.2 C=C Bond Cleavage 140
4.2.2.1 Ozonolysis 140
4.2.2.2 Metal Catalysis 142
4.2.2.3 Microbial Oxidation 144
4.2.2.4 Acid-Catalyzed Oxidation 144
viii Contents

4.2.3 C=C Bond Metathesis 145

4.2.4 Polymerization Reactions of Vegetable Oils 148
4.2.4.1 Homopolymerization 149
4.2.4.2 Copolymerization 149
4.2.4.3 Oxypolymerization 153
4.2.5 Hydrogenation 155
4.2.6 Dihydroxylation 158
4.2.6.1 Anti-Dihydroxylation 158
4.2.6.2 Syn Dihydroxylation 159
4.2.7 Addition 160
4.2.7.1 Hydroxybromination 160
4.2.7.2 Addition of Acetone/Malonic Acid 161
4.3 Reactions of Ester Groups 162
4.3.1 Hydrolysis of Ester Groups 162
4.3.1.1 Chemical Hydrolysis 162
4.3.1.2 Enzymatic Hydrolysis 163
4.3.2 Alcoholysis/Glycerolysis 164
4.3.3 Transesterification 167
4.3.4 Aminolysis 168
4.4 Reactions of Hydroxyl Groups 170
4.4.1 Dehydration 170
4.4.2 Esterification 170
References 171
5 Polyols from Triglycerides 177
5.1 Introduction 177
5.2 Reactions of Epoxides 178
5.2.1 Hydrolysis of Oxirane Rings 179
5.2.1.1 With Inorganic Acids 179
5.2.1.2 With Organic Acids 180
5.2.2 Alcoholysis of Oxirane Rings 182
5.2.2.1 Clay Catalyzed 182
5.2.2.2 HBF4 Catalyzed 184
5.2.3 Esterification of Oxirane Rings 185
5.2.3.1 With Carboxylic Acids 185
5.2.3.2 Acid Anhydrides 188
5.2.3.3 Hydroxy Carboxylic Acids 188
5.2.4 Aminolysis 189
5.3 Reactions of Ozonides 191
5.3.1 Ozonolysis Followed by Hydrogenation 191
 Contents ix

5.3.2 Polyols from the Transesterification of Ozonolysis

Intermediates 193
5.3.2.1 Amidification of Esters 194
5.3.2.2 Interesterification with Glycerol 194
5.4 Hydroformylation 196
5.5 Examples of Synthetic Methods 199
5.5.1 Glycerol Propoxylates 199
5.5.2 Castor Oil Alkoxylates 199
5.5.3 Mixed Alkoxylates 200
5.5.4 Oxidation in the Presence of Organometallic
Complexes 200
5.5.5 Use of Double-Metal Cyanide (DMC)
Complex Catalysts 201
5.5.6 Polyols from Palm Oil 203
5.5.7 Polyols from Oleic Acid (or Canola Oil) 206
5.5.8 Polyols from Soybean Oil and Chicken Fat 207
5.5.9 Autocatalytic Polyols 208
5.5.9.1 From Diethanolamine and Epoxidized
Soybean Oil 208
5.5.9.2 Mannich Polyols from Cardanol 210
References 213
6 Carbohydrate-Based Polyols 219
6.1 Introduction 219
6.2 Bio Ethylene Oxide 219
6.3 Bio Propylene Glycol 223
6.3.1 1,3-Propanediol 223
6.3.1.1 Fermentation 224
6.3.1.2 Hydrogenation 225
6.3.2 1,2-Propanediol 225
6.3.2.1 Hydrocracking 225
6.3.2.2 Fermentation 226
6.4 Bio-Butanediol 226
6.5 Sucrose 228
6.5.1 Introduction 228
6.5.1.1 Sucrose from Cane Sugar 229
6.5.1.2 Sucrose from Beets 230
6.5.2 Propoxylated Sucrose Initiated Polyols 231
6.5.3 Propoxylated/Ethoxylated Polyols
with Mixed Initiators 232
6.5.3.1 Sucrose/Ethylene Diamine Initiators 233
6.5.3.2 Sucrose/Glycerol Initiators 233
x Contents

6.5.4 Propoxylation of Glucose Obtained from Starch 234

6.6 Sorbitol 235
6.6.1 Synthesis 235
6.6.2 Synthesis of Polyols from the Alkoxylation of Sorbitol 236
6.6.3 Sorbitol Derivatives 237
6.7 Carbohydrates from Corn Fibers 239
6.7.1 Chemical Treatment 239
6.7.2 Biochemical Treatment 240
References 242
7 Biobased Polyols and Their Applications 247
7.1 Commercial Vegetable Oil Polyols 247
7.1.1 Producers 247
7.1.2 PU Applications 247
7.1.2.1 Rigid Foams 247
7.1.2.2 Flexible Foams 269
7.1.2.3 Viscoelastic Foams 275
7.1.2.4 Castings/Sealants 284
7.1.2.5 Carpet Backing 289
7.1.2.6 Elastomers and Coatings 295
7.1.3 Epoxies 302
7.1.4 Polyesters 306
7.1.4.1 Alkyd Resins 306
7.1.4.2 Thermoplastic Polyesters 309
7.1.5 Acrylate Coatings 311
7.1.5.1 Introduction 311
7.1.5.2 Examples 311
7.2 Commercial Carbohydrate-Derived Polyols 313
7.2.1 Producers 313
7.2.2 General Technical Considerations 314
References 315
Appendix 319
Index 327
 Preface

The use of naturally occurring molecules in the production of industrial

polymers and polymeric intermediates attracts more and more the atten-
tion of manufacturing companies. From a scientific point of view, the labo-
ratory preparation of commodity polymers based on natural products was
already examined many decades ago. However, the recent advent of issues
related to terms such as biobased, biodegradable, sustainability and cyclic
economy, all of which concern the protection of the environment from the
deleterious effects of some petrochemicals as well as from the irreversible
accumulation of thermoplastics and thermosets in nature, has prompted
governments and industries alike to examine the marketing of polymers
that consist at least partly of naturally sourced components in their macro-
molecular structure.
This book is addressed to readers interested in learning the basics of the
chemistry of biobased polyols in the manufacture of commercial polymers.
The latter include, among others, polyurethanes, epoxides and polyesters,
both saturated and unsaturated.
The introductory chapter of this book gives an account of the various
biobased polyols and their initiators, as well as the prices of vegetable oils
compared to crude oil. The ubiquitous word, sustainability, is also sub-
ject to the author’s comments. The second chapter briefly describes most
applications in which the polyols may be commercially valuable. This is
followed by a thorough investigation of the chemical structures as well as
the extraction processes of fatty acids, which are the major constituents
of naturally occurring fats and oils. The fourth chapter is dedicated to an
understanding of the basic chemistry of the groups present in triglyceride
molecules. Several examples of routes to the synthesis of biobased polyols
from fatty acids, as well as from vegetable oils, are given in the fifth chapter.
Carbohydrate initiated polyols are not new in the industrial world. They
cannot be considered as fully biobased unless they are ethoxylated or prop-
oxylated with epoxides originating from natural products. The synthesis
of those epoxides from natural sources is described in the sixth chapter

xi
xii Preface

and several practical examples are included. The last chapter addresses the
technology of products made from biobased polyols.
Accompanying the text of each chapter of this book are many graphs
and photographs.
The author wishes to thank all the scientists, engineers, technicians and
marketers whose work is mentioned in this book, often in great detail.
Thanks are also extended to the originators of the photographs included
herein. Finally, the initiatives of all manufacturing companies, the man-
agement of which operate their businesses with a commitment to solving
environmental problems, are also acknowledged.

Dr. Deny Kyriacos

Brussels, Belgium
January 2020
 1
Vegetable Oils, Animal Fats,
Carbohydrates and Polyols

1.1 Introduction
This chapter describes polyols in detail, including diols, the chemical com-
ponents of which are obtained from sources other than crude oil.
The polyols are used in the manufacture of commercial polymers and
polyurethanes, for example.
Among the major natural chemicals from which polyols can be derived
are:

• Vegetable oils
• Fish oils
• Animal fats
• Carbohydrates

For industrial purposes vegetable oils and carbohydrates are the most
approachable sources of chemicals. Work on polyols derived from animal
fats can be found in the patent literature [1].
Those products are, quite rightly, described as green products because
they originate from natural sources, the production of which humans can
control almost at will. They are renewable because, in contrast to crude oil,
they originate from non-depletable sources. Their availability is not the
monopoly of some countries which possess vast amounts of oil reserves.
Agricultural products require the right weather conditions to grow as well
as an area large enough for them to be cultivated on.
The first detailed studies on the use of vegetable oils and animal fats in
polyurethane technology date back to the late fifties and early sixties.

Deny Kyriacos. Biobased Polyols for Industrial Polymers, (1–24)

© 2020 Scrivener Publishing LLC

1
2 Biobased Polyols for Industrial Polymers

Among the reasons given for utilizing polyols from natural sources were:

• Since a favorable price differential exists for castor oil over

most polyesters, information concerning the properties of
various castor urethane foams should be useful to manufac-
turers and consumers of expanded foams [2].
• Dimer acids are commercially available and are produced
by the polymerization of polyunsaturated fatty acids derived
from soybean, cottonseed, and linseed oils. Less expensive
polyols should result from the condensation of ethylene
oxide with dimer acid [3, 4].
• The properties of the castor oil-based foams (PU) are compa-
rable to those of foams obtained from more costly polyols [5].
• A large potential market exists for polyols from natural
sources in the rapidly expanding urethane foam industry [6].

In general, the price of oil (Figure 1.1) used to produce the components
of polyether and polyester polyols is determined by speculation largely
founded on the production policies of the OPEC cartel.
Unfortunately, the pricing of basic carbohydrates or bean oils generally
is not much different from that of crude oil.
Soybean oil futures are traded at the Chicago Futures Market, where the
price of soybean oil is still lower than that of petroleum (Figure 1.2).
This means that, triglycerides, even if considered renewable sources
of chemicals, are subject to speculative pricing the same way crude oil is.
However, the difference is that their production is not restricted to only a

70
68
Crude oil price, USD/barrel,

66
64
Brent Texas-Dubai

62
60
58
56
54
52
50
Sep-18 Oct-18 Dec-18 Feb-19 Mar-19 May-19 Jul-19

Figure 1.1 Crude oil (petroleum) price chart (1barrel of crude ~ 140 kg) [7].
 Vegetable Oils, Animal Fats, Carbohydrates and Polyols 3

800
750
700
Soybean oil
650
Price, USD/Ton

600
550
500
450
400 Crude brent
350
300
Sep-18 Oct-18 Dec-18 Feb-19 Mar-19 May-19 Jul-19

Figure 1.2 Soybean oil price variation compared to that of crude oil in USD/ton [7].

few countries. Bean oil, or carbohydrate cartels, will be difficult to establish

and organize on a global scale. This trading approach does not exclude
speculative price hikes similar to those of crude oil.
Polyols based on renewable raw materials, such as fatty acid triglycerides,
sugar, sorbitol, glycerol and dimer fatty alcohols, are already used in diverse
ways as raw materials in the preparation of polymer chemicals.
It is claimed that soybean-oil-based polyols cost less than the petro-
leum polyols they replace, because they require considerably less energy
to produce; can be used in a broad range of polyurethane applications; and
produce polyurethane products with equivalent or better physical charac-
teristics [8].
In any event, polyols manufactured from petrochemical sources con-
stitute the majority of the polyols, polyesters as well as polyethers used in
industry.
Another source of polyols has emerged from the co-polymerization of
CO2 and epoxides [9].

1.2 Sustainability
During the last few years, the term sustainability has been mentioned
repeatedly in published articles, speeches, presentations as well as in com-
pany reports, to say the least. This was not the case when fluorocarbons, for
example, were widely used as blowing agents in the polyurethanes indus-
try. Many decades have elapsed since their deleterious effect on the ozone
layer was discovered.
4 Biobased Polyols for Industrial Polymers

The negative effect of CO2 on the atmosphere and the migration of

bisphenol A from polycarbonate utilized in feeding bottles are additional
examples which indicate that the consequences of chemicals are spotted
only after a type of specific damage has already been inflicated on the envi-
ronment, the economy, human health, etc.
According to the Cambridge Dictionary, the verb “to sustain” has the
following meanings:

• To allow something to continue for a period of time;

(The economy looks set to sustain its growth into next year.)
• To keep alive; (Many planets are unable to sustain human or
plant life.)
• To experience; (The company has sustained heavy losses this
year.)
• To support emotionally.

A succinct but detailed definition of the name derived from the

verb “to sustain,” i.e., sustainability is given in Wikipedia. Accordingly,
“Sustainability is the process of maintaining change in a balanced fashion,
in which the exploitation of resources, the direction of investments, the
orientation of technological development and institutional change are all
in harmony and enhance both current and future potential to meet human
needs and aspirations.”
Not long ago, the course of the polyurethanes industry was sluggish.
Sustainablility studies carried out by some multinationals pointed to the
closure of old isocyanate plants. A few months later, the state of the econ-
omy changed. The polyurethanes market picked up and the same plants,
instead of being shut, were upgraded. Ironically, a short time later, the
same companies showed poor earnings because the market did not follow
the predicted growth trend. But this is not the exception.
The biobased chemicals market has recently seen the collapse of bio-­
succinic acid producer BioAmber, despite the numerous reorganizations
aimed at reviving the sales of the company. A year before the company
was shut, BioAmber was planning a seven-fold increase of its production
capacity. According to their management, the business plan the company
put forward to its creditors was sustainable.
Succinic acid is a dicarboxylic acid widely used in the manufacture of
polyester polyols. The manufacturing process from natural sources proves
to be expensive, even if the science involved is brilliant. Therefore, the profit
margins generated to sustain its production must be high. BioAmber’s capac-
ity was 30 Ktpa, but the returns did not justify the operation of the company.
 Vegetable Oils, Animal Fats, Carbohydrates and Polyols 5

Whereas the applications of succinic acid in the polymers industry

are well known, the production of polyols from natural sources has only
recently gained momentum. Their successful inclusion in current technol-
ogies will show whether their use is sustainable. There is no need to use a
polyol produced from palm or rapeseed oil in a polyurethane formulation
if its contribution to the properties of the end product does not offer any
economic or qualitative appeal to the consumer.
There is no doubt that the final outlet of all industrial and agricultural
products are aimed at the direct or indirect consumption by humans. The
higher the production rates, the more energy will be required by the pro-
duction processes. A simple mathematical model will certainly prove that
sustainabilty as well as cyclic economy will be convincigly achieved and
implemented, at least, when the growth of the world population will be
controllable. But this is a very difficult target to attain.

1.3 Polyols from Vegetable Oils

Vegetable oils have been known to mankind since prehistoric times.
Humans have used fats and oils for food, healing and other ends. Over the
years, the extraction of oils from agricultural products has been elaborated.
Nowadays, for some polymerization purposes, many vegetable oil mole-
cules must be chemically transformed in order to include hydroxyl groups
in their structure.
For instance, soybean oil does not contain any hydroxyl groups but
has an average of 4.6 double bonds per triglyceride molecule. The unsat-
uration of the vegetable oil molecule can accommodate hydroxyl groups.
However, many reactions for preparing polyols from vegetable oils are not
very selective.
By-products are created during the transformation. Furthermore, many
conventional methods of preparing polyols from vegetable oils do not pro-
duce polyols having a significant content of hydroxyl groups, and the avail-
able methods do not produce products having a desirable viscosity. Greases
or waxes often result as a consequence of such chemical transformations.

1.3.1 Polyols from Triglycerides

Chemically, vegetable oils are defined as triglycerides (also called glyceryl
trialkanoates) because they are esters of glycerol and fatty acids (Figure 1.3).
The structures in Figure 1.4 put the glyceride definition in a broader
context.
6 Biobased Polyols for Industrial Polymers

CH2-O-CO-R1 CH2-OH R1-COOH

CH-O-CO-R2 Hydrolysis CH-OH + R2-COOH

CH2-O-CO-R3 CH2-OH R3-COOH
Triglyceride Glycerol Fatty acids
(R1,R2 & R3 are saturated of unsaturated
unbranched chains of 4 to 28 C atoms)

Figure 1.3 Products resulting from the hydrolysis of triglycerides.

CH3(CH2)7CH=CH(CH2)7C(O)O-CH2 CH3(CH2)7CH=CH(CH2)7C(O)O-CH2 HO-CH2

CH3(CH2)7CH=CH(CH2)7C(O)O-CH HO-CH HO-CH
CH3(CH2)14C(O)O-CH2 CH3(CH2)14C(O)O-CH2 CH3(CH2)14C(O)O-CH2
Triglyceride Diglyceride Monoglyceride

Figure 1.4 The definition of glycerides reflects the number of esterified hydroxyl groups
of glycerol.

In practice, the carboxylic acid moieties are not all the same, but mixtures
of several ones, as shown in Figures 1.3 and 1.4. They are also present in
different triglyceride molecules in variable ratios. The acids are called fatty
because their structure is similar to the acidic constituents of triglycerides
found in fats. Fats are solid triglycerides whereas oils are liquids. The car-
boxylic acids are monobasic with a long hydrocarbon tail chain. Fatty acids,
as shown in Figure 1.5, can be fully saturated but they can also contain
unsaturated sites as well as hydroxyl groups (ricinoleic acid for example).
Further down in the text, it will be shown how unsaturated triglycerides
are hydroxylated.
The hydroxylated compounds can be made useful, for example, in the
formation of urethanes, by reacting the hydroxyl groups with isocyanates.
Coatings, adhesives, elastomers, foams and composites can be made from
elastomers using such hydroxy functional compounds.
For example, in a first step an excess of a diisocyanate, such as MDI
or TDI, the structures of which are shown in Figure 1.6, is reacted with
a hydroxyl-containing triglyceride, such as castor oil, so as to form a pre-
polymer containing an excess of isocyanate groups [10, 11].

O
O
OH
OH

OH
Palmitic acid Ricinoleic acid

Figure 1.5 Structures of some saturated and unsaturated fatty acids.

 Vegetable Oils, Animal Fats, Carbohydrates and Polyols 7

CH3 CH3
3 2 2' 3' 1 1
NCO OCN NCO
6
4 1 1' 4' 2
OCN CH2 NCO 6 2

5 6 5 3
6' 5'
5 3
4
4
NCO
Methylene diphenyl 4,4'-diisocyanate Toluene 2,4 Toluene 2,6
(MDI) diisocyanate diisocyanate

Figure 1.6 Chemical structures of some commercial aromatic diisocyanates.

Those free NCO groups originate either from free isocyanates or from
the reaction products of castor oil with TDI (or MDI), as shown in the
reaction scheme in Figure 1.7.
By reacting the isocyanate mixture with water in the presence of an
amine catalyst a foamed product is obtained, because of the evolution of
CO2. The reaction is shown in Figure 1.8.

O
CH2-O-C-(CH2)7-CH=CH-CH2-CH-OH
CH3
(CH2)5-CH3
N
O C
O
CH-O-C-(CH2)7-CH=CH-CH2-CH-OH
(CH2)5-CH3
O + C
N
O
CH2-O-C-(CH2)7-CH=CH-CH2-CH-OH
(CH2)5-CH3
Castor oil (OH value 161.5) 2,4 Toluene diisocyanate (TDI)
The ricinoleic acid moiety (excess)
is the major component

CH3
N=C=O
CH3
N
O C
NH CH3 O
CH2-O-C-(CH2)7-CH=CH-CH2-CH-O C
O
+
(CH2)5-CH3 N=C=O
N
O O C
O
CH-O-C-(CH2)7-CH=CH-CH2-CH-O C NH
CH3
(CH2)5-CH3
O O
N=C=O
CH2-O-C-(CH2)7-CH=CH-CH2-CH-O C NH
(CH2)5-CH3
Castor oil/TDI prepolymer (NCO terminated) 2,4- Toluene diisocyanate
(unreacted)

Figure 1.7 Reaction products of castor oil with an excess of 2,4-toluene diisocyanate (TDI).
8 Biobased Polyols for Industrial Polymers

R-NCO+ H2O → R-NH-COOH → R-NH2 + CO2↑

Figure 1.8 Reaction of isocyanate with water.

Polyols obtained from triglycerides are very often propoxylated and/or

ethoxylated with propylene oxide or ethylene oxide respectively in order
to increase their molecular weight and subsequently their chain flexibility.
The structure of each alkylene oxide is shown in Figure 1.9.

An example of such a polyol synthesis is described below [12]:

First, 267.2 g castor oil and 5.73 g KOH are flushed with nitrogen in an
autoclave at 110°C with stirring. Then, 747.3 g of propylene oxide are
added. After a reaction time of 4 h, 186.8 g ethylene oxide is metered
under pressure. After 1 h, the contents of the reactor are cooled to
40°C and neutralized by the addition of 132 g distilled water and 32.4
g, 11.85% sulfuric acid. After addition of 0.65 g Irganox 1076 (antiox-
idant), dehydration is carried out in vacuo and the mixture is heated
thoroughly for 3 h at 110°C and then filtered.
The OH number of the product is 51.7 mg KOH/g, and the viscos-
ity at 25°C is 500 mPas.

The reaction sequences of the above-described experiment are shown

in Figure 1.10. It should be noted that propoxylation leads to alcohols with
secondary hydroxyl end groups for steric reasons. Ethoxylation, in turn,
introduces primary OH groups, which are more reactive towards carbox-
ylic acids and isocyanates.
Therefore, in order to synthesize a completely biobased polyol, chem-
icals such as propylene oxide and ethylene oxide must also emerge from
natural sources. This text will examine if such a process is feasible.
Nevertheless, the final polyurethane cannot be defined as fully biobased
as long as the isocyanate component is aromatic. The source of aromatics
being, until now, petrochemical.
The same argument is valid for other technologies where polyols origi-
nating from natural sources are constituents of thermosets, such as unsat-
urated polyesters, for example.

O H H H
H C C H H C C C H
H H O H
Ethylene oxide Propylene oxide

Figure 1.9 Chemical structures of ethylene and propylene oxide.

 Vegetable Oils, Animal Fats, Carbohydrates and Polyols 9

O
CH2-O-C-(CH2)7-CH=CH-CH2-CH-OH H H H O CH3
H CH2-O-C-(CH2)7-
(CH2)5-CH3 H C C CH=CH-CH2-CH-O-CH2-CH−OH
C z
O O (CH2)5-CH3
H
O CH3
CH-O-C-(CH2)7-CH=CH-CH2-CH-OH
CH-O-C-(CH2)7-CH=CH2-CH-O-CH2-CH−OH
(CH2)5-CH3 y
(CH2)5-CH3
O Propoxylation O CH3
CH2-O-C-(CH2)7-CH=CH-CH2-CH-OH CH2-O-C-(CH2)7-CH=CH-CH2-CH-O-CH2-CH−OH
y
(CH2)5-CH3 (CH2)5-CH3
Castor oil O
H C C H
Ethoxylation H H

O CH3
CH2-O-C-(CH2)7-CH=CH-CH2-CH-O-CH2CH−O−CH2-CH2−OH
z p
(CH2)5-CH3
O CH3
CH-O-C-(CH2)7-CH=CH-CH2-CH-O-CH2CH−O−CH2-CH2−OH
y n
(CH2)5-CH3
O CH3
CH2-O-C-(CH2)7-CH=CH-CH2-CH-O-CH2CH−O−CH2-CH2−OH
x m
(CH2)5-CH3

Figure 1.10 Propoxylation followed by ethoxylation of castor oil.

The U.S. Federal Procurement Process has provisions which may favor
products which are biobased over those that are petroleum-based. For
example, for wall construction, the U.S. Department of Agriculture
(USDA) has proposed a minimum biobased content of 8% to be clas-
sified as a biobased product for federal procurement purposes.
Furthermore, in the United States, again, the Code of Federal
Regulations (CFR Title 7 Part 2902) details guidelines for designat-
ing biobased products for federal procurement. In this guideline, the
preferred procurement product must have a biobased content of at
least 7%, based on the amount of qualifying biobased carbon in the
product as a percent of the weight (mass) of the total organic carbon
in the finished product. The guideline is specifically for spray-in-place
plastic foam products designed to provide a sealed thermal barrier for
residential or commercial construction applications [13].
The biobased content is determined according to ASTM D6866.
ASTM D6866-08 includes Standard Test Methods for Determining
the Biobased Content of Solid, Liquid, and Gaseous Samples Using
Radiocarbon Analysis.
10 Biobased Polyols for Industrial Polymers

1.3.2 Polyols from Glycerol

Synthetic glycerol is manufactured on an industrial scale mainly from the
hydrolysis of epichlorohydrin, as shown in Figure 1.11 [14].
Since glycerol forms the backbone of triglycerides, it is produced upon
their saponification or transesterification. This method is a preferred green
method, epichlorohydrin being an unsafe product.
Glycerol has been used as such in rigid foam formulations, even if its
efficiency as well as its role are very often doubtful. The reactivity of the
secondary OH group is low compared to the reactivity of the primary OH
groups. The use of glycerol in spray foam formulations contributes to the
volume/equivalent weight requirements of the polyol and the isocyanate
components. Glycerol is also used in the manufacture of triols through
propoxylation and ethoxylation.
Those triols have applications in rigid as well as in flexible polyurethane
foams.
For example, Voranol 9815 is a glycerol initiated polyoxypropylene
polyoxyethylene (propoxylated and then ethoxylated to introduce primary
OH groups) polyol having an average hydroxyl number of 28, which is
available from the Dow Chemical Company.
Voranol CP 4702 is a glycerol initiated polyoxypropylene polyoxyeth-
ylene polyol having an average hydroxyl number of 32.
Voranol CP 3001 is a glycerol initiated polyoxypropylene polyoxyeth-
ylene polyol having an average hydroxyl number of 56.
These polyols are used in flexible foam formulations because of their low
OH value or high molecular weight.
On the other hand, Daltolac R 570 is a rigid foam, glycerol initiated
polyoxypropylene polyoxyethylene triol produced by Huntsman. Its OH
value is 570 mg KOH/g.

C12 HC1 HOC1 C1-CH2-CHC1-CH2(OH)

CH3-CH=CH2 + +
500ºC C1-CH2-CH=CH2 C1-CH2-CH(OH)-CH2C1
Propylene Allyl chloride 13-dichlorohydrin
Ca(HO)2

H2C HC CH2

C1 O
Epichlorohydrin

Figure 1.11 Reactions involved in the synthesis of epichlorohydrin.

 Vegetable Oils, Animal Fats, Carbohydrates and Polyols 11

Glycerol has become the source of diols, such as 1,3-propane diol, through
a fermentation process (Figure 1.12) first developed in the 19th century [15].
DuPont and Genencor have developed an Escherichia coli (E. coli) strain
capable of producing 1,3-propanediol (PDO) from glucose. However, glu-
cose is not the only component of corn.
DuPont and Tate & Lyle have developed a fermentation system that con-
verts corn sugar into propanediol (“BioPDO”). Such a bioprocess is more
energy efficient than conventional petrochemical processes (conversion of
propylene into propanediol). The bioprocess has smaller environmental
impact, lower operating costs, smaller capital investment, and greater sus-
tainability due to the use of renewable corn feedstock [16].
1,3-Propanediol is also a monomer employed in the industrial produc-
tion of polyester fibers [17] and diols for polyurethanes. It has been used as
a chain extender in thermoplastic polyurethanes [18].
1,3-Propane diol can also be condensed with biobased succinic acid to
produce polyester diols [19], as shown in Figure 1.13. The diols can be
reacted with a chain extender like butane diol to give a thermoplastic
polyurethane.
Biobased 1,3-propane diol is used by DuPont to manufacture the more
resilient and comfortable Sorona polyester. This polypropylene terepthal-
ate has applications in apparel, upholstery, home fashions, and carpets.

CH2-OH Fermentation CH2-OH Fermentation OH

O
HO OH Corn
CH-OH CH2 HO
Chlostridium diolis OH
Clostridium
CH2-OH pasteurianium CH2-OH
Kelbsiella pneumoniae
Glycerol 1,3 propane D-Glucose
diol

Figure 1.12 Propane diol obtained from the fermentation of glucose and glycerol.

HO-(CH2)3-OH HO-[(CH2)3-OOC-(CH2)2-COO-]n(CH2)3-OH
Condensation
1,3 propane diol Low molecular weight polyester diol
+ OCN-R-NCO
di-isocyanate
HOOC-(CH2)2-COOH OCN-R-NH-CO[O(CH2)3-OOC-(CH2)2-CO]nO(CH2)3-OCO-NH-R-NCO
Succinic acid
HO-(CH2)3-OH

-{[O(CH2)3-OOC-(CH2)2-CO]n[O(CH2)3-OOC-NH-R-NHCO]m}x-
Polyester polyurethane

Figure 1.13 Synthesis of a thermoplastic polyurethane.

12 Biobased Polyols for Industrial Polymers

1.4 Polyols from Carbohydrates

Carbohydrates are renewable, which makes them an attractive source of
chemicals. The main sources of carbohydrates are:

• Ligno-Cellulosics (Lignin, Cellulose, Hemicellulose)

• Sucrose
• Starch

Carbohydrates bear hydroxyl groups and can therefore be regarded as a

viable source of polyols.

1.4.1 Ligno-Cellulosics
Lignocellulose refers to plant biomass that is composed of cellulose, hemi-
cellulose, and lignin. The percentage of each constituent of lignocellulose
is shown in Figure 1.14.
Cellulosic biomass can be pretreated with dilute sulfuric acid to recover
high yields of sugars directly from hemicellulose and, subsequently, by
enzymatic hydrolysis of the residual cellulose.

1.4.2 Cellulose
Cellulose is the most common organic compound on Earth. Its structure
is shown in Figure 1.15. About 33% of all plants is cellulose (the cellulose
content of cotton is 90% and that of wood is 50%).

Lignin
Cellulose 15-25%
38-50%
Hemicellulose
23-32%

Cellulose macromolecule consisting of glucose units

Hemicellulose branched macromolecule from pentoses
Lignin Three-dimensional macromolecule from
methoxyphenyl-propane units

Figure 1.14 Lignocellulose composition.

 Vegetable Oils, Animal Fats, Carbohydrates and Polyols 13

OH OH OH
OH OH OH
HO O HO O HO O
HO O O O O O OH
O HO O HO O HO
OH OH OH
OH OH n OH
Cellobiose unit
H H
O HO OH O HO OH
O O
O O O O
O O
HO OH O HO OH O
H H
H H
O HO OH O HO OH
O O O
O O O O
O OH O
HO OH O HO
H H
H H
O HO OH O HO OH
O O O
O O O O
O OH O
HO OH O HO
H H
H H
O HO OH O HO OH
O O O
O O O
O O
HO OH O HO OH O
H H

Figure 1.15 Cellulose structure (macromolecules build up from glucose units).

For industrial use, cellulose is mainly obtained from wood pulp and cot-
ton. It is mainly used to produce cardboard and paper. To a lesser extent, it
is converted into derivative products such as cellophane and rayon.
Cellulose is composed of linear chains of covalently linked glucose
residues. Chemically, it is very stable. It is extremely insoluble. Cellulose
chains form crystalline structures called microfibrils. A microfibril with a
diameter of 20–30 nm contains about 2000 glucose molecules. Cellulose
undergoes the following basic reactions.

1.4.2.1 Hydrolysis
Acids attack the acetal linkages, cleaving the 1-4-glycosidic bonds. Since
acetals are quite stable toward alkali, hydrolysis at high pH requires very
vigorous conditions. Cellulose is also degraded by cellulase enzymes.
Termites and fungi digest cellulose, but the synthetic process of obtaining
ethanol from cellulose remains slow. The drawback is the sluggish rate at
which the cellulose enzyme complex breaks down tightly bound cellulose
into sugars, which are then fermented into ethanol.

1.4.2.2 Oxidative Degradation

In general, oxidation of cellulosic hydroxyls forms aldehydes, ketones, and
carboxyl groups. Strong oxidizing agents and/or vigorous reaction condi-
tions convert cellulose into CO2 and H2O.
14 Biobased Polyols for Industrial Polymers

1.4.2.3 Thermal Degradation

The applied temperature determines the nature of the degradation prod-
ucts. At low temperatures the degradation products are water, CO, CO2
and a carbonaceous char. At high temperatures, depolymerization of the
cellulose chain takes place. Anhydroglucose derivatives, volatile organic
materials and tars are formed. At still higher temperatures, more-or-less
random bond cleavage of cellulose and intermediate decomposition prod-
ucts results in formation of a variety of low molecular weight compounds.
The conversion of cellulose to glucose is described in several patents
[20–23]. For example, a mixture of coniferous wood chips is heated at
200°C in the presence of water, CaCl2 and HCl. The conversion of cellu-
lose to glucose is 80.5%. Other products formed include 5-hydroxymeth-
ylfurfural, xylose and furfural. Their structures are shown in Figure 1.16.

1.4.3 Hemicellulose
Hemicellulose consists of shorter chains of 500–3000 sugar units as opposed
to 7000–15000 glucose molecules per polymer chain present in cellulose.
Its main constituent carbohydrate molecules are shown in Figure 1.17.

O OH
OH O HO H HO OH
O O O
HO OH
HO OH H O
OH
Glucose Furfural 5(hydroxy methyl) furfural Xylose

Figure 1.16 Products resulting from the hydrolysis of coniferous chips.

H-C=O H-C=O H-C=O

H-C-OH CH2-OH COOH CH2-OH
H-C-OH HO-C-H
O O O
HO-C-H HO-C-H HO-C-H
H-C-OH H-C-OH H-C-OH
H-C-OH H-C-OH H-C-OH
CH2-OH COOH CH2-OH
D-glucose D-glucuronic acid D-mannose
H-C=O H-C=O
HO-C-H H-C-OH
H-C-OH HO-C-H
H-C-OH H-C-OH
CH2-OH
CH2-OH
D-arabinose D-xylose

Figure 1.17 Some monomers of hemicellulose. Xylose is always the sugar present in the
largest amount.
 Vegetable Oils, Animal Fats, Carbohydrates and Polyols 15

In contrast to cellulose that is crystalline and resistant to hydrolysis,

hemicellulose has a random, amorphous structure with little strength.
It is easily hydrolyzed by dilute acids or bases as well as by hemicellulase
enzymes.

1.4.4 Lignin
Lignin is found in the cell walls of plants. Lignin constitutes approximately
30–35 wt% of the dry weight of softwoods, about 20–25% of hardwoods and
15–20% of non-woods. Lignin is a branched phenolic natural biopolymer
primarily composed of three phenylpropanoid building units (Figure 1.18).
It is obtained industrially in large quantities especially from kraft pulp-
ing processes in the form of “black liquor.” Because of the abundance of
OH groups in their structure, certain lignins can function as polyol com-
ponents in polyurethane systems. They are mainly used in combination
with other polyols [24, 25].

Example [26]:

In this procedure, 300 parts of a lignin produced from a solvent pulping

process and 700 parts of a polyether polyol are mixed. This mixture is
heated to 93°C to improve the rate of dissolution. The mixing is contin-
ued until a dark solution results. Its viscosity is 1532 centistokes at 38°C.

In addition, depolymerization of lignin is a viable route for the prepara-

tion of low molecular weight products such as polyols, for the preparation of
polyurethanes, phenol formaldehyde resins and epoxy biomaterials [27–30].
Coniferyl alcohol derivatives
Sinapyl alcohol moiety

O
OH
O HO OH
HO OH
OH
OCH3

CH3O OCH3 OCH3

CH3O
OH
OH OH OH
O HO OH
OH
O
OH
HO
p-

OH O
Cu der

OCH3
m iva

O
ar ti

HO
yl ve

O HO
alc
oh

O OCH3
H3C
ol

HO OCH3 O
OCH3
HO O O O
HO
O
O
OH
OH OH CH3 OH CH3
O
OCH3
CH3O OH
O
OCH3
OH
HO OH
OCH3

Lignin structure and components Cumaryl Coniferyl Sinapyl

alcohol alcohol alcohol

Figure 1.18 Lignin and its components.

16 Biobased Polyols for Industrial Polymers

1.4.5 Sucrose
Sucrose (table sugar or saccharose) is a disaccharide of glucose and fruc-
tose. The chemical structures of the latter are shown in Figure 1.19.
Sucrose, the chemical structure of which is shown in Figure 1.20, is
extracted from sugar cane or sugar beet and then purified and crystallized.
Polyols with a sucrose initiator have eight hydroxyl groups. They are
obtained from the propoxylation/ethoxylation of sucrose. Because of their
high functionality they are used in rigid polyurethane foam applications.
The preparation of the first alkoxylated sucrose polyols is disclosed
in several references [31–33]. A general reaction scheme is shown in
Figure 1.21.

In an early patent, the propoxylation of sucrose was carried out as

follows:

About 4.76 kg of sucrose is dissolved in 1 liter of water. About 120 g of

KOH is added and the mixture is heated close to boiling. Then 4.85 kg
of propylene oxide is added under pressure over a period of 3 h. This
is followed by the addition of another 4.85 kg of propylene oxide over

Haworth Cyclohexane Fischer

projection projection projection CH2OH
CHO1

OH
O
6CH2OH H OH H
2
5 O OH 4 6 HO H HO H
5 H O 3 CH2OH OH
4 OH 1 HO H OH O
HO OH 4 H OH
3 H 2 HO
OH 3 2 OH 1 H OH
H H 5 H OH
OH CH2OH
CH2OH
6 OH CH2OH
(β-D-Fructofuranose) Fischer projection
α-D-Glucose Fructose

Figure 1.19 Chemical components of sucrose.

OH

CH2OH O
H O H CH2OH H HO OH
O HO
OH H HO OH
O OH
OH O CH2OH O
H OH OH H OH
OH

Figure 1.20 Chemical structure of sucrose.

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196

Prognosis,

200

Symptoms,

178

Delusions, characters,

187

188

190-192

Mental,

179

190-193
 Moral sense, perversion of,

190

of demented and paralytic form,

187

of hypochondriacal form,

188

Onset, mode of,

178

Physical symptoms,

193

Ataxia,

188

189

,
193

Bones, state,

196

Gait,

194

Handwriting,

183

186

193

Hyperæsthesiæ,

194

Knee-jerk, significance,

195
 Pupils, state,

195

Remissions,

194

Sexual functions in,

195

Speech, alteration in,

194

Urine in,

1195

Prodromal,

178

Temperature in,
179

with melancholia,

188

with mania,

188

Synonyms,

176

Treatment,

201

Cod-liver oil, use,

201

Ergot, use,

201
 Hypophosphites, use,

201

Potassium bromide and iodide, use,

201

Rest and quiet, value,

201

Insanity, chronic alcoholic,

202

from gross lesions of brain,

202

secondary delusional,

203

Terminal dementia,

203
 Treatment,

203

204

States of Mental Defect and Degeneration

138

Circular insanity,

151

Constitutional affective mental disease,

142

Prognosis,

142
 Treatment,

143

Epileptic insanity,

149

Hypochondriacal insanity,

150

Hysterical insanity,

148

149

Idiocy,

138

Classification,

139
 Impulsive insanity, or instinctive monomania,

146

Dipsomania,

147

Erotomania,

147

Homicidal insanity,

147

Nymphomania and satyriasis,

147

Pyromania and kleptomania,

147

Treatment,

148
 Suicidal insanity,

146

Insane temperament,

140

Treatment,

141

Moral insanity,

143

Symptoms,

143-146

Treatment,

146

Periodic insanity,
150

Primary insanity,

151

Prognosis and treatment,

152

Psycho-neuroses

153

Affective mental disease,

153

Prognosis and treatment,

154

Climacteric insanity,
173

Delirium, acute,

163

Dementia, primary,

164

secondary,

165

Treatment,

165

Doubting insanity,

170

Hebephrenia,

171
 Treatment,

172

Hypochondriasis,

154

Prognosis and treatment,

155

Insanity of childhood,

171

Katatonia,

166

Mania,

161

acute,

161
 Treatment,

161

simple,

162

Treatment,

162

Melancholia,

155

Agitata,

158

Duration and prognosis,

159

in children,
158

simple,

155

Treatment,

159

Asylums, removal to,

159

Narcotics and sedatives, use,

160

Tonics, use,

160

with delusions,

156
 with stupor,

158

Menstrual insanity,

173

Primary confusional insanity,

167

Primary delusional insanity,

167

Primary mental deterioration or brain atrophy,

170

Puerperal insanity,

173

Senile dementia,

174
 insanity,

173

Transitory insanity,

164

Mental emotion, influence on causation of neurasthenia,

354

influences as a cause of cerebral anæmia,

780

shocks, influence on causation of general paralysis of the insane,

178

strain, influence on causation of insanity,

118
 symptoms of external pachymeningitis,

705

of general paralysis of the insane,

190

Mercurial tremor,

429

Mercury, use of, in cerebral hyperæmia,

1016

in chronic spinal meningitis,

754

in hæmatoma of the dura mater,

710
 in spinal sclerosis,

900

in tetanus,

555

in tubercular meningitis,

736

Metallic salts, use, in catalepsy,

338

in labio-glosso-laryngeal paralysis,

1175

in progressive unilateral facial atrophy,

702
Metallo-therapy, use, in hysteria,

284

in hystero-epilepsy,

313

Metastasis as a cause of cerebral abscess,

796

Microcephalism,

138

Migraine,

406

1216