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Chemistry and Technology
of Polyols for Polyurethanes,
2nd Edition

Volume 1
Mihail Ionescu
 Chemistry and
Technology of Polyols for
Polyurethanes, 2nd Edition

Volume 1
Mihail Ionescu

A Smithers Group Company

Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom

Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118
http://www.polymer-books.com
 First Published in 2016 by

Smithers Rapra Technology Ltd

Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK

©Smithers Information Ltd., 2016

All rights reserved. Except as permitted under current legislation no part

of this publication may be photocopied, reproduced or distributed in any
form or by any means or stored in a database or retrieval system, without
the prior permission from the copyright holder.

A catalogue record for this book is available from the British Library.

Every effort has been made to contact copyright holders of any material reproduced
within the text and the author and publishers apologise if
any have been overlooked.

ISBN: 978-1-91024-213-1 (hardback)

978-1-91024-214-8 (softback)
978-1-91024-215-5 (ebook)

Typeset by Argil Services

D
edication

This book is dedicated to the memory of Dr Jack Buist, an exceptional personality

in the field of polyurethane chemistry and technology. His vision on the advanced
technologies in the polyurethane industry, his brilliant scientific activity leading to
unanimous worldwide recognition, the exceptional career at ICI Polyurethanes, his
work as founding editor of the international journals, Cellular Polymers and Progress
in Rubber and Plastics Technology has had great impact on the general worldwide
development of polyurethane chemistry and polyurethane technology in the last
five decades of the 20th century. Dr Jack Buist will be forever, one of polyurethane’s
great men and has truly earned his place alongside Professor Otto Bayer, Professor
Kurt C Frisch, Dr Adnan AR Sayigh, Dr Carlo Fiorentini and Dr Guenter Oertel in
the Polyurethane’s Hall of Fame.

iii
Chemistry and Technology of Polyols for Polyurethanes, 2nd Edition, Volume 1

iv
A
cknowledgements

I express my profound gratitude to my wife Adriana for her continuous and

unconditional help and support.

I am grateful to Professor Dr. Zoran S. Petrović, Research Director of Kansas Polymer

Research Center (between 1994–2014), unanimously recognised as a world leader in
the area of renewable polyols and polyurethanes (PU) based on natural compounds,
for his continuous support and capability to open new valuable directions for scientific
investigations.

I thank you very much to my colleagues from Kansas Polymer Research Center:
Dr. Andy Myers, Dr. Ivan Javni, Xianmei Wan, Alisa Zlatanić, Dragana Radojčić,
Nikola Bilić and others for helpful discussions, for synthesis and characterisation of
new renewable polyols and of bio-based PU from these polyols.

I would like to thank Mrs. Helene Chavaroche, Commissioning Editor, and

Mrs. Eleanor Garmson, Development Editor, from Smithers Rapra, for their effort,
high competency and professionalism in producing the 2nd Edition of the book
‘Chemistry and Technology of Polyols for Polyurethanes’ into two high quality
volumes.

v
Chemistry and Technology of Polyols for Polyurethanes, 2nd Edition, Volume 1

vi
P
reface

The first polyurethane(s) (PU) were synthesised by Dr Otto Bayer in 1937 at

IG Farbenindustrie (Germany) by the reaction of a polyester diol with a diisocyanate.
This strategy opened strategy a new path in macromolecular chemistry because
polymers could be synthesised by a new reaction: polyaddition.

PU have a history of slightly more than 75 years. They have become one of the
most dynamic groups of polymers. Their use covers practically all fields of polymer
application: foams, elastomers, thermoplastics, thermorigids, adhesives, coatings,
sealants, and fibres. Furniture, bedding, seating for cars, shoe soles, thermoinsulation
for refrigerators and buildings, wood substitutes, packaging, and coatings, are only
a few common examples of PU use in everyday life.

PU are obtained by the reaction of an oligomeric polyol [low-molecular weight (MW)

polymer with terminal hydroxyl groups] and a diisocyanate (or polyisocyanate). The
structure of the oligomeric polyol used for PU manufacture has a very profound effect
on the properties of the resulting polymer.

A large variety of chemical reactions for the synthesis of oligo-polyols are used to build
the chemical architecture of oligo-polyols. These include: ring-opening polymerisation
of cyclic monomers by anionic, cationic or coordinative mechanisms; polycondensation
reactions (polyesterification, transesterification, Mannich reactions, phenol-aldehydes
condensations); alkoxylation; radical polymerization; transformation of double-bonds
in hydroxyl groups (e.g., epoxydation-hydrolysis, hydroxylation, hydroformylation,
ozonolysis-reduction); oxidation; thiol-ene; amidation reactions. These varieties of
chemical reactions need deep knowledge of organic and macromolecular chemistry.
The author tries to explain, in a very simple and accessible manner, the very complex
phenomena involved in oligo-polyol fabrication.

The scientific literature dedicated to oligo-polyols is really impressive, and most

information is based on patent literature. There are excellent books dedicated to PU,
and an excellent book dedicated to the chemistry and technology of isocyanates. This
monograph, in two volumes, is dedicated to a second, very important component of
PU fabrication: oligo-polyols.

vii
Chemistry and Technology of Polyols for Polyurethanes, 2nd Edition, Volume 1

This book attempts to link, in a general, organized, and systematic manner, the
most important knowledge, data and information concerning the chemistry and
technology of oligo-polyols for PU. This general viewpoint results from the fact that
all oligo-polyols used for PU have many common features. In order not to provide
too much information and to avoid presentation of confidential data, the commercial
names of oligo-polyols are not mentioned. Thus, each oligo-polyol is identified by its
chemical structure or chemical name. Simultaneously and for identical reasons, the
names of companies that developed and produced the various types of oligo-polyols
are not mentioned. The commercial name and company name are specified only for
unanimously accepted and very important developments in oligo-polyols [e.g., Poly
Harnststoff dispersion (PHD)-polyols of Bayer (Germany)].

A decade has passed from the first edition of the book Chemistry and Technology of
Polyols for Polyurethanes. Due to the appreciable amount of new developments in
polyols for PU carried out in 2005–2015, the second edition of the book has been
divided into two volumes. Volume 1 is dedicated to polyols for elastic PU and volume
2 is dedicated to polyols for rigid PU.

Supplies of crude oil and petrochemical raw materials are limited and, in 50–100
years, may be finished. However, raw materials from natural resources have practically
infinite renewability.

Petrochemical polyols (polyethers and polyesters) remain stable and are the
most important polyols for elastic PU. Polyols for elastic PU, irrespective of their
structure, are characterised by high molecular weight (2,000-6,000 daltons) and low
functionality (2–3 hydroxyl groups/mol). Reaction of these long-chain polyols with
diisocyanates results in highly elastic PU.

Volume 1 of the second edition details the main knowledge regarding the synthesis
of the most important oligo-polyols for preparation of elastic PU (polyether polyols,
graft polyether polyls, PHD, polyisocyanate polyaddition polyols, polyester polyols,
polytetramethylene glycols, polybutadiene polyols, acrylic polyols, polysiloxane
polyols). New developments in petrochemical polyether polyols, such as the most
important polyols for elastic PU (e.g., synthesis of high solid content graft polyols;
continuous processes for the synthesis of polyether polyols with double metal cyanide
catalysts) are described.

Covering all aspects and describing all the oligo-polyol structures created from
companies, universities, research centers and institutes is not possible. Nevertheless,
the most important aspects of oligo-polyols for manufacture of elastic PU are
presented.

viii
 Preface

This monograph is addressed to all specialists working in PU: students; researchers;

scientists; engineers; professors; experts from industry, universities, research centers
and research institutes.

I hope that the monograph will be the start of novel developments in oligo-polyols
for elastic PU. I hope that this will lead to creation of new oligo-polyols with new
designs and new chemical architectures, as well as new (and possibly unconventional)
manufacturing technologies. Good luck in your endeavours!

Mihail Ionescu

February 2016

ix
Chemistry and Technology of Polyols for Polyurethanes, 2nd Edition, Volume 1

x
C
ontents

1. Polyols........................................................................................................ 1
1.1 Introduction..................................................................................... 1

2 Basic Chemistry of Polyurethanes.............................................................. 15

2.1 Reaction of Isocyanates with Alcohols........................................... 15
2.2 Reaction of Isocyanates with Water............................................... 16
2.3 Reaction of Isocyanates with Urethanes......................................... 17
2.4 Reaction of Isocyanates with Urea Groups.................................... 18
2.5 Reaction of Isocyanates with Carboxylic Acids.............................. 18
2.6 Dimerisation of Isocyanates........................................................... 19
2.7 Trimerisation of Isocyanates.......................................................... 19
2.8 Reaction of Isocyanates with Epoxide Compounds........................ 20
2.9 Reaction of Isocyanates with Cyclic Anhydrides............................ 20
2.10 Prepolymer Technique.................................................................... 26
2.11 Quasiprepolymer Technique.......................................................... 27
2.12 One-Shot Technique....................................................................... 28
2.13 Several Considerations on the Polyaddition Reaction.................... 29

3 General Characteristics of Oligo-Polyols................................................... 33

3.1 Hydroxyl Number......................................................................... 34
3.2 Functionality.................................................................................. 36
3.3 Molecular Weight and Molecular Weight Distribution . ................ 41
3.4 Equivalent Weight.......................................................................... 44
3.5 Water Content............................................................................... 44
3.6 Primary Hydroxyl Content............................................................ 45

xi
Chemistry and Technology of Polyols for Polyurethanes, 2nd Edition, Volume 1

3.7 Reactivity....................................................................................... 49
3.8 Specific Gravity.............................................................................. 51
3.9 Viscosity........................................................................................ 51
3.10 Colour........................................................................................... 52
3.11 Acid Number................................................................................. 52
3.12 Renewable Content........................................................................ 53

4 Polyether Polyols for Elastic Polyurethanes............................................... 59

4.1 Polyalkylene Oxide Polyether Polyols............................................ 59
4.1.1 Synthesis of Polyether Triols Based on Glycerol
Homopolymers of Propylene Oxide.................................. 68
4.1.1.1 Anionic Propylene Oxide Polymerisation
Reaction Initiated by Glycerol............................ 69
4.1.1.2 Transfer Reactions in Anionic Polymerisation
of Alkyleneoxides............................................... 71
4.1.2 Kinetics of Propylene Oxide Addition to Glycerol ........... 81
4.1.2.1 General Considerations....................................... 81
4.1.2.2 Kinetics of Propylene Oxide and Ethylene
Oxide Anionic Polymerisation (Propagation
Reaction)............................................................ 84
4.1.3 Random Copolyethers Propylene Oxide–Ethylene Oxide
(Heteropolyether Polyols) .............................................. 100
4.1.3.1 Other Random Copolyethers Obtained by
Anionic Polymerisation..................................... 106
4.1.4 Polyether Polyols Block Copolymers Propylene Oxide–
Ethylene Oxide............................................................... 109
4.1.4.1 Synthesis of Polyether Polyols, Block
Copolymers Propylene Oxide–Ethylene Oxide
with Terminal Poly[EO] Block.......................... 109
4.1.4.1.1 The Effect of the Catalyst
Concentration on the Primary
Hydroxyl Content................................ 115

xii
 Contents

4.1.4.1.2 The Effect of Ethylene Oxide Addition

Rate on the Primary Hydroxyl
Content................................................ 116
4.1.4.1.3 The Effect of Ethoxylation Temperature
on the Primary Hydroxyl Content........ 117
4.1.4.1.4 The Effect of the Catalyst Nature on
the Primary Hydroxyl Content............. 118
4.1.4.1.5 Removing Propylene Oxide before the
Ethoxylation Reaction.......................... 120
4.1.5 Technology for Polyether Polyol Fabrication................... 128
4.1.5.1 Preparation of Starter-Catalyst Solution............ 129
4.1.5.2 Anionic Polymerisation of Alkylene Oxides
Initiated by Polyolic Starters............................. 129
4.1.5.3 Digestion.......................................................... 138
4.1.5.4 Degassing.......................................................... 138
4.1.5.5 Polyether Polyols Purification........................... 138
4.1.5.5.1 Neutralisation with Acids of
Poptassium Hydroxide, Followed by
the Crystallisation of the Resulting
Potassium Salts and Filtration.............. 140
4.1.5.5.2 Treatment with Adsorbents.................. 140
4.1.5.5.3 Treatment with Solid Inorganic
Compounds.......................................... 141
4.1.5.5.4 Treatment with Ion Exchange Resins.... 141
4.1.5.5.5 Polyether Polyol Purification by
Extraction Processes............................. 142
4.1.5.5.6 Other Methods of Polyether
Purification........................................... 142
4.1.5.6 Polyether Polyols Stabilisation.......................... 143
4.1.5.6.1 The Problem of the Presence of
High-Molecular Weight Polypropylene
Oxide in Propylene Oxide Monomer.... 146
4.1.5.7 The Problem of Colour in Polyether Polyol
Fabrication....................................................... 147

xiii
Chemistry and Technology of Polyols for Polyurethanes, 2nd Edition, Volume 1

4.1.5.7.1 The Oxygen Content in the Inert Gas... 147

4.1.5.7.2 The Propionaldehyde Content of
Propylene Oxide Monomer (or
Acetaldehyde in Ethylene Oxide) and
the Aldehyde Content of Starter........... 147
4.1.5.7.3 Effect of the Purification Step on the
Polyether Polyol Colour....................... 148
4.1.5.8 The Problem of Odour of Polyether Polyols...... 149
4.1.5.9 Considerations of the ‘Scorching’
Phenomenon..................................................... 154
4.2 Anionic Polymerisation of Alkylene Oxides Catalysed by
Phosphazenium Compounds........................................................ 158
4.3 High-Molecular Weight Polyether Polyols Based on Polyamine
Starters: Autocatalytic Polyether Polyols...................................... 163

5 Synthesis of High-Molecular Weight Polyether Polyols with Double

Metal Cyanide Catalysts......................................................................... 177
5.1 Continuous Process for Synthesis of Polyether Polyols with a
Double Metal Cyanide Catalyst (IMPACT Catalyst Technology,
a Greener Polyether Polyols Process)............................................ 189

6 Polymer Polyols (Filled Polyols).............................................................. 197

6.1 Graft Polyether Polyols................................................................ 198
6.2 The Chemistry of the Graft Polyether Polyol Synthesis................ 199
6.2.1 Generation In Situ of Non-Aqueous Dispersant by
Grafting Reactions.......................................................... 205
6.2.2 Stabilisation of Polymer Dispersions in Polymer Polyols
with Macromers (Reactive Non-Aqueous Dispersant).... 209
6.2.3 Non-reactive Non-Aqueous Dispersants......................... 217
6.2.4 The Mechanism of Polymer Particle Formation in
Polymer Polyols Synthesis by Radical Polymerisation..... 219
6.3 The Technology of Polymer Polyols Manufacture by Radical
Processes...................................................................................... 222
6.3.1 Graft Polyether Polyols with High Solid Content............ 227
6.3.1.1 Synthesis of a Macromer................................... 229

xiv
 Contents

6.3.1.2 Synthesis of a Preformed Stabiliser.................... 231

6.3.1.3 Synthesis of Graft Polyether Polyols.................. 232
6.3.2 Synthesis of Polymer Polyols by using Preformed
Aqueous Polymeric Lattices............................................ 234
6.4 Poly Harnststoff Dispersion Polymer Polyols (Polyurea
Dispersions)................................................................................. 235
6.5 Polyisocyanate Polyaddition Polymer Polyols.............................. 240
6.6 Other Polymer Polyols................................................................. 243
6.7 Epoxy Dispersions....................................................................... 244
6.7.1 Polyamide Dispersions.................................................... 245
6.7.2 Aminoplast Dispersions.................................................. 246

7 Polyether Polyols by Cationic Polymerisation Processes.......................... 255

7.1 Polytetrahydrofuran (Polytetramethylene Glycols)....................... 255
7.2 High-Molecular Weight Polyalkylene Oxide Polyols by
Cationic Polymerisation............................................................... 266
7.3 Polyether Diols and Triols, Copolymers Tetrahydrofuran-
alkylene Oxides........................................................................... 270

8 Polyester Polyols for Elastic Polyurethanes.............................................. 285

8.1 Chemistry of Polyester Polyol Synthesis....................................... 286
8.2 Consideration of the Kinetics of Polyesterification Reactions....... 293
8.2.1 Self-Catalysed Polyesterification Reactions (Without
Catalyst)......................................................................... 293
8.2.2 Side Reactions in Polyesterification................................. 297
8.2.3 Hydrolysis Resistant Polyester Polyols............................ 299
8.3 Technology for Polyester Polyols Fabrication............................... 300
8.4 Poly(ε-caprolactone) Polyols........................................................ 303
8.5 Polycarbonate Polyols.................................................................. 309

9 Polybutadiene Polyols............................................................................. 319

9.1 Polybutadiene Polyols by Radical Polymerisation of Butadiene.... 319

xv
Chemistry and Technology of Polyols for Polyurethanes, 2nd Edition, Volume 1

9.2 Synthesis of Polybutadiene Polyols by Radical Polymerisation

of Butadiene................................................................................. 323
9.3 Synthesis of Polybutadiene Polyols by Anionic Polymerisation
of Butadiene................................................................................. 326

10 Acrylic Polyols........................................................................................ 331

11 Polysiloxane Polyols................................................................................ 337

Postface.............................................................................................................. 343

Abbreviations..................................................................................................... 345

Index ............................................................................................................... 349

xvi
1
Polyols

1.1 Introduction

Polyurethanes (PU) are a special group of heterochain polymers characterised

by the following structural unit [1–33]:

OCONH R NHCOO R′
n

Structure 1.1 General chemical structure of PU

The urethane groups -NH-COO- are esters of carbamic acid, a hypothetically

unstable (and impossible to obtain under normal conditions) acid [R-NH-
COOH]. One can synthesise urethane groups by various methods [22], but the
most important method is the reaction between an isocyanate and an alcohol
(Reaction 1.1) [1–33]:

R N C O + HO R′ R NHCOO R′
Isocyanate Alcohol Urethane (1.1)

The first urethane was synthesised by this route as early as 1849 by Wurtz [6, 16,
22, 30]. In 1937, after very systematic and intensive research work at IG Farben
(Interessen-Gemeinschaft Farbenindustrie AG, Germany), Dr. Bayer synthesised the
first PU by reaction of a diisocyanate with a polyester having two terminal hydroxyl

1
Chemistry and Technology of Polyols for Polyurethanes, 2nd Edition, Volume 1

groups (called a ‘polyester diol’: an α,ω-telechelic polymer with terminal hydroxyl

groups) [1, 2] (Reaction 1.2):

n
n
O C N R N C O + HO OH
Diisocyanate Polyester diol

OCONH R NHCOO O
n
PU (1.2)

In fact, Bayer invented a new method for the synthesis of macromolecular

compounds, the ‘polyaddition reaction’, which is a special case of polycondensation,
with the difference that the reaction product is exclusively the polymer. In classical
polycondensation reactions, the products are the polycondensation polymer
and a low-molecular-weight (MW) compound (water, alcohols and so on). The
fact that in the polyaddition reactions the only product is the polymer is of great
technological importance, especially for the purity and morphology of the resulting
macromolecular compound.

In slightly more than 75 years of the existence of PU, except for the global
financial recession during 2008–2010, the growth of PU was constant.
Predictions for the future are very optimistic due to the new markets opened in
Eastern Europe, Asia and South America [34–36]. China has become an important
‘player’ in the PU industry. In terms of worldwide polymer consumption,
China produces 35.5% of PU, 33.3% of 2,4-toluene diisocyanate, and 33.3%
of diphenylmethane diisocyanate, and has important capacities for production
of polyether polyols and polyester polyols [35, 36].

In Figure 1.1, one can see the growth of PU consumption between 2012 and 2014.

PU represent only 5% of the worldwide consumption of polymers (Figure 1.2),

but the dynamics of their growth is constantly high ( ≈ 5–6%) [35–37].

2
 Polyols

22,000,000
20,000,000

18,000,000
16,000,000

14,000,000
Tonnes

12,000,000
10,000,000

8,000,000
6,000,000
4,000,000
2,000,000

0
2004 2012 2013 2014 2015

Figure 1.1 Global production of PU (2004–2015) [35–37]

Thermosets
15% PU 5%
Other
thermoplastics Polyethylene
13% 29%

Polyvinyl Polypropylene
chloride 12%
Polystyrene 9%
17%

Figure 1.2 PU and worldwide production of plastics

3
Chemistry and Technology of Polyols for Polyurethanes, 2nd Edition, Volume 1

Figure 1.3 shows the worldwide consumption of polyether polyols and polyester
polyols for PU in 2012–2014 [35–37].

Global production of polyether and polyester

polyols (2004-2014)
8,000

7,000

6,000

5,000
Kilo tonnes

4,000 Polyether

3,000 Polyester

2,000

1,000

0
2004 2012 2013 2014

Figure 1.3 Global production of polyether and polyester polyols for PU in

2004–2014 [35–37]

The main field of application of PU is the furniture industry. Around 30% of

the total PU produced worldwide is used for the production of mattresses from
flexible slabstock foams. Automotive manufacture is the second most important
application for flexible and semiflexible PU (seat cushioning, bumpers, sound
insulation, etc.). Rigid PU foams are used in thermal insulation of buildings and
refrigerators, cold stores, pipe insulation, refrigerated transport, a s w e l l a s
thermal insulation in chemical and food industries. PU elastomers are used for shoe
soles, athletic shoes, pump and pipe linings, industrial tyres, and microcellular
elastomers. PU adhesives, sealants, coatings, binders and fibres represent another
group of PU with specific applications. Main applications of PU are presented
in Figure 1.4 [36, 38].

4
 Polyols

Figure 1.4 shows that most PU used worldwide are foams (flexible, semiflexible,
rigid foams), and ≈69–70% of total PU. In 2004–2014, worldwide production of
CASE (coatings, adhesives, sealants, elastomers, binders) surpassed the worldwide
production of rigid PU foams.

Adhesives
Coatings 4%
13% Flexible
foams
39%

Rigid
foams
26%

Binders
Elastomers Sealants 4%
12% 2%

Figure 1.4 Main applications of PU (2013) [36]

A foam is a composite solid–gas material. The continuous phase is the PU polymer

and the discontinuous phase is the gas phase. PU are an extremely versatile group
of polymers produced in a wide range of densities, crosslink densities and stiffness,
from very soft to very hard structures (Figure 1.5).

Upon consideration of practical and applicative reasons, PU can be divided into two
main categories: elastic (e.g., flexible foams, elastomers, coatings, adhesives, fibres),
and rigid (e.g., rigid PU foams, structural foams, wood substitutes, solid PU). This
common classification of PU is based mainly on the oligo-polyol structure. Thus,
the general reaction for the PU synthesis is:

Reaction 1.3 shows the general reaction for synthesis of crosslinked PU:

5
Chemistry and Technology of Polyols for Polyurethanes, 2nd Edition, Volume 1

Rigid
PU
Crosslink (28%) Rigid PU foams
density Structural foams
Wood substitute
Solid PU

Elastic Semiflexible PU foams

PU Integral skin foams
(72%)
Flexible PU foams
Microcellular elastomers
Adhesives, coatings, sealants
PU elastomers PU fibres Paints

Soft Hard
Stiffness

Figure 1.5 Classification of PU as a function of crosslink density and stiffness

OH n
OCN R NCO HO
Diisocyanate +

HO
Oligo-polyol

OCOHN R NHCOO n
OCOHN R NHCOO

n = 0,1,2.......6

OCOHN R NHCOO

PU

where = polyether chain, polyester chain, polyhydrocarbon chain

(1.3)

6
 Polyols

The MW of the oligo-polyols used in PU synthesis is 300–12,000 daltons (Da),

which is in the region of low- MW polymers (oligomers), In general, the number
of hydroxyl groups/molecule of oligo-polyol (oligo-polyol functionality) i s 2–8
OH groups/mol.

Polyols of low functionality, having ≈2–3 hydroxyl groups/mol and with a high-MW
of 2,000–12,000 Da, lead to an elastic PU. In contrast, a low-MW oligo-polyol of
300–1,000 Da with high functionality of ≈3–8 hydroxyl groups/mol leads to a rigid
crosslinked PU.

Diisocyanate reacted with a high- MW diol (e.g., a polyether or polyester diol of

MW of 2,000–4,000 Da) leads to very elastic linear PU (PU elastomers) [3, 6,
13, 14, 24, 25]. Urethane linkages (and urea linkages) generate the ‘hard domain’
or ‘hard segment’ of a PU elastomer because of the possibility of association
by hydrogen bonds. The high mobility of high- MW polyol chains represent the
‘soft domain’ or ‘soft segment’, and ensure the high elasticity of the resulting PU
elastomer (Figures 1.6 and 1.7).

Hard domain Soft domain

N C O

C N
H O
Hydrogen bonds
O H
O H
H O
C N
N C O N C O

H O

Figure 1.6 ‘Hard domains’ and ‘soft domains’ of PU elastomers

7
Chemistry and Technology of Polyols for Polyurethanes, 2nd Edition, Volume 1

Hard domains

Soft
domain

Figure 1.7 ‘Virtually’ crosslinked PU elastomers

Interestingly, this structure is virtually crosslinked by secondary bonds (hydrogen

bonds). At high temperatures, the hydrogen bonds are destroyed and the linear
PU elastomer can be processed in the melt state, in a similar way to all common
thermoplastics (thermoplastic elastomers) [3–10, 23–25, 29].

A polyol of high-MW (3,000–6,500 Da) and with low functionalityof ≈2–3 hydroxyl
groups/mol, if reacted with a diisocyanate, leads to a low-crosslinked, flexible PU
structure. This structure is characteristic of flexible PU foams. The resulting
structure is crosslinked, s o the MW of the resulting PU is infinite in value. Only
linear PU have a finite and determinable MW.

In Figure 1.8, one can see a hypothetical crosslinked structure of a flexible PU foam
resulting from an oligo-triol with a MW of 3,000–6,500 Da and a diisocyanate
[3–16, 20].

The rigid structures of PU are created using low-MW polyols (150–1,000 Da)
that have high functionalities of ≈3–8 hydroxyl groups/mol. By reacting these
low-MW oligo-polyols of high functionality with a diisocyanate or polyisocyanate
(having 2–3 –NCO groups/mol), a hard, rigid PU structure is obtained (Figure
1.9). This high rigidity is an immediate consequence of the high crosslink density of
the resulting PU polymer [3–6, 10, 11, 14, 39]. Figure 1.9 shows a hypothetical,
highly crosslinked structure of a rigid PU.

8
 Polyols

O O O O O
H H
= O C HN R NH C O or O C HN R N C N R NH C O

Urethane bond Urea bond

= oligo-polyol chain

Figure 1.8 Hypothetical crosslinked structure of a flexible PU foam

a b

Figure 1.9 Crosslinking in rigid PU foams. a) short chain derived from 1

OH group (polyether, polyester and so on) and b) urethane or urea derived
from diisocyanate (toluene diisocyanate, diphenylmethane diisocyanate) or
polyisocyanate

9
Chemistry and Technology of Polyols for Polyurethanes, 2nd Edition, Volume 1

Several general aspects of the profound influence the oligo-polyol structure has on
the properties of the resulting PU have been discussed briefly in this chapter. To
understand fully the role of the polyol structure on PU properties, the method of
chemical insertion of oligo-polyol into PU macromolecules will be discussed in
Chapter 2 with the most important aspects of PU chemistry. Then, the general
and common characteristics of oligo-polyols for PU will be presented. Subsequent
chapters will deal with a detailed presentation of the main types of oligo-polyols
for PU, as well as the chemistry and technology of these oligo-polyols (including
their manufacture). Oligo-polyols are presented in two main groups: oligo-polyols
for elastic PU and oligo-polyols for rigid PU. The final chapter details all knowledge
concerning oligo-polyols, and describes the relationship between oligo-polyol
structure and properties of the final PU.

References

1. O. Bayer, Angewandte Chemie, 1947, A59, 257.

2. O. Bayer, Modern Plastics, 1947, 24, 149.

3. Polyurethane Technology, Ed., P.F. Bruins, Interscience Publishers, London,

UK, 1969.

4. The ICI Polyurethanes Book, 2nd Edition, Ed., G. Woods, John Wiley & Sons,
Chichester, UK, 1990.

5. Telechelic Polymers, Synthesis and Applications, Ed., E.J. Goethals, CRC

Press, Boca Raton, FL, USA, 1989, p.203.

6. M. Szycher in Szycher’s Handbook of Polyurethanes, CRC Press,

Boca Raton, FL, USA, 1999.

7. Advances in Polyurethane Technology, Eds., J.M. Buist and H.A. Gudgeon,

Maclaren and Sons, London, UK, 1968.

8. S.D. Gagnon in Kirk-Othmer Encyclopedia of Chemical Technology,

4th Edition, Ed., J.I. Kroschowitz, John Wiley & Sons, New York, NY,
USA, 1996, 19, 7 22.

9. H. Ulrich in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition,

Ed., J.I. Kroschowitz, , John Wiley & Sons, New York, NY, USA, 1997, 24,
695.

10
 Polyols

10. J.H. Saunders and K.C. Frisch in Polyurethanes: Chemistry and Technology,
Part I, Interscience Publishers, New York, NY, USA, 1962.

11. J.H. Saunders and K.C. Frisch in Polyurethanes: Chemistry and

Technology, Part II, Interscience Publishers, New York, NY, USA, 1964.

12. Handbook of Polymeric Foams and Foam Technology, Eds., D. Klempner

and K.C. Frisch, Hanser, Munich, Germany, 1991.

13. Plastic Foams, Eds., K.C. Frisch and J.H. Saunders, Marcel Dekker,
New York, NY, USA, 1972.

14. Polyurethane Handbook, Ed., G. Oertel, Hanser Verlag, Munich,

Germany, 1985.

15. Developments in Polyurethanes – I, Ed., J.M. Buist, Applied Science

Publishers, London, UK, 1978.

16. Flexible Polyurethane Foams, 2nd Edition, Eds., R. Herrington and K. Hock,
Dow Chemical Company, Midland, MI, USA, 1997.

17. H. Ulrich in Reaction Polymers, Eds., W.F. Gum, W. Riese and H. Ulrich,
Hanser Publishers, New York, NY, USA, 1992, p.50.

18. A.A.R. Sayigh, H. Ulrich and W.J. Farrisey in Condensation Monomers,

Eds., J.K. Stille and T.W. Campbell, Wiley Interscience, New York, NY,
USA, 1972, p.231.

19. Analytical Chemistry of the Polyurethanes, Eds., D.J. David and H.B. Staley,
Wiley Interscience, New York, NY, USA, 1969, Volume 16, Part III, High
Polymers.

20. G.W. Woods in Flexible Polyurethane Foams, Chemistry and Technology,

Applied Science Publishers, Englewood, NJ, USA, 1982.

21. H. Ulrich in Encyclopedia of Polymer Science and Engineering, Ed.,

J.I. Kroschowitz, John Wiley & Sons, Inc., New York, NY, USA, 1987, 8,
448.

22. H. Ulrich in Chemistry and Technology of Isocyanates, John Wiley &

Sons, Chichester, UK, 1996.

11
Chemistry and Technology of Polyols for Polyurethanes, 2nd Edition, Volume 1

23. G. Woods in Polyurethanes, Materials, Processing & Applications, Rapra

Review Report No. 15, Smithers Rapra Technology, Shawbury, Shropshire,
UK, 1988.

24. A.F. Johnson, P.D. Coates and M.W.R. Brown in Reactive Processing of
Polymers, Rapra Review Report No. 73, Smithers Rapra Technology,
Shawbury, Shropshire, UK, 1994.

25. J.A. Brydson in Thermoplastic Elastomers – Properties and Applications,

Rapra Review Report No. 81, Smithers Rapra Technology, Shawbury,
Shropshire, UK, 1995.

26. MDI and TDI: Safety, Health and the Environment - A Source Book and
Practical Guide, Eds., D.C. Allport, D.S. Gilbert and
S.M. Outterside, Wiley Publishers, Chichester, UK, 1998.

27. R.M. Evans in Polyurethane Sealants, Technology and Applications,

2nd Edition, Technomic Publishing, Lancaster, PA, USA, 1993.

28. B.A. Dombrow in Polyurethanes, 2nd Edition, Reinhold Publishing

Corporation, New York, NY, USA, 1965.

29. Kunststoff–Handbook, Volume 7, Polyurethane, Eds., R. Vieveg and

A.Höchtlen, Carl Hanser Verlag, Munich, Germany, 1966. [In German]

30. Houben Weyl: Methoden der Organische Chemie, Eds., E. Muller, O. Bayer,
H. Meerwein and K. Ziegler, Georg Thieme Verlag, Stuttgart, Germany,
1963, 14, 2, 57. [In German]

31. Ullmanns Encyklopädie der Technischen Chemie, 4th Edition, Eds.,

E. Bartholome, E. Biekart, H. Hellman, H. Ley, M. Wegert and E. Weise,
Verlag Chemie, Munich, Germany, 1980, p.31.

32. Ullmanns Encyklopädie der Technischen Chemie, 4th Edition, Eds.,

E. Bartholome, E. Biekart, H. Hellman, H. Ley, M. Wegert and E. Weise,
Verlag Chemie, Munich, Germany 1980, p.297.

33. Ullmanns Encyklopädie der Technischen Chemie, 4th Edition, Eds.,

E. Bartholome, E. Biekart, H. Hellman, H. Ley, M. Wegert and E. Weise,
Verlag Chemie, Munich, Germany 1980, p.302.

34. Proceedings of an International Symposium on 60 Years of Polyurethanes,

1998, Detroit, MI, USA.

12
Another random document with
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 to that time. Consult also Dreschfeld, Brain, July, 1884, and January, 1886.

Hun concludes that alcoholic paralysis may be regarded as a special

form of disease with the following symptoms: “Neuralgic pains and
paræsthesiæ of the legs, gradually extending to the upper
extremities, and accompanied at first by hyperæsthesia, later by
anæsthesia, and in severe cases by retardation of the conduction of
pain. Along with these symptoms appears muscular weakness,
which steadily increases to an extreme degree of paralysis, and is
accompanied by rapid atrophy and great sensibility of the muscles to
pressure and to passive motion. Both the sensory and motor
disturbances are symmetrically distributed. The paralysis attacks
especially the extensor muscles. In addition to these motor and
sensory symptoms, there is also a decided degree of ataxia. The
tendon reflexes are abolished, and vaso-motor symptoms, as
œdema, congestion, etc., are usually present. Symptoms of mental
disturbance are always present in the form of loss of memory or
transient delirium.”

Lesions of the cord are absent, but degenerative processes in the

peripheral nerves have been discovered in a number of cases. The
symptoms are those of multiple neuritis, and the essential lesions
consist in degenerative changes in the peripheral nerve-fibres. The
associated mental derangement, tremor, and ataxia have been
ascribed to changes in the cerebral cortex.

Dreschfeld has divided the cases, according to the more prominent

symptoms, into two clinical groups—alcoholic ataxia and alcoholic
paralysis.

The ataxic form represents a milder type. The symptoms are

lancinating and shooting pains in the lower extremities, sometimes in
the upper, with areas of anæsthesia and retarded sensibility. The
muscles are painful upon pressure, and atrophy may be moderate or
absent altogether. Inco-ordination is marked. The tendon reflexes
are absent. Shooting pains down the legs to the toes of a
paroxysmal character, and followed by a sense of numbness, also
occur. Eye symptoms are wanting.
The paralytic form is usually associated with atrophy, affecting chiefly
the extensors of the fingers and toes. The paralysis and atrophy in
some cases come on acutely, in others more slowly. When the
patients come under observation they are usually unable to stand or
walk, and it is therefore not easy to make out whether or not the
paralytic stage has been preceded by a stage of ataxia. As the
sensory phenomena in these cases are the same as in the first
group, it is probable that pseudo-ataxic symptoms have preceded
the slowly oncoming paralysis. Paralysis and atrophy of the
extensors of the fingers and toes, with paresis of the other muscles,
are associated with the sensory phenomena above described.
Tendon reflexes are absent; the superficial reflexes are much
diminished. Recovery takes place in a considerable proportion of the
cases upon the withdrawal of alcohol. The atrophy and paralysis
pass away altogether, the tendon reflexes are restored, and the
disturbances of sensation disappear. In the greater number of these
cases persistent delusions are present.

Lancereaux45 describes alcoholic paralysis as symmetrical, affecting

either the upper or lower extremities and gradually extending toward
the trunk. The lower extremities are invariably more affected than the
upper, and the extensor than the flexor muscles. There is diminished
reaction to electricity, and anæsthesia is present. The brain and
spinal cord are normal, but the peripheral nerves show extensive
degenerative changes.
45 Gazette des Hôpitaux, No. 46, 1883.

4. Disorders of the Special Senses.—a. The Sight.—Disorders of

vision are among the most frequent and the earliest symptoms of
chronic alcoholism. Phosphenes, scintillations, sensations of
dazzling, muscæ volitantes, and streams of light are often
complained of. These phenomena may be constant or transient.
Diplopia and other visual disturbances of the most irregular and
annoying character also occur. Sometimes there is dyschromatopsia;
the colors are confounded: red appears brown or black, and green
appears gray, etc. In the more advanced stages amblyopia may
occur. The acuity of vision rapidly diminishes, sometimes to the point
that the patient with difficulty distinguishes the largest print. Objects
appear as seen through a fog, and their outlines are distinguished
only after repeated and close effort. Again, blindness almost
absolute occurs for the course of some minutes—passes away
rapidly, only to return again at intervals. Not infrequently the sight is
better in the morning and evening than during the day.
Achromatopsia, characterized by enfeeblement, and not infrequently
by the momentary loss of the power to recognize colors, and
particularly the secondary tints, also occurs. Cases of Daltonism
occasionally seem to depend, to some extent at least, upon alcoholic
disturbances of vision. Impairment of the power to distinguish colors
must not, however, be confounded with the difficulty experienced by
many alcoholic subjects in recognizing different colors successively
presented to the eye with some degree of rapidity. Such individuals
are able to distinguish colors when sufficient time is permitted them.
Their difficulty depends upon tardiness of perception, such as is
often experienced by neurasthenic subjects in recognizing faces in a
crowd, rather than upon any failure in the power of recognizing
colors. As a rule, the disorders of vision are not permanent, at least
in the beginning. Later, they are of longer duration, and alcoholic
amblyopia occasionally degenerates into irremediable amaurosis.
Ophthalmoscopic examination reveals at first no appreciable lesion,
and the disturbance of circulation, venous stasis, and peri-papillary
infiltration thus observed appear to be inadequate to explain the
visual disturbance. Atrophy of the optic nerve occasionally occurs as
a direct result of alcoholism. Nystagmus has been frequently
observed. The state of the pupils is variable and without constant
relation to the acuity of vision. The pupils are not infrequently
uniformly dilated, contracting slowly under the influence of light.
More rarely they are permanently contracted; occasionally they are
unequal. These modifications are often without demonstrable
relation to anatomical lesions.46
46 Vide this System of Medicine, Vol. IV. p. 803.
b. The Hearing.—The disturbances of hearing encountered in
chronic alcoholism are in many respects analogous to those of sight.
Patients complain of curious subjective sensations, which are
described as humming or whistling sounds, the ringing of bells,
music, or the murmur of a crowd. At times the sense of hearing is so
exquisite that the least noise causes pain. On the other hand,
hearing may be greatly impaired, diminishing by degrees until it
becomes in some cases, without recognizable lesion, almost or
completely lost.

c. The Taste.—As a rule, the sense of taste is impaired in chronic

alcoholism; occasionally it is wholly lost.

d. The Smell.—The sense of smell is in most cases to some extent,

and in many cases greatly, impaired, the most powerful odors being
scarcely perceived by old topers.

Alcoholic Epilepsy.—Alcohol, and especially that combination of

alcohol with oil of wormwood and aromatics known as absinthe, is
capable of producing convulsive seizures resembling epilepsy.
Certain forms of alcoholic convulsions can scarcely be distinguished
from ordinary epilepsy. Acute alcoholism may be an exciting cause
of the convulsive seizures in an epileptic. Alcoholic epilepsy is,
however, peculiar to chronic alcoholism, and particularly in
individuals in whom there is an hereditary tendency to nervous
disorders. Once established, alcoholic epilepsy may continue even
after the alcoholic habit has been discontinued. The attack is usually
followed by marked mental disturbances. These vary from profound
dulness to stupor or mania; they last from some hours to several
days, and present the characters of similar conditions following non-
alcoholic epileptic paroxysms.

C. PSYCHICAL DERANGEMENTS.—Yet more important than the visceral

and nervous lesions of chronic alcoholism are the indications which it
affords of a progressive debasing influence upon the mind. The
moral sense, the will, and the intellect are involved successively in a
process of deterioration, which, manifesting itself only in part and by
little at first, becomes after a time general and plain to all the world,
and ends at length in ruin more complete and more hopeless than
that of the body. Indeed, it not infrequently happens that while the
general health appears to be good and the nervous system, save in
transient disturbances of function, presents no evidence of the toxic
action of alcohol upon its tissues, serious psychical disorders are
established. The alcoholic subject develops propensities, otherwise
latent, that tend to refer him to the criminal or the insane classes of
society. The psychical debasement, of which these propensities are
the outcome, is, like the alcohol habit itself, progressive. This fact
cannot be too strongly insisted upon. Like the loss of vascular tone,
the sclerosis, the steatosis which alcohol induces in the body, this
mental deterioration is cumulative and destructive. It is to its
psychical manifestations that alcoholism owes its chief importance,
not only as a study in pathology, but also as a problem of the gravest
moment in social science.

1. The Moral Sense.—Deterioration of the sense of moral obligation

is among the earlier of the mental phenomena of alcoholism. The
moral sense is perverted and enfeebled. Sentiments of honor, of
dignity, of reputation, and of decency are no longer cherished or
regarded. The amenities of social life and the proprieties of personal
conduct are disregarded or set at naught. He who was punctilious,
considerate, and thoughtful becomes negligent, selfish, and
indifferent to sentiments of honor and emulation; he gives himself up
to indulgences formerly considered unworthy; his reputation and that
of his family are no longer matters of concern to him; respect for
public opinion is replaced by cynicism. Little by little the conception
of duty, of justice, of honor are lost to him, or if he regards them at all
it is rather as subjects for idle and purposeless discussion than as
motives to regulate his life. These changes are gradual and
progressive, their evolution being largely influenced by the hereditary
traits and previous moral culture of the individual. The deterioration
of the sense of right, and the coincident exaltation of those passions
which are normally under its control, lead to the commission of the
crimes peculiar to the early period of alcoholism. Indifference is
another characteristic of this period—indifference not incompatible
with a selfishness of the most intense kind. The sense of obligation
to the family is forgotten, and the responsibility of providing for and
caring for others is unfelt. If the drunkard's own wants, and
especially his craving for drink, are gratified, the necessities of those
formerly dear fail to move him. The affections are not only enfeebled,
but they are also perverted; not rarely they are replaced by aversion,
disdain, and hatred. The individual who has been calm, reasonable,
and patient becomes excitable, perverse, and intolerable of
contradiction or opposition. Prone to acts of sudden violence, he
becomes gloomy, taciturn, and preoccupied. He is disturbed by fixed
tormenting ideas or by vague pursuing terrors. He thus becomes
self-conscious, irritable, fault-finding, and easily provoked to passion.
The character, after a time, undergoes still more decided change:
alternations of indifference and irritability characterize his varying
moods. After a time the joys and the sorrows of life alike fail to
provoke real feeling. At length the confirmed sot manifests moral
traits that are simply infantile; he laughs without motive, he weeps
without cause.

2. The Will.—At the same time the will undergoes an enfeeblement

even more marked. Except in paroxysms of transient excitement it is
feeble and uncertain. The subject of chronic alcoholism scarcely
knows his own mind under ordinary circumstances. Aware of his
duties and his obligations, he is unable to discharge them. Especially
does he lack the power to say No. Vacillation, indecision, and
dependence upon others become characteristic traits. This loss of
moral energy, combined with the loss of physical power brought
about by continued and repeated excesses, begets at once a
distaste for the ordinary occupations of life and an inability to perform
them.

3. The Intellect.—Loss of intellectual power comes last. In some

cases it shows itself only after the most prolonged excesses, when
the body itself is becoming thoroughly broken down. Exceptionally,
fitful intellectual power is curiously sustained to the last. The first
evidence of intellectual failure consists in diminution of vivacity and
readiness. The intellectual state is marked by apathy, obtuseness,
and indifference; mental processes are performed slowly and with
difficulty. This is perhaps one of the causes of the mental indolence
characteristic of alcoholism. After a time the drunkard becomes
timid, loses confidence in himself, and is unwilling to engage in
enterprises demanding mental effort. Some tardiness of appreciation
then shows itself; conversation becomes difficult; ideas are not
spontaneous, but must be sought for; replies are not made with the
usual promptness; it is difficult to arouse and fix the attention. The
sense of self-respect is now lost, and it is almost impossible to make
the subject comprehend his degradation. The intellectual
deterioration becomes more and more marked. The memory fails
little by little and becomes treacherous. Names and dates are
recalled with difficulty. The conversation is interrupted by an inability
to choose the proper words with precision, hence hesitancy,
interruptions, and various forms of circumlocution. The power of
argument and of reasoning is now much impaired, the judgment is
uncertain, the association of ideas is inexact, and at length the
intellectual degradation attains a degree that unfits the subject for
the ordinary relations of life.

The above-described derangements of the viscera, of the nervous

system, and of the mind are the morbid phenomena induced by long-
continued excesses in alcohol. Whether merely functional or
dependent upon recognizable anatomical lesions, they indicate
pathological changes in the organism which are radical, and which
under the influence of the continuously acting cause are progressive.
Taken together, they constitute the condition known as chronic
alcoholism. In view of the familiar experiences of every-day life, it is
hardly necessary to repeat that these derangements are manifested
in all degrees of intensity and in the most variable and complex
combinations. The specific nature of chronic alcoholism is, in truth,
due not to the derangements themselves, the greater number of
which are such as we may encounter in morbid states not
occasioned by alcoholic excesses, but to the combinations in which
they occur in consequence of the action of the specific cause upon
the organism as a whole. The prominence of particular symptoms or
groups of symptoms in any given case is to be accounted for largely,
if not wholly, by individual peculiarities.
Chronic alcoholism, however latent it may be, however sedulously
concealed, warps the life of the individual in all its relations. In its
advanced degrees it amounts to mental and physical dyscrasia.
Between these extremes is every grade of incapacity and
degradation. It is beyond the scope of this article to discuss the
moral, social, or medico-legal bearings of this condition. Its purely
medical relations are sufficiently obvious from what has gone before.
It has been the writer's aim to make clear the existence and nature
of the continuing condition.

It remains to describe certain other psychical disturbances which

occur in chronic alcoholism, and which require separate
consideration for the reason that they are accidental rather than
essential, many cases running their course without their
manifestation.

4. Alcoholic Delirium in General.—True alcoholic delirium, presenting

the traits about to be described, is never the result of the direct
primary action of alcohol upon the nervous system. Transient
excesses produce acute alcoholism, drunkenness, which, varied as
its manifestations are, differs essentially from that peculiar delirium
which occurs only in individuals in whom the nervous system has
undergone those nutritive changes that are brought about by
prolonged alcoholic saturation.

The most striking peculiarity of this delirium relates to the

hallucinations which attend it. These are almost invariably visual;
occasionally they are also auditory. Their objects, whether men,
animals, or things are in constant and unceasing motion, appearing
and disappearing, coming and going, and changing from place to
place with extreme rapidity. In this respect they differ from the
hallucinations of other forms of delirium, of which the objects are
fixed and more or less permanent. As a result of this peculiarity, the
objects of alcoholic delirium are almost invariably multitudinous, as
swarms of vermin, herds of animals, multitudes of demons, and the
like.
A second peculiarity is the restlessness of the delirium. The patient
is invariably uneasy, apprehensive, always on the alert, declaring
that some calamity threatens him or that some evil is about to befall
him. In consequence of these apprehensions even momentary
repose is wanting. If he lies down for a moment, it is only to rise
again and peer under the bed or into the corners, turning his head
from side to side in search of some realization of the fears that
torment him. This sense of apprehension impels the patient to hurry
ever onward from place to place in search of the repose which he
nowhere finds. It is increased to positive terror by the ever-varying
and constantly-renewed hallucinations which torment him, and from
which he seeks to escape, no matter how great the obstacles to be
overcome.

A third peculiarity of alcoholic delirium is insomnia. This condition is

of the must marked and stubborn character, even continuing for
several days in succession.

5. Delirium Tremens.—This is the characteristic form of alcoholic

delirium, and, as is indicated by the name, is invariably accompanied
by tremor. It must be looked upon as an episode or epiphenomenon
of chronic alcoholism. It is rare that even prolonged temporary
excesses in persons ordinarily sober are followed by delirium
tremens. Such excesses in the subjects of chronic alcoholism are,
however, perhaps the most common cause of this condition. Orgies,
especially when associated with venereal excesses, very frequently
terminate in delirium tremens. Occasionally also, but much less
frequently than was formerly supposed, the abrupt discontinuance of
alcohol is followed by the outbreak. Other exciting causes are violent
emotions, as anger or fright; hardships, such as prolonged hunger,
over-exertion, or watching; acute maladies, as pneumonia,
dysentery, erysipelas, the exanthemata, or rheumatism; finally,
serious traumatisms, with or without great loss of blood. Delirium
tremens usually occurs in those addicted to the abuse of spirits, less
frequently in beer-drinkers, and comparatively rarely in those whose
excesses have been restricted to wine. The attack does not, as a
rule, begin abruptly; its prodromes usually consist in an exaggeration
of the previously existing symptoms of chronic alcoholism. The
patient complains of malaise, restlessness; he becomes depressed,
morose, anxious without cause, apprehensive of some calamity, or
he is more impatient and choleric than before. The ability to apply
himself to his ordinary occupations is lost. He complains of vertigo,
ringing in the ears; sleep is disturbed, or there is already insomnia.
At the same time the stomach is deranged, appetite is lost, the
tongue is covered with a thick yellowish-white fur, and there is
constipation or diarrhœa. The period of prodromes may last from a
few days to a week.

The outbreak is characterized by delirium, without, at least in the

greater number of cases, absolute loss of consciousness. That is to
say, it is possible by addressing the patient with energy or by
strongly arousing his attention to interrupt the delirium and for a
moment recall the patient to himself. In the graver cases, however,
loss of consciousness appears to be complete. The subjective
impression of the delirium, as recollected at the termination of the
attack, is that of a sense of overwhelming confusion and inability to
recollect or co-ordinate the ideas that were crowding upon the brain.
The hallucinations, as has already been indicated, relate almost
exclusively to the organ of sight, more rarely to the hearing; also,
and exceptionally, to the other organs of sense. They are almost
always either terrifying or repugnant. The objects of the
hallucinations of the sight have already been described. They consist
of animals, serpents, and monsters, which crowd into the apartment,
coming usually toward the patient, disappearing in the walls, in the
floor, under the bed, or among the bed-clothing. These visions are
usually aggressive, threatening the patient, throwing themselves
upon him, striking him, or tearing at his vitals. They are sometimes
replaced by phantoms, spectres of the most horrible character,
skeletons, death's-heads, or by flames which surround the patient
and threaten to consume him. Sometimes the hallucinations relate to
the daily occupation of the patient, and he pursues his tasks with a
feverish and distressing anxiety. These hallucinations are almost
invariably of the most fleeting, incoherent, and variable kind.
Auditory hallucinations occur usually in individuals of marked
neurotic tendencies. They are apt to be more coherent than the
hallucinations of vision, and are often of the nature of those which
occur in the delirium of persecution. Sometimes they consist of cries,
of chiding, of menacing voices, of the repetitions of obscene words
and suggestions; sometimes they are cries of horror or the roars of
animals, sometimes explosions or the discharge of firearms; or,
again, they are terrifying threats. Hallucinations of taste and smell
are much more rare, and occur in the subacute forms of delirium
tremens. The patient complains of annoying odors or disagreeable
tastes, either constantly present or upon the taking of food or drink.
Disturbances of general sensibility show themselves in hallucinations
in regard to sensations of pricking, burning, or tearing of the surface
of the body, or of animals or vermin crawling over the patient.
Hallucinations relating to the sexual instinct are far from rare. The
hallucinations of every form are apt to be more frequent and more
troublesome during the night than during the day.

Restlessness, fear, and anxiety are characteristic phenomena of

delirium tremens. The patient is not only terrified by the imaginary
objects which surround him, but often in their temporary absence he
experiences an equal degree of fear for which he can assign no
cause. It is to this condition of apprehension that is due the desire to
escape from his present surroundings which is so characteristic of
the delirium in question. Under its influence the patient occasionally
commits acts of violence of the most serious kind. Sometimes the
delirium is more quiet: the patient converses with individuals whom
he supposes to surround him; he busies himself with his familiar
occupations, giving orders, directing work, dictating letters, and
arranging his affairs. At other times the delirium takes the form of
apprehension of poisoning, and food and medicine are alike
stubbornly refused.

The countenance, as a rule, is animated, the eyes brilliant and

injected, the look fixed or peering, but always eager, or the
expression may be haggard and agitated. The physiognomy,
although largely influenced by the character of the delirium, may be
said to be in most cases characteristic.

Sensation is usually impaired; especially is this true of sensibility to

pain.

Tremor, although occasionally slight, may be said to be never wholly

absent. Sometimes it affects the muscles of all parts of the body;
more commonly it is limited to the hands, arms, tongue, and lips;
less frequently it manifests itself in the lower extremities. Slight
tremor may be increased by causing the patient to hold his hands
extended with the fingers separated. The movements of the hands
consist of rapid rhythmical oscillations of nearly equal extent and
duration. The tongue is protruded with a rapid jerking movement,
and withdrawn with equal suddenness. It shows fibrillar trembling.
The trembling is increased by voluntary movement, and is ordinarily
associated with some loss of motor power. The gait is often
hesitating and awkward; movements of the upper extremities are
executed with difficulty, and speech is irregular and interrupted. The
motor disturbances are occasionally associated with choreiform
movements or actual epileptic convulsions.

Insomnia is a constant condition. It usually persists throughout the

attack, and occasionally proves troublesome for several weeks after
convalescence is in other respects complete.

In the absence of pulmonary complications the respiration is not

disturbed, save as a result of the restlessness and physical effort
which sometimes quicken it. The same statement is true of the
pulse. The action of the heart is usually enfeebled, and the first
sound weak. The temperature is normal. The skin is frequently
bathed in copious perspiration. There is complete loss of appetite,
and in most cases inability to retain food. Thirst is constant, often
tormenting. The tongue is sometimes moist, and coated with thick
white or yellow fur; sometimes hard and dry, sometimes red. The
urine is scanty, dark-colored, and sedimentary. It occasionally shows
traces of albumen. Constipation is the rule.
The duration of delirium tremens is from three to seven, or even ten
or twelve, days. The course of the attack is paroxysmal or remittent.
The symptoms usually undergo some improvement during the day,
only to become more urgent at night. The periods of remission are
occasionally marked by transient slumber; the recovery by prolonged
and deep sleep. But this is by no means the rule. Several varieties of
delirium tremens have been described by writers upon the subject.
These are—the grave form, characterized by violence of the motor
disturbances, aggravated delirium, and gravity of the general
condition; the febrile form, in which after the third or fourth day the
temperature, without pulmonary or other discernible complications,
suddenly rises to 104° F. or beyond that point, with great aggravation
of the general symptoms; the adynamic form, marked by failing
heart-power, feeble or imperceptible pulse, profuse sweats, collapse,
stupor, which deepens into coma and ends in death; and finally, the
subacute form. Here the patient is quiet, but restless. The delirium
scarcely passes beyond the limits of occasional wandering, and
relates chiefly to matters connected with the daily interests and
occupations of the patient. Tremor is more or less marked, and
sleeplessness is stubborn.

The termination of delirium tremens is in—1, recovery; 2, in death; 3,

in the chronic form; and 4, in other forms of insanity.

1. Recovery.—Except in the grave forms recovery may be said to be

the rule. Occasionally ushered in by a prolonged, almost critical,
sleep, more frequently it takes place by gradual improvement. In the
latter case the remissions are more and more prolonged, and
attended by increasing repose alike of body and of mind, and by
tendency to sleep. The hallucinations become feebler and less
tormenting, at length recurring only in the evening or at night, and
especially as the patient is about falling asleep. The anxiety and
restlessness grow less urgent, consciousness becomes more
secure, the trembling diminishes, and recovery is slowly established.
The tremor is apt to persist some days into convalescence.
2. Death.—This mode of termination is not very common in the
ordinary forms of delirium tremens. In the grave forms it is usual,
sometimes occurring suddenly, sometimes gradually from
intensification of the symptoms and failure of nervous power; or it
may occur in consequence of pulmonary, cerebral, or renal
complications; finally, the fatal termination is often due to the acute
disease or the traumatism by which the delirium tremens has been
excited, and of which it is, in fact, a complication.

3. Chronic Delirium Tremens.—This mode of termination, described

by Lentz, is rare. The acute phenomena subside; the restlessness
and the mental agitation diminish. Insomnia gives place to sleep,
which is light and disturbed by dreams and nightmare; most of the
hallucinations lose their activity and frequency, and finally disappear.
The changing delirium settles into a fixed delirium of persecution; the
tremor, while it becomes fainter, persists, and the condition is
permanent.

4. Other Forms of Insanity.—This mode of termination has been

studied especially by Magnan, who has classified the cases of
delirium tremens into three different groups, according to their
tendency to recover or to the development of mental alienation. The
first group includes those cases which run a favorable course and
terminate in complete convalescence; the second group, those
cases in which the convalescence is prolonged and characterized by
repeated relapses; the third group is composed of cases which
likewise show a strong tendency to relapse, but in which the delirium
continues after the other active symptoms have subsided. This form
shows itself most frequently among the subjects of hereditary
alcoholism. After repeated attacks the delirium becomes chronic.
Morbid mental phenomena replace or accompany symptoms more
directly referable to organic disturbances of the nervous system.
Tremor gradually diminishes and disappears, the gastric symptoms
subside, insomnia passes away, even hallucinations disappear, or at
all events become infrequent; but the delirium which developed
coincidently with these symptoms continues, and finally becomes
chronic, losing to a great extent its original characteristics and
constituting a form of insanity. Finally, dementia constitutes an
occasional mode of termination in delirium tremens. It does not often
develop immediately, although cases of this kind have been
recorded. More commonly, the alcoholic subject, losing little by little
his mental activity after each attack of delirium tremens, subsides by
degrees into absolute and irremediable dementia. Paretic dementia
may also develop after prolonged alcoholic excesses characterized
by repeated attacks of delirium tremens.

The anatomical lesions after death from delirium tremens shed no

light on the pathogenesis of the condition. Meningeal congestion,
œdema of the pia mater and of the cortical substance of the brain,
scattered minute extravasations of blood, and some augmentation of
the cerebro-spinal fluid have been observed. In the greater number
of cases no lesions whatever beyond those characteristic of chronic
alcoholism have been discovered.

6. Alcoholic Insanity.—Among the psychical derangements, it

remains to notice briefly the more prominent forms of insanity which
develop in the course of chronic alcoholism, in consequence either
of hereditary or of acquired morbid mental tendencies. These are—
a, melancholia; b, mania; c, chronic delirium; d, dementia; e, paretic
dementia.

Alcohol is the most common of all the causes of insanity. Clouston47

estimates that from 15 to 20 per cent. of the cases of mental disease
may be put down to alcohol as a cause, wholly or in part. Those
forms of insanity in the production of which alcohol is merely an
occasional cause are not, however, properly included in the group of
alcoholic insanities. Still less are we to include in this group cases of
symptomatic dipsomania; that is to say, cases of insanity in which
morbid impulse to drink constitutes a prominent symptom of the
prodromic or fully-developed periods of various forms of mental
disorder.
47 Clinical Lectures on Mental Diseases, Am. ed., 1884.
Alcoholic insanity manifests itself as an outcome of chronic
alcoholism, just as epileptic and hysterical insanity show themselves
as the outcomes of epilepsy and hysteria. This group properly
includes various forms of mania-a-potu, especially the maniacal form
of acute alcoholism, delirium tremens, and other transitory
psychoses which occur in acute and chronic alcoholism.

In truth, the mental derangements of ordinary drunkenness

constitute in many cases a form of transient insanity. These forms,
have, however, already been considered at sufficient length.
Dipsomania, for reasons already stated, cannot be regarded, either
in its symptomatic form or in its essential form, as belonging to the
group of alcoholic insanities.

a. Melancholia.—Melancholia is the most frequent form of true

alcoholic insanity. It may begin abruptly or gradually, with changes of
character, vague disquietude, great irritability, and disturbances of
sleep amounting in many cases to insomnia. Hallucinations of
hearing are characteristic. In this respect the morbid mental
condition in question is in strong contrast with delirium tremens, in
which the hallucinations are principally visual. The hallucinations of
hearing usually consist of accusing or threatening voices. These
voices inform the patient that he is to be poisoned, assassinated,
murdered, or that outrages of all kinds are to be committed upon
him; they accuse him of murder, of robbery, of rape, and of other
shameful crimes. Præcordial distress is also apt to be present. In
consequence of these hallucinations of hearing the patient falls into
a profound melancholia, often characterized by suicidal impulses
which are sometimes the direct outcome of hallucination, at other
times blind and unreasoning. There is apt to be cephalalgia and
insomnia. Trembling is not usually a marked symptom. Local
anæsthesia and hyperæsthesia, if they occur, are transient. The
ordinary duration of this form of alcoholic melancholia is much longer
than that of delirium tremens, sometimes extending throughout
several months. The termination usually is in recovery, less
frequently in chronic delirium.
b. Mania.—This form of alcoholic insanity is characterized by various
hallucinations which present peculiar characters. Thus, the
hallucinations of vision commonly relate to supernatural apparitions,
attended with luminous phenomena of various kinds. These visions
may be occasional or they may be frequently repeated, or the
hallucinations may consist of images of emperors, kings, princes,
and potentates, or of military chieftains, in the midst of whom the
patient passes his existence. Or, again, the hallucinations may be
made up of historical scenes, pageants, the movements of armies,
battles, and the coronations of kings, or they may be landscapes
pleasant to the eye—snow-clad mountains, valleys filled with
flowers, magnificent forests, and the like. These phantasmagoria are
by no means fixed; on the contrary, they are of the most shifting
character.

Auditory hallucinations are even more frequent, and quite as

changeable. They bear a more or less well-defined relationship to
the hallucinations of vision. They consist not rarely of promises of
money, honors, titles, and the like. Sometimes they are voices from
heaven, even the voice of God himself, commanding the patients to
perform definite acts and promising in return equally definite
blessings.

Hallucinations of general sensibility occur much less frequently.

When present, they consist of various painful sensations, giving rise
to the delusions of blows, stabs, bites of animals, electrical
discharges, etc. In consequence of these hallucinations the
delusions are often of a grandiose character. Patients believe
themselves to be God, the pope, or some great potentate, or
enormously rich, etc.

The somatic condition depends upon the degree of chronic

alcoholism existing at the time of the manifestation of the mania.
There are usually marked tremor, hesitation and uncertainty of
speech, stubborn sleeplessness. Acute mania may show itself
abruptly, attaining its full development in the course of a few days, or
the development may be gradual. The prognosis in alcoholic mania
is unfavorable; recoveries are rare. The fatal termination is
sometimes the result of the maniacal condition itself, and sometimes
the result of visceral complications. This form of insanity occasionally
terminates in chronic delirium.

c. Chronic Delirium.—This form of alcoholic insanity is one of the

terminations of acute alcoholic melancholia and of acute alcoholic
mania. It is also one of the results of repeated attacks of delirium
tremens. Finally, it may develop independently of these affections.

Developing independently, chronic delirium is usually of rapid

invasion, and is characterized by the prodromes common to the
various forms of alcoholic insanity—irritability, headache, vertigo,
insomnia, etc. Hallucinations of hearing are very common, and relate
principally to the sexual life of the patient. Voices taunt him with the
fact that he is maimed or impotent; he hears persons whispering that
he is about to be castrated or that he is the subject of loathsome
venereal diseases, or they declare that he is known to be addicted to
vile crimes and bestiality. Hallucinations of sight are much less
common; those of the other special senses occasionally occur. The
delirium takes the form of delusion of persecution. The patient
believes himself the object of plots and conspiracies; his enemies
are seeking to ruin his good name, to tarnish his reputation, to
poison him. They put filth in his food or charge him with electricity;
they steal away his vital force or his sexual power; they taunt him;
they mock him; they beat him and rob him.

A delusion so frequent as to be almost characteristic of chronic

alcoholic delirium relates to marital infidelity.48 The patients cherish
unjust and often absurd suspicions of the virtue of their wives. These
delusions arise independently of hallucinations either of sight or
hearing, and are of the greatest importance, because they supply
logical motives for the most appalling and brutal crimes.
48 “The combination of a delusion of mutilation of the sexual organs with the delusion
that the patient's food is poisoned, and that his wife is unfaithful to him, may be
considered to as nearly demonstrate the existence of alcoholic insanity as any one
 group of symptoms in mental pathology can prove anything” (Spitzka, Insanity, N. Y.,
1883).

Alcoholic delirium differs in the transitory and incoherent character of

its delusions from ordinary chronic delirium, in which the delusions
are much more apt to be fixed and permanent.

d. Dementia.—This is a common terminal condition of alcoholism. It

may develop, without the intervention of other forms of mental
disease, in the course of chronic alcoholism as a mere intensification
of the intellectual and moral degradation of that condition. This is
especially liable to occur in hereditary alcoholism. Dementia also
closes the scene in a considerable proportion of cases characterized
by repeated attacks of delirium tremens. It likewise constitutes the
terminal condition in other forms of alcoholic insanity.

The symptoms are sometimes so slight as to escape ordinary

observation. More commonly they are fully developed. As compared
with ordinary dementia, they present but little that is characteristic.
Alcoholic dements are perhaps more filthy and more difficult to
manage, duller and more mischievous, than others. Their somatic
disorders are more marked. In them hyperæsthesias are replaced by
anæsthesias; sleep is apt to be irregular and disturbed; the
hallucinations characteristic of the antecedent alcoholic psychosis
now and then reappear. Slowly-developing failure of intellect,
forgetfulness, stupor, end in more or less complete loss of mental
power. Nevertheless, a small proportion of the milder cases are
capable of arrest under treatment.

e. Paretic Dementia.—Alcoholism is an important etiological factor in

the production of this condition. The intellectual disorders and motor
disturbances which characterize it, varied as they are, are
associated with cerebral lesions, and especially with lesions of the
cortex equally varied—lesions which are common in chronic
alcoholism. These lesions vary from meningeal congestion and
inflammation to profound inflammatory and degenerative alterations
in the cerebral substance.
Paretic dementia may develop after long-continued excesses without
previous appreciable mental or cerebral symptoms. In such cases it
presents no specific indications of its alcoholic origin. The difficulty of
determining the influence of alcohol in its causation is increased by
the fact that alcoholic excesses—symptomatic dipsomania—are
frequent in the prodromic and early stages of this form of mental
disease. Paretic dementia may also develop after repeated attacks
of delirium tremens. Here the early attacks end in recovery
apparently complete; later, the convalescence is unsatisfactory and
prolonged, leaving some indications of intellectual enfeeblement,
which, after renewed attacks, increases, and is accompanied by
delusions of grandeur, embarrassment of speech, unequal dilatation
of the pupils, and general paresis. The prognosis is practically
hopeless.

III. Hereditary Alcoholism.

This term has been used in a somewhat vague manner to designate

the morbid tendencies and pathological conditions directly
transmitted by alcoholic subjects to their offspring. Chronic
alcoholism on the part of one or both parents may be followed by
morbid manifestations in the child. The hereditary transmission of the
effects of alcoholism has been recognized from remote antiquity.
Aristotle believed that a woman given to drunkenness would bear
children with the same tendency. Plutarch affirms that the children of
drunkards will abandon themselves to the same vice. Hippocrates
speaks of the distressing effects of drunkenness upon the product of
conception. Bacon states that many idiots and imbeciles are born of
drunken parents. In more recent times the fact has been generally
recognized that many maladies caused by the abuse of alcohol are
liable to be transmitted to succeeding generations, and that
alcoholism may in this way, in the course of two or three generations,
lead to the complete extinction of families. Alcoholism on the part of
the parents certainly exerts an unfavorable influence upon the health
of their children, who are especially disposed to cerebral congestion,