Full Pressure Sensitive Design and Formulation Application First Edition Benedek Ebook All Chapters

Full download ebook at ebookgate.
com
Pressure sensitive design and formulation

application First Edition Benedek
https://ebookgate.com/product/pressure-sensitive-
design-and-formulation-application-first-edition-
benedek/
Download more ebook from https://ebookgate.com

More products digital (pdf, epub, mobi) instant
download maybe you interests ...
Technology of Pressure Sensitive Adhesives and Products

Handbook of Pressure Sensitive Adhesives and Products
1st Edition Istvan Benedek
https://ebookgate.com/product/technology-of-pressure-sensitive-
adhesives-and-products-handbook-of-pressure-sensitive-adhesives-
and-products-1st-edition-istvan-benedek/
Fundamentals of Pressure Sensitivity 1st Edition Istvan

Benedek (Editor)
https://ebookgate.com/product/fundamentals-of-pressure-
sensitivity-1st-edition-istvan-benedek-editor/
Pressure Vessel Design Manual Illustrated procedures

for solving major pressure vessel design problems Third
Edition Dennis R. Moss
https://ebookgate.com/product/pressure-vessel-design-manual-
illustrated-procedures-for-solving-major-pressure-vessel-design-
problems-third-edition-dennis-r-moss/
JavaScript Application Design A Build First Approach

1st Edition Nicolas Bevacqua
https://ebookgate.com/product/javascript-application-design-a-
build-first-approach-1st-edition-nicolas-bevacqua/
Site Analysis Informing Context Sensitive and
Sustainable Site Planning and Design 3rd Edition James
A. Lagro
https://ebookgate.com/product/site-analysis-informing-context-
sensitive-and-sustainable-site-planning-and-design-3rd-edition-
james-a-lagro/
Mobility protocols and handover optimization design

evaluation and application 1st Edition Schulzrinne
https://ebookgate.com/product/mobility-protocols-and-handover-
optimization-design-evaluation-and-application-1st-edition-
schulzrinne/
Affinity Electrophoresis Principles and Clinical

Application First Edition Breborowicz
https://ebookgate.com/product/affinity-electrophoresis-
principles-and-clinical-application-first-edition-breborowicz/
Recent Advances in Design and Usage of Pressure Vessels

and Piping Components 1st Edition Mahendra Kumar Samal
https://ebookgate.com/product/recent-advances-in-design-and-
usage-of-pressure-vessels-and-piping-components-1st-edition-
mahendra-kumar-samal/
Fatigue of Materials and Structures Application to

Design 1st Edition Claude Bathias
https://ebookgate.com/product/fatigue-of-materials-and-
structures-application-to-design-1st-edition-claude-bathias/
Volume 2 Pressure-Sensitive D esign and Formulation, Application
Taylor & Francis
Taylor & Francis Group
http://taylorandfrancis.com
Volume 2
Pressure-Sensitive
Design and
Formulation,
Application
Istvan Benedek
Boca Raton London New York
CRC Press is an imprint of the

Taylor & Francis Group, an informa business
First Published 2006 by Koninklijke Brill NV
Published 20 I 8 by CRC Press

Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2006 by Taylor & Francis Group, LLC

CRC Press is an imprint of Taylor & Francis Group, an lnforma business
No claim to original U.S. Government works
ISBN 13: 978-90-6764-440-2 (hbk)
This book contains information obtained from authentic and highly regarded sources. Reasonable
efforts have been made to publish reliable data and information, but the author and publisher cannot
assume responsibility for the validity of all materials or the consequences of their use. The authors and
publishers have attempted to trace the copyright holders of all material reproduced in this publication
and apologize to copyright holders if permission to publish in this form has not been obtained. If any
copyright material has not been acknowledged please write and let us know so we may rectify in any
future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced,
transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or
hereafter invented, including photocopying, microfilming, and recording, or in any information storage
or retrieval system, without written permission from the publishers.
For permission to photocopy or use material electronically from this wmk, please access www.
copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC),
222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that
provides licenses and registration for a variety of users. For organizations that have been granted a
photocopy license by the CCC, a separate system of payment has been arranged.
Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are
used only for identification and explanation without intent to infringe.
Visit the Taylor & Francis Web site at

http://www.taylorandfrancis.com
and the CRC Press Web site at

http://www.crcpress.com
A C.I.P. record for this book is available from the Library of Congress
Contents
Volume 2
1
Design- and Formulation Basis 1
1 RAW MATERIALS FOR PSPs 1
1.1 Raw Materials as a Function of the End-Use 1

Performances
1.1.1 Raw Materials for Different Product Classes 1
Raw Materials for Labels 2
Raw Materials for Tapes 2
Raw Materials for Protective Films 3
Raw Materials for Special Products 3
1.2 Raw Materials as a Function of the Manufacturing 4
Technology
1.2.1 Main Raw Materials for Coated PSPs 5
Raw Materials for Solvent-Based PSPs 5
Raw Materials for Water-Based PSPs 5
Raw Materials for 100 % Solids 6
1.2.2 Main Raw Materials for Extruded PSPs 6
1.3 Raw Materials as a Function of the Advances 6
in Macromolecular Chemistry
1.3.1 Monomers 7
1.3.2 Oligomers 7
1.4 Natural Rubber 9
1.5 Polymers with Segregated Structure 10
1.5.1 Styrene Block Copolymers 11
Common Products 11
Multiblock Copolymers 15
Functionalized Products 16
1.5.2 Thermoplastic Polyurethanes 17
1.5.3 Special TPEs 18
1.6 Alternating or Random Copolymers as Elastomers 19
1.6.1 Raw materials for Solvent-Based Formulations 20
1.6.2 Synthetic Rubber Dispersions 21
1.7 Polymeric Alkene Derivatives 22
1.7.1 Poly(butenes/isobutenes) 23
1.7.2 Amorphous Polyalphaolefins 24
1.8 Heteropolymers 25
1.8.1 Silicones 25
1.8.2 Polyurethanes 27
1.9 Vinyl Acetate Copolymers 31
1.9.1 Ethylene-Vinyl Acetate Copolymers 31
1.9.2 Vinyl Acetate-Vinyl Pyrrolidone Copolymers 34
1.10 Acrylates 34
1.10.1 Pure Acrylates 34
1.10.2 Ethylene-Acrylate Copolymers 37
1.10.3 Acrylic Rubber 38
1.10.4 Acrylic Oligomers and Macromers 38
1.10.5 Acrylic Block Copolymers 39
1.11 Polyvinylether 39
1.12 Tackifier Resins 40
1.12.1 The Molecular Weight of the Resin 40
1.12.2 Chemical Composition and Polarity of the Resin 41
1.12.3 Resin Colour 42
1.12.4 Resin Dispersions 43
Formulation of Resin Dispersions 43
Manufacture of the Resin Dispersion 44
Dispersion Stability 44
1.12.5 Rosin Derivatives 45
1.12.6 Hydrocarbon Resins 47
1.12.7 Coumarone-lndene Resins 50
1.12.8 Polyterpene Resins 50
1.12.9 Terpene-Phenol Resins 51
1.12.10 Phenolic Resins 52
1.12.11 Ketone Resins 52
1.12.12 Reactive Resins 53
1.12.13 Hybrid Resins 53
1.12.14 Economical Comparison of the Tackifier Resins 53
1.13 Additives 53
1.13.1 Chemical Additives 54
Crosslinking Agents 54
Initiators 57
Antioxidants 59
Fillers 69
Plasticizers 78
Compatibilizers 83
Detackifiers 83
Flame Proof Agents 83
1.13.2 Technological Additives 84
Wetting Agents 84
Neutralization Agents 92
Thickeners 93
Viscosity Reducers 96
Stabilizers 96
Solubilizers 97
Humidification Agents 99
Antimigration Agents 99
Cuttability Additives 100
Solvents 100
1.14 Economic considerations 105
2 FORMULATION EQUIPMENT 106
2. 1 Blending Equipment 106

2.1.1 Blending of Rubber-Resin Adhesives 106
Wet Blending Technology 107
Dry Blending Technology 108
Mastication 108
Blending in Molten State 109
2.1.2 Blending of Viscoelastomers 113
Solution-Based Formulations 114
Water-Based Formulations 114
2.2 Manufacturing Equipment 117

References 118
2
Hot-Melt PSAs Based on Styrenic Polymer 141
¥.J.Park
1 HOT-MELT PRESSURE- SENSITIVE ADHESIVES 141
2 STYRENIC BLOCK COPOLYMER 143
2.1 Introduction
2.2 Synthesis of Styrenic Block Copolymers 144
2 .2.1 Di-Block Copolymers 145
2 .2.2 Tri-Block Copolymers 146
2.2.3 Star Block Copolymers 148
3 TACKIFIERS FOR SBC-BASED HOT-MELT PSAs 149
3.1 Rosin Resins 151

3.1.1 Rosin Chemistry 151
3.2 Terpene Resins 151
3.3 Hydrocarbon Resins 153
3.3.1 Aliphatic Hydrocarbon Resins, C5 153
3.3.2 Aromatic Hydrocarbon Resins, C9 154
3.3.3 Dicyclopentadiene Hydrocarbon Resins, DCPD 154
3.3.4 Hydrogenated Hydrocarbon Resins 155
3.3.5 Hydrogenated C9 Hydrocarbon Resins 155
4 ADHESION PERFORMANCE OF SBC-BASED HMPSAs 157
4.1 Viscoelastic Behavior of Hot-melt PSAs 157

4.1.1 General Performance of PSAs 157
4.1.2 Miscibility 160
4.2 Peel Strength of SBC-Based Hot-melt PSAs 161
4.2.1 Failure Mode 163
4.2.2 Surface Tension of Substrate and Peel Rate 163
4.2.3 Effect of Tackifying Resin 166
4.3 Probe Tack of SBC-Based Hot-Melt PSAs 168
4.3.1 Tack and Viscoelastic Property 168
4.3.2 Tack and Fracture Energy 168
4.4 Shear Creep Resistance of SBC-Based Hot-Melt 172
PSAs
4.4.1 Holding Power 173
4.4.2 Shear Adhesion Failure Temperature (SAFT) 174
4.5 Effect of Blend and Coating Method on Adhesion 176
Performance
References 176
3
Pressure-Sensitive Adhesives of 181
Controlled Water-Absorbing Capacity
Mikhail M. Feldstein, Gary W. Cleary and
Parminder Singh
1 MOLECULAR NATURE OF PRESSURE-SENSITIVE 181

ADHESION
2 BASIC TYPES OF INTERPOLYMER COMPLEXES 183
3 THERMODYNAMIC PRINCIPLES OF INTERPOLYMER 184

COMPLEX FORMATION
3.1 Ladder- Like Complexes 185

3.2 Carcass-Like Complexes 186
4 ADHESIVES BASED ON LADDER- LIKE COMPLEXES 188
4.1 Factors Providing the Preparation 188

4.2 Phase Behavior and Mechanical Properties 189
4.3 Adhesive Properties 191
4.3.1 Effect of Ladder-Like Crosslinker 191
4.3.2 Effects of Plasticizer and Tackifier 192
4.3.3 Effects of Bonding Type and Nature of Ladder-Like 195
Crosslinker 197
4.4 Water-Absorbing Capacity 197
5 ADHESIIVES BASED ON CARCASS-LIKE COMPLEXES 201
5.1 Mechanical Properties 202
5.2.1 PVP - PEG Complexes 205
5.2.2 Polyelectrolyte Complexes 207
5.2.3 Blends with Acrylic Adhesives 209
5.3 Solubility and Swelling in Water 210
6 ADHESIVES BASED ON THE COMBINATION OF 210

LADDER-LIKE AND CARCASS-LIKE TYPES OF
INTERPOLYMER COMPLEXES
6.1 Mechanical Properties 211

6 .2.1 Effects of Ladder-Like Crosslinker and the Type of 214
Interpolymer Bonding
6 .2.2 Effects of Carcass-Like Crosslinker (Plasticizer) 217
and Absorbed Water
6.3 Water-Absorbing Capacity 219
7 CORPLEX™ ADHESIVES OF CONROLLED WATER 222

ABSORBING CAPACITY
7.1 Classification of Corplex™ Adhesives in Terms of Their 223

Hydrophilicity
7.2 Corplex™ Adhesive Absorbents Compared with Conventional 223
Pressure-Sensitive Adhesives and Bioadhesives
7.3 Pharmaceutical Application of Corplex™ Adhesives 225
CONCLUSIONS 229
References 229
4
Removable and Repositionable 231
Pressure-Sensitive Materials
Zbigniew Czech
1 INTRODUCTION 231
2 REMOVABLE AND REPOSITIONABLE PRESSURE- 232

SENSITIVE ADHESIVES
2.1 Mixture of Pressure-Sensitive Adhesives with 232

Inherently Tacky Elastomeric Microspheres
or Glass Bubbles
2.2 Low Melt-Viscosity PSAs 233
2.3 Emulsion Polymer Formulations 233
2.3.1 Influence of Internal Emulsifiers on Removability 234
2.3.2 Influence of Plasticizers on Removability 237
2.4 Solvent-Based PSA Compositions 238
2.4.1 Removable PSA Crosslinked with Multifunctional Isocyanates 239
2.4.2 Removable PSA Modified with Stearinic Acid 240
2.4.3 Removable PSA Modified with Ethoxylated Amines 241
2.4.4 PSA Blends with Polyalkylene Oxides 241
2.4.5 PSA Crosslinked with Multifunctional Aziridines 243
2.4.5 UV-Crosslinked Removable PSA 244
3 INFLUENCE OF THE COATING WEIGHT ON TACK 245

AND PEEL ADHESION
4 TEST METODS FOR REMOVABLE PSAs 246
4.1 Removability 246

4.2 Peel Adhesion at Diverses Angles 247
4.2.1 90° Peel Adhesion 247
4.2.2 180° Peel Adhesion 247
4.3 Curved Panel Lifting Test at 150°C 248
5 PROSPECTS FOR REMOVABLE AND 248

REPOSITIONABLE PSA
References 248
5
UV-Curable Pressure-Sensitive Adhesives 251
Hyun-Sung Do and Hyun-Joong Kim
1 WHAT ISUV? 251
1.1 Principles of Photocuring 252

1.1.1 Photoinitiator 252
1. 1.2 Photoinitiated Polymerization 254
2 UV-CURABLE PRESSURE-SENSITIVE- ADHESIVES 256
2.1 Techniques in UV-Polymerizable PSAs 258

2.1.1 Thickened Monomer Mixtures 258
2 .1.2 Prepolymerized Monomer Mixtures 259
2.2 Techniques for UV-crosslinkable PSAs 260
2 .2.1 UV-Crosslinkable Acrylic PSAs 261
2 .2.2 UV-Crosslinkable Hot-Melt PSAs 266
3 ADHESION PROPERTIES OF UV-CURABLE PSAs 270
3.1 UV-Polymerizable PSAs 271

3.2 UV-Crosslinkable PSAs 276
4 KINETICS OF UV-CURABLE PSAs 284
5 CONCLUSION 288
References 288
6
Pressure-Sensitive Design and Formulation 291
in Practice
Istvdn Benedek
1 DESIGN AND FORMULATION FOR ADHESIVE 291

PROPERTIES
1.1 Design and Formulation of Permanent Adhesives 291

1.2 Design and Formulation of Removable Adhesives 296
1.2.1 Solvent-Based Removable Formulations 299
1.2.2 Water-Based Removable Formulations 299
1.2.3 Hot-Melt-Based Removable Formulations 304
1.3 Design and Formulation for Special Adhesive 306
Properties
1.3.1 Design and Formulation for Water Resistance/Solubility 306
1.3.2 Design and Formulation for Low Temperature Applications 313
2 DESIGN AND FORMULATION FOR PRESSURE- 315

SENSITIVE PRODUCT CLASSES
2.1 Design and Formulation of Labels 315

2 . 1.1 Solvent-Based Label Formulations 317
Paper Labels 317
Film Labels 318
Special Labels 319
Permanent/Removable Label Formulations 320
2 .1.2 Water-Based Label Formulations 320
2.1.3 Hot-Melt Label Formulations 322
2.2 Design and Formulation of Tapes 323
2 .2.1 General Formulation of Tapes 324
Raw Materials for Tapes 325
Formulation of Hot-Melts for Tapes 327
Formulation of Solvent-Based Adhesives for Tapes 330
Formulation of Water-Based Adhesives for Tapes 330
Packaging Tapes 331
Rubber-Resin Formulations for Packaging Tapes 332
Water-Based Formulations for Packaging Tapes 334
2 . 2.2 Formulation of Special Tapes 336
Insulation Tapes 337
Conductive Tapes 339
Masking Tapes 340
Double-Sided Tapes 341
Splicing Tapes 342
Mounting Tapes 343
Carrierless Tapes 343
Foam-like Tapes 346
Medical Tapes 347
2.3 Formulation of Protective Films 353
References 355
Abbreviations and Acronyms 367

Index 373
volum e 2 Contributors
Chapter 1 Design- and Formulation Basis
Istvan Benedek
Pressure Sensitive Consulting
Wuppertal,Germany
Chapter 2 Hot-Melt PSAs Based on Styrenic Polymer
Young-Jun Park
Seoul National University
Laboratory of Adhesion and Bio-Composites
Seoul, S. Korea
Chapter 3 Pressure-Sensitive Adhesives of

Controlled Water-Absorbing Capacity
Mikhail M. Feld stein

Topchiev Institute for Petrochemical Synthesis
Russian Academy of Sciences
Moscow,Russia
Gary W. Cleary
Corium International
Redwood City, California
USA
Parminder Singh
University of Virginia, VA
USA
Chapter 4 Removable and Repositionable

Pressure-Sensitive Materials
Zbigniew Czech
Sczecin University of Technology
Polymer Institute
Sczecin,Poland
Chapter 5 UV-Curable Pressure-Sensitive Adhesives
Hyun-Sung Do
Seoul, S. Korea
Hyun-Joong Kim
Seoul, S. Korea
Chapter 6 Pressure-Sensitive Design and Formulation
in Practice
Istvan Benedek
Pressure Sensitive Consulting
Wuppertal,Germany
1
Design- and Formulation Basis
Istvan Benedek
The goal of this chapter is to discuss the hardware required to formulate pressure-
sensitive products. The formulation basis includes knowledges about the raw materials
of the formulation and about the equipment employed for the formulation. These are
the main parameters of the formulation. Such parameters are interdependent.
1. RAW MATERIALS FOR PSPs
The raw materials used for a formulation depend on the end-use performance
characteristics, and on the manufacturing technology of the pressure-sensitive
product.They are strongly affected by advances in macro-molecular chemistry and
by economic considerations.
1.1. Raw Materials as a Function of the End-Use Performances
The first industrially manufactured pressure-sensitive products were based on natural

rubber as main elastomer. Such formulations contained tackifiers as viscous
components to provide the viscoelastic properties required for pressure-sensitivity.
Later, viscoelastic high polymers were synthesized.
Such raw materials allowed one-component formulations with optional use of
viscous components. Further development of macromolecular chemistry imposed the
use of viscous materials (e.g., oligomers) as base components of the formulation with
the need to post-transform them (in situ) in viscoelastic compounds ( Fig. 1.1 ).
As discussed in Vol.l,Chapt. 4, there are many possibilities for design,
formulation and manufacturing of pressure-sensitive adhesives and pressure-sensitive
products, and PSPs with quite different build-up or the same build-up but different
chemical basis can be used in the same application field [1]. The product class
decidedly affects the choice of the raw materials.
1.1.1. Raw Materials for Different Product Classes
The end-use requirements for various PSPs are different. Related to the application
field of the product the economical considerations are restrictive for the choice of the
1
2 Vol.2y Chapter 1
Figure 1.1 Manufacturing methods for pressure-sensitive adhesives.
manufacturing technology. Although theoretically almost each raw material class can
be used for each pressure-sensitive product class, there are preferred raw materials
for different PSPs. The main pressure-sensitive products include labels, tapes and
protective films [2].
Raw Materials for Labels
Labels are manufactured mostly by coating of a pressure-sensitive adhesive on a

solid-state carrier. Labeling is the most important field of water-based pressure-
sensitive adhesives [3]. Acrylics and styrene-butadiene copolymers are the main
water-based raw materials for adhesives for labels. For special applications, vinyl
acetate copolymers, chloroprene emulsions, polyvinyl ethers and polyurethanes were
suggested also. As solvent-based formulations for general label use natural rubber-resin
compositions were suggested; for special applications acrylates were proposed. The
adhesive formulation for labels is described in Vol.2,Chapt. 6.
Raw Materials for Tapes
Tapes are manufactured mainly by coating of a pressure-sensitive adhesive on a

solid-state carrier but „full carrier,, or „full adhesive,, products were developed too.
Special self-adhesive films can be used as tape ( e.g., masking tape ) and self-
supporting adhesive layers are employed as tape too (e.g., sealants ). In certain cases
temporary carrier materials are inserted in the laminate ( e.g., transfer tapes ). The
preferred PSA is water-based (Tab. 1.1 ). Taking into account the various build-up of
tapes, the raw material basis for tapes is much wider than for labels. On the other
hand, a pronounced difference exists between the requirements with tapes for
general use and special products. Thus, each of the above product classes needs
different raw materials. Packaging and fastening tapes are manufactured mainly with
rubber-resin solution adhesives, water- based acrylates or styrene block copolymer-
based hot-melts. Special tapes use solution acrylate, silicone, polyurethane, polyvinyl
ether, etc. -based pressure-sensitive adhesives. The design formulation of such
adhesives is described in Vol.l,Chapt.3, Sect. 2.2.
Design and Formulation Basis 3
Table 1.1 The Main Raw Materials for Various Pressure-Sensitive Product Classes.
Pressure-Sensitive Product Raw Material
Label Acrylic dispersions

tackified
untackified
Rubber-resin solutions
Acrylic solutions
Tapes
general Rubber-resin solutions
Acrylic dispersions
Thermoplastic elastomers-hot-melts
special Special elastomer solutions
tackified
Special viscoelastomer solutions
tackified,
untackified
Plastomers
tackified
Self-adhesive plastomers
Protective films Rubber-resin solutions

Acrylic solutions
untackified
Acrylic dispersions
untackified
Plastomers
tackified
Self-adhesive plastomers
Raw Materials for Protective Films
Protective films are manufactured as adhesive-coated products or as self-adhesive

plastic films. Protective coatings are known too. The adhesive-coated protective films
use mostly rubber-resin solutions or acrylate solutions ( untackified) and acrylate
dispersions ( untackified ). The adhesiveless protective films can be virtually adhesive-
free or really adhesiveless products. They can be formulated with common plastics
which are tackified in bulk, or with pressure-sensitive plastics that do not need classic
pressure-sensitive adhesives [4]. The design and formulation of protective films is
discussed in Vol.l,Chapt.3, Sect.2 and Vol.2,Chapt. 6.
Raw Materials for Special Products
Special pressure-sensitive products exhibit special adhesive characteristics (e.g., dry-

or wet-removability, time-related removability, controlled release, etc.) and/or combine
the adhesive properties with other functions (e.g., dosage,visual information, tamper
evidency, etc.). For such products, sophisticated adhesive formulations were
developed. Such formulations can include special additives ( e.g., curing agents,
detackifiers, flame retardants, photoinitiators, solubilizers, etc.).The most used
additives are described in Sect. 1.1.3
4 VoL2, Chapter 1
Table 1.2 The Main Manufacture Technologies for PSPs.
Manufacture Technology Product Components
Coating Adhesive
direct Carrier
transfer
Extrusion Carrier
plastic
Adhesive
hot-melt
Casting Carrier
plastic
Adhesive
in situ manufacture
1.2. Raw Materials as a Function of the Manufacturing

Technology
The main manufacturing technologies for pressure-sensitive products ar based on

coating and extrusion. Both, coating and extrusion can lead to carrier-like or adhesive
like products. Both procedures allow the manufacture of mono-web or multi-web
pressure-sensitive products and the manufacturing of monolayer and multilayer
products. Generally, the raw materials determine the usability of a manufacturing
technology because of their intrinsic mechanical and adhesive performance
characteristics and their processibility by a given technology. For instance, in the
early stage of pressure-sensitive product development such products were
manufactured mainly by coating of a pressure-sensitive adhesive on a solid-state carrier
material.The use of a PSA with pronounced fluidity required a construction having a
solid-state non adhesive carrier material. The carrier was coated with the pressure-
sensitive adhesive.The coating technology was influenced by the nature of the raw
materials. As is known, rubber-resin formulations are mostly solvent-based
compositions.The use of such adhesive solutions with medium viscosity required
special coating devices and drying technology. It allowed direct coating. Later, the
introduction of water-based acrylics with low viscosity forced transfer coating. The
development of thermoplastic elastomers made possible hot-melt coating by
technologies known from the processing of plastics (Tab. 1.2 ).
Advances in crosslinking and radiation polymerization allowed casting of carrier
like adhesive products by a technology used earlier for PVC film processing. The
development of highly viscous compoundable tackifiers forced the production of
compounded pressure-sensitive products where blends of plastomer-viscous
component-elastomer were processed as plastic films. Advances in the chemistry of
raw materials for plastic films made possible the manufacture of one-component
pressure-sensitive products based on tacky plastomers.
Although different technologies can be used in the manufacture of pressure-
sensitive products, certain raw materials are universally used; others are tailored to
the special products. This chapter discusses the raw materials for coating technology
only.
1.2.1. Main Raw Materials for Coated PSPs
The raw materials for coated pressure-sensitive products include macromolecular

compounds and formulation additives for pressure-sensitive adhesives. Such
components differ according to the coating technology of the adhesive. The coating
technology itself is a function of the physical status of the adhesive ( 100% solids or
dispersed).
Raw Materials for Solvent-Based PSPs
Solvent-based pressure-sensitive adhesives are the most used coating components for
pressure-sensitive products. The use of solvents allowed the uniform tackification of
the rubber and thin layer coating of natural rubber-based PSAs on continuous webs
and thus it made possible the development of the pressure-sensitive industry. As
discussed earlier, solvent-based adhesives are formulated as rubber-resin and
viscoelastomer-resin formulations (where the resin may include other tackifying
additives, e.g., plasticizer, wet-tackifier, etc.) or as pure viscoelastomer formulations.
The base elastomers and viscoelastomers for solvent-based adhesives include the
polymers that can be dissolved or dispersed in a common organic solvent. Such
polymers can undergo a (post-synthesis ) dissolving, or they can be prepared as organic
solutions or dispersions.
The main raw materials for solvent-based PSAs are natural and synthetic rubbers,
acrylic copolymers , copolymers of vinyl acetate, polyvinyl ethers, polyurethanes and
silicones (see Sect. 1.6.1 ). Rubber-based adhesives offer good normal- and high
temperature-cohesion and water resistance, but low ageing resistance. They exhibit low
plasticizer resistance because they are tackified systems. Such products display high
shrinkage [5]. Rubber-based adhesive solutions are suggested for packaging and office
tapes, medical and protective tapes, etc. Solvent-based formulations comprise a liquid
vehicle also ( see Sect. 1.13.2). Additives ( fillers,wetting agents, etc.) are also used for
solvent-based pressure-sensitive adhesives.
Raw Materials for Water-Based PSPs
Water-based pressure-sensitive adhesives are based mostly on acrylate copolymers.

Such raw materials can be used without or with tackifiers. For special products vinyl
acetate copolymers (with ethylene, acrylates, maleic acid derivatives, vinyl ethers,
styrene, vinyl chloride etc.) can be used also. Styrene-diene copolymers, diene-vinylic
acid derivative copolymers and heteropolymers (e.g., chloroprene ) were developed
too. The main aqueous pressure-sensitive compositions are CSBR, SBR, NR,EHA,
BuA, neoprene, EVAc and PUR-based systems [6]. Water-based formulations need a
broad range of technological additives also. The main base elastomers and
viscoelastomers for water-based formulations are described in Sects. 1.6.2 ,1.9
and 1.10. The additives used for water-based formulations are discussed in Sect.
1.13.2.
6 VoL2, Chapter 1
Raw Materials for 100 % Solids
Formulations with 100 % solids include hot-melts and-warm melts, i.e., high
polymer-based recipes and oligomer-based formulations. Hot-melts are based mostly
on thermoplastic elastomers. Such compounds were discussed in the chapter
concerning tackification. Typically a hot-melt-based adhesive contains various ( 5-12 )
ingredients for a good balance of performances. Hot-melts are used in high coating
weight strapping tapes, mounting tapes, labels and packaging envelops. Hot-melt
pressure-sensitive adhesives have aggressive tack, high peel resistance and good
adhesion on cardboard [5]. For applications which need high coating weight (e.g., for
mounting and carpet laying tapes where the surface is rough ) they can be used
economically, supposing that the adhesive is protected from the environment.
Unfortunately, they are plasticizer-sensitive. Warm-melts were described in the
Vol.Chapt.4, Sects. 1.1 and 1.2 concerning in situ synthesis and crosslinking, and in
Vol.l.Chapt.6. Some special aspects of the development of such raw materials will be
discussed in Vol.2, Chapt. 5.
1.2.2. Raw Materials for Extruded PSPs
As discussed in detail in Ref. [1], advances in polymer chemistry and processing of

plastic films allowed the manufacture of self-adhesive films with and without adhesive.
Their build-up, raw materials and manufacture were discussed in our book concerning
pressure-sensitive products.
1.3. Raw Materials as a Function of the Advances in

Macromolecular Chemistry
In principle, the raw materials for PSPs are elastomers (which have to be transformed
into viscoelastomers) or „ready to use,, viscoelastomers. Their elasticity and
viscoelasticity is a function of their chemical composition and macromolecular
characteristics. Both can be modified as advances in macromolecular chemistry
provide new possibilities for macromolecular synthesis and polymer analogous
reactions.Thus, the raw materials for PSPs are in continuous development.
Although developments in macromolecular chemistry allowed the synthesis of
elastomeric materials with a natural rubberlike build-up ( e.g., stereoregulated
polydienes ), the ma-nufacture of PSPs was based mainly on natural rubber or special
rubberlike diene copolymers. The breakthrough made by the synthesis of viscoelastic
polymers ( which can be used as one-component PSAs ) was not followed by a
similar advance in the domain of rubber-like products. The introduction of
thermoplastic elastomers has been a progress concerning easy processibility, but the
formulation freedom of such materials as adhesive was (at least in the first period of
their development) very limited. This arosed because of the limited availability of
methods that could be used to build up an ordered structure without the loss of certain
mechanical or adhesive properties.
Further developments in the copolymerization chemistry and technology allowed
the synthesis of other viscoelastomers ( e.g., vinyl acetate, maleinate, etc.,
copolymers) which compete with acrylics in numerous special domains. Such raw
materials can be formulated in water, or in solvents. The functionalization of
synthetic rubber-like copolymers made possible the synthesis of water-dispersible or
water-soluble elastomers , i.e ., the formulation of rubber-resin recipes that are water-
based ( like common acrylics ). Such functionalized diene-styrene copolymers are
used mostly for economic reasons.
Actually the main macromolecular raw materials for PSPs are elastomers,
viscoelastic high polymers,plastics, viscous high polymers and oligomers. Such
compounds are based on monomers.
1.3.1. Monomers
The role of the monomer as base unit in the control of the macromolecular and
chemical characteristics of a polymer was discussed in detail in Chapt. 4. A
special role is played by such monomers which can be used for in situ adhesive
synthesis also. Reactive diluents are such monomers.Their function in the off-line or
in-line synthesis of pressure-sensitive raw materials or pressure-sensitive adhesives
was discussed in the Vol.l,Chapt.4, Sects. 1.1.1 and 1.1.2. In certain cases, they are
used as supplemental crosslinking agents too (see Vol.l,Chapt. 4, Sects. 1.2. and 2.2.1
and Vol. 1, Chapt.6).
The radiation-curable reactive diluents ( monomers ) are used for viscosity control
and fine regulation of the final properties. In some cases the formulations with
reactive diluents are supplied as a solution of the oligomer in a reactive monomer .
Such reactive diluents must be compatible with the other components of the recipe,
must exhibit low shrinkage and low vapour pressure [7]. Generally, the recipe
contains prepolymers, reactive diluents ( di,- tri- and multifunctional monomers ) and
additives like wetting agents, fillers, adhesion promoters, and matting agents also.
The main reactive monomers are multifunctional acrylates . For instance, as reactive
diluents, hexanediol diacrylate,trimethylol propane triacrylate, tripropyleneglycol
triacrylate and pentaerythritol tetraacrylate were suggested. Low irritation
multifunctional monomers were developed based on alkoxylated di-, tri- and
tetrafunctional acrylates [8]. Such a reactive diluting agent is for instance a 80 %
solution in tripropyleglycol diacrylate, or 75 % solution in trimethylolpropane
triacrylate [9] or in hexanedioldiacrylate [10]. Sherman [11] introduced new diluting
monomers for UV-light-induced curing, e.g., dicyclopentadienyl acrylate, polybutane
-diol diacrylate, p-carboxyethyl acrylate, 3-chlor-2-hydroxypropyl acrylate,
thiodiethyleneglycol diacrylate and isobomyl acrylate.The main reactive diluents
suggested for EB curing include: HDDA,TMPTA,TPGTA [9] and PETA [12].
Triallylcyanurate is recommended as crosslinking agent for EB curing too [13]. As
crosslinking agent for styrene-butadiene-styrene block copolymers (Cariflex-1107)
and styrene-isoprene-styrene block copolymers ( Cariflex D-1101 ) pentaeryithritol
triacrylate and trimethylol propane thioglycolate were proposed [14]. The various
crosslinking monomers used for acrylates were discussed in detail in [15]. Recently the
preparation and adhesion performances of UV-crosslinkable acrylic PSAs were
investigated by Hyun-Joong Kim et al. [16] (see Chapt. 5 also).
1.3.2. Oligomers
As discussed in Vol.l, Chapt. 4, Sect. 1.2.3 oligomers were developed for in situ
manufacture of pressure-sensitive adhesives. Such oligomers ( 50 -10 % of the recipe)
can possess various chemical composition ( hydrocarbon- based or heteroatom
based) and different functionalities. Thus they can undergo various types of
reactions (polymerization, polyaddition and polycondensation ) which lead through
different initiation mechanisms (thermal or radiation-induced ) to various polymers
(see Macromerization also).
The most used radiation-curable oligomers are: polyester acrylates, epoxy acrylates,
urethane acrylates and polyetheracrylates [7]. As reactive oligomer, polybutadiene
8 Vol. 2,Chapter 1
diacrylate, methacrylate terminated polystyrene, and hydroxy terminated polystyrene

are supplied also [17]. They contain acrylate and vinyl functionality and can be used
for EB curing.
Acrylated polyester oligomers can be used as raw material for HMPSA [18]. They
can be coated at 100-150 °C. Modified by celluloseester, the hot melt pressure-
sensitive adhesives on polyester oligomer basis display good cohesion at high
temperature (160 °C ). By the build in of branched aliphatic side chains in polyether-
copolyesters, oligomers were manufactured which beware their pressure-sensitivity
after EB-curing [19]. Such acrylated polyester oligomers ( having a molecular
weight of 3000-8000 ) with a comb-like structure were proposed for HMPSA [20].
Methacrylate terminated polyurethanes are common prepolymers used. Their
photoinitiated free radical polymerization occurs through their reactive acrylic head
group.
Ultraviolet light-curable reactive oligomers were synthesized also. They are low
molecular products having special functional groups. For instance, Acronal-DS 3429 is
a UV-curable acrylate copolymer for HMPSAs [21]. The photoinitiator is built into the
polymer; no C=C double bonds exist in the raw material.Therefore this product is not
suitable for EB-curing. During its curing, crosslinking occurs . Acronal-DS 3429 is a
highly viscous clear liquid, that can be processed at 100-140 °C ( preferred coating
device is the slot die ). It possesses a viscosity of about 15.000 mPas at 120°C. It is
polymerized in solvent and therefore such acrylate contains traces of solvent ( 0.4 %
isobutanol ). Its price is lower than that of acrylic solutions. UV-curable acrylic
copolymers were synthesized in Ref. [16]. The PSAs were synthesized by solution
polymerization of EHA,vinyl acetate and acrylic acid, and unsaturated benzophenone
derivative with varying content of 2-HEMA.
For heat-activatable adhesive mixtures of high molecular weight macromers,
polystyrene polymers having methacrylate end groups at one end were proposed [22].
Other functionalities like epoxy or amino groups can be used also to prepare or
to crosslink reactive oligomers. Dienes can be oligomerized to products having
controlled length using triisobutyl aluminum [23]. New epoxy resins based on
bromostyrene-butadiene cotelomers were prepared by telomerization and
epoxidation. Such resins can be crosslinked. Their bromine content improves the
flame-resistant properties [24]. Hydrogenated styrene block copolymers have excellent
light and heat stability but have high viscosities and cannot be crosslinked. Therefore,
new, low viscosity, curable raw materials were synthesized. Ultraviolet light-curable
reactive oligomers were manufactured. They are low molecular products having
special functional groups which participate in UV-light-induced crosslinking
(specially by cationic UV-curing). The so-called Kraton Liquid Polymers with
hydroxyl and oxirane functionalities can be UV-crosslinked with a triarylsulfonium salt
system.They can be coated like hot -melts with a slot-die coating device [25-29J.A
poly(ethylene-butylene ) rubber bearing a primary hydroxyl functionality on one and
and epoxidized polyisoprene functionalities on the other end , with a Tg of -53 °C
was developed ( Kraton-EKP-207 ) by Shell [30]. Shell-EKP-207 is an epoxidized
mono-ol and L I203 is a mono-ol. Their frilly saturated backbone consists of
polyethylene-butylene rubber, with a low glass transition temperature . This
product is a viscous liquid, that has an epoxy equivalent close to 670 g/mol and a
hydroxyl equivalent weight of about 6000 g/mol. This gives epoxy and hydroxyl
equivalent values of 1.5 and 0.17 milliequivalents per gram of polymer. The
grade L-1203 is a linear poly(ethylene-butylene) rubber bearing a terminal aliphatic
primary hydroxyl group on the same backbone and possesses a Tg of -63 °C. It is a
viscous liquid and has a hydroxyl equivalent weight of 3600 g/mol. Another
macromer possesses a terminal hydroxyl functionality on both polymer ends. Generally
a blend of such products having different functionalities is used. According to Ref. [31],
the epoxy/mono-ol ratio is critical to optimizing PSA properties.A ratio of 2.5-1.5
provided high peel tack and shear.
Oligomeric or macromolecular crosslinking agents with epoxy groups can be used
too (see Chapt. 4). For instance, a crosslinkable formulation contains 0.1-10 pts a ,(3-
unsaturated carboxylic acid and a macromolecular crosslinking agent (e.g. > 2 pts
epoxy containing polyglycidyl compounds) at an epoxy/carboxy ratio of 0.1-3.0. The
polymer has been crosslinked with 1 phr polyethyleneglycol diglycidyl ether [32].
Multi-block copolymers based on polybutadiene and aromatic polyamides were
prepared by the reaction of amine terminated telechelic aromatic oligoamides with
a,Q-dicarboxylatopolybutadienes. The aromated oligoamides are prepared from
bis(aminophenylether) and isophthalic acid [33].
Functionalized polystyrene can be used as macroinitiator for the synthesis of block
copolymers. Bromine terminated polystyrene with a molecular weight of > 20,000 was
used with Mn2 (CO)io as a free radical poly-merization catalyst; block copolymers of
methyl methacrylate, chloroprene or methyl acrylate, ethyl acrylate, butyl acrylate and
butadiene were prepared with this technique [34].
Sugar acrylate copolymers were synthesized by emulsion polymerization of
macromers containing reactive end groups with conventional vinyl monomers such as
vinyl acetate or acrylates. The macromers are made from modified sugar units. Such
copolymers are easily recyclable, biodegradable and compostable [35]. It should be
accentuated that radiation-curable adhesive raw materials ( monomers, oligomers or
polymers) possess only a limited use. According to Ref. [3 6], in 1996, lacquers
accounted for 82.8 % of the European market of radiation curable systems , with inks
representing 10.5 % and adhesives 6.7 %. Now their participation attains about 70%.
Elastomers were the first base materials for PSAs. First natural Rubber, later
synthetic elastomers were used.
1.4.1. Natural Rubber
By the use of natural rubber as raw material for PSPs, chemical interventions are
directed towards molecular weight regulation (by mechano-chemical destruction,
crosslinking or cyclization). For instance, according to Ref. [37], the first removable
price labels used almost exclusively a paper carrier coated with rubber-resin
adhesive.In such formulations, natural rubber, synthetic rubber and polyisobutylene
were added. The rubber was calendered (masticated ). Cyclised rubber was suggested
also as elastomer component with low viscosity.
According to Ref. [38], the use of natural rubber latex for pressure-sensitive
adhesives is limited by the following factors: low compatibility with resins; low
mutual solubility of resin and rubber ; low homogeneity of the films and too high
drying temperature in comparison to the softening point of the resins. Really, the low
compatibility of NRL and resins causes the inhomogeneity of the films and the low
mutual solubility too. Such low compatibility is related to the high molecular weight
of the rubber ( in comparison with masticated rubber used for solvent-based
formulations), to the low polarity of the rubber and to the different non-rubber-like
impurities in the NRL). However, contrary to the forecast in Ref. [39], in special
applications ( e.g., envelopes) NRL was not replaced by acrylics. Such formulations
which work like contact adhesives ( i.e., adhesive to adhesive) are based mostly on
natural rubber latex. For instance, a PSA that adheres to itself only is based on natural
rubber (15 pts ) and Alresen-PA 101 (5 pts ). The rubber is masticated and dissolved in
petrol, with a boiling point of 80-100 °C ( 85 pts ) [40].
10 VoL2,Chapter 1
1.5. Polymers with Segregated Structure
It has been shown, that the properties of polymers can be significantly improved by
build-up of a multiphase, composite structure. In such heterogeneous systems, one
polymer exists above the Tg ,while the other exists below its Tg.The one component is
glassy,the other is rubbery. Such interpenetrating networks can be made by several
methods including latex blending and sequential [41-43] or simultaneous
polymerization [44-46]. Multipolymers are synthesized by block copolymerization,
grafting reactions and side-chain and end-group reactions through unsaturation or
functional groups [47]. The smallest degree of phase separation and the highest
degree of interpenetrating results in simultaneous polymerization. In sequential
polymerization a two-step crosslinking may occur [46]. The network first formed is
to be a continuous network. Crosslinking is responsible for the control of the size of
the phase separated domains of the second network. A full interpenetrating network
may be formed when both of the components are crosslinked; the so-called pseudo-
interpenetrating network may be produced when only one of the components is
crosslinked. For instance, interpenetrated networks were made by swelling of PUR in
MMA monomer and polymerization of the compound. The introduction of the glassy
PMMA in the polyurethane elastomer leads to a polymer with broad glass transition
temperature domain.This is generated by the restriction imposed by the rigid polymer
component on the segmental mobility of the elastomer. Styrene block polymers are the
most important macromolecular products with segregated structure used for adhesives.
The off-line and in-line synthesis of multipolymers having segregated structure
was discussed in Vol.l,Chapt. 4, Sects. 1.1 and 1.2. Their modification by crosslinking
leads to more sophisticated networks (see Vol.l,Chapt. 4, Sect.2.2.1 ). Details of the
formulation of styrene block copolymers were described in the chapter discussing
tackification. Therefore in this chapter, only special aspects of the development of
the elastomer and viscoelastomer basis will be covered. Such aspects are related to
advances in macromolecular chemistry, which provide new pressure-sensitive raw
materials.
As mentioned earlier, multipolymer latex systems are produced too. In this case
the latex is made by multiphase reactions and not necesarily by emulsion
polymerization.
According to Ref. [48], the main thermoplastic elastomers include block
copolymers ( e.g.,styrene and styrene diene ,copolyester, polyurethanes and
polyamides); thermoplastic polymer mixtures ( blends of an elastomer and of a
thermoplast, e.g., nitrile rubber-PVC or EPDM rubber-polyolefins) and elastomeric
alloys ( that possess a highly crosslinked elastomer component).According to
Ref. [49], thermoplastic elastomers can be classified into the following main
categories [50]: styrene copolymers, olefin copolymers, vulcanized compounds,
polyesters, polyurethanes and polyamides. The main commercial grades are listed in
Ref. [48]. According to Ref. [51], the following macromolecular compounds are the
most important commercially available thermoplastic elastomers : thermoplastic
polyurethanes, thermoplastic polyesters, thermoplastic polyolefins and thermoplastic
styrene-butadiene copolymers.
The thermoplastic polyurethanes contain long flexible polyether or polyester
chains, which alternate with polar polyurethane segments , which associate by
hydrogen bonding. The polyether-ester copolymers possess flexible polyether chains
and polyester segments. The crystallization of the polyester segments causes domain
build up and phase separation. The olefinic TPEs are based on blends of polypropylene
with ethylene-propylene copolymers. Polyurethane and polyester based TPEs exhibit
high strengths and excellent environmental resistance, polyolefin TPEs display good
environmental resistance but low elasticity. According to Rader [48], the thermo-
plastic elastomers can be classified as : block copolymers, thermoplastic polyolefins

and thermoplastic vulcanizates.Thermoplastic elastomers combine the excellent
processing characteristics of thermoplastic materials with the physical properties of
elastomers. They bridge the gap between conventional elastomers and thermoplastics
[52].
Styrene block copolymers and multipurpose rubbers (MPR) can be processed on
rubber processing equipment (a t 110-160 °C ), polyurethanes and polyolefins can be
processed on machines for thermoplasts only ( at 160-210 °C). Polyamides and
polyesters require higher processing temperature (230-250 °C and 180-240 °C
respectively) [53]. Thermoplastic elastomers are manufactured as pellets: they do not
need granulation.They display the following disadvantages [54]: low elastic memory,
low application temperature range and no procissability with rubber processing
equipment. From such compounds, styrene block copolymers are suggested for
adhesive use [51]. The costs for different common elastomers (taking into account
their versatility too ) vary in the following range [55]:
SBR < NR < SBC < Butyl rubber (1.1)
1.5.1. Styrene Block Copolymers
Various thermoplastic elastomers were prepared by using different synthesis

methods. Such polymers are synthesized mainly using anionic living
polymerization(see Vol.2,Chapt.2 also). Because of the versatility of styrene
derivatives to undergo ionic living polymerization the most block copolymers contain
styrene blocks although acrylate blocks have been copolymerized also. Anionic
synthesis was achieved in 1956; styrene-diene block copolymers commercial
compounds) were synthesized in 1965 using living polymerization and styrene-olefin
block copolymers were manufactured in 1975. The styrene-butadiene block
copolymers of Shell have been supplied since the begining of the 1960s under the trade
name Kraton (USA )and Cariflex (Europe ). According to Ref. [56], ABA block
copolymers were introduced on the market in the mid-1960s. According to Ref.[57],
styrene block copolymers have been commercialized since 1965. Thermoplastic
elastomers have been used since 1970 for HMPSA [58].Later (in 1983), hydrogenated,
saturated block copolymers were synthesized. Such products were marketed by Shell
under the trade names Kraton-G and Elexar [59]. The grade Kraton-G is an SEBS
copolymer. Copolymers with controlled sequence distribution ( di-block /tri-block
ratio) were developed also. For instance, Vector SIS polymers (Dexco Polymers) have
been supplied since 1990 [60],
Common Products
According to Ref.[61], the main mid-block sequences are built-up from polybutadiene
(in SBS ), polysioprene (in SIS), ethene-buthene ( in SEBS), ethene-propene (in
SEPS) and functionalized ( maleinized or silanized) midblocks. The application field
of the copolymers is strongly influenced by the nature of the mid-block. Because of
the higher stiffness of the polybutadiene blocks, SBS polymers are recommended
mostly for non pressure-sensitive applications; SIS polymers are suggested for PSPs;
SEBS and SEPS polymers with hydrogenated ( saturated) structure are proposed for
severe application conditions. Functionalized polymers with polar groups exhibit
better adhesion to polar substrates. The nature of the mid-block affects the end use
domain of the copolymer too. As discussed earlier, commercially available SBCs
12 VoL2, Chapter 1
include isoprene and butadiene copolymers with styrene or a-methyl-styrene.

Common SIS copolymers contain styrene or a-methyl-styrene ( 10-35 % ) [62].
Styrene-isoprene-styrene copolymers based on a-methylstyrene end-block were
introduced on the market in 1985. For instance, the grade XU-16500 ( Dow ) is a
block copolymer of AMS-I-AMS .
The first known trademarks for SIS were Kraton-D-1107, D-l 117, D-l 112, and
D-l 111 (from Shell Chemicals), Europrene -Sol T 190 (from Eni-Chem Elastomeri),
Finaprene-414 ( from Fina Ltd. ). The literature data about their first marketing are
contradictory. According to Ref.[ 61], Cariflex thermoplastic elastomers have been
marketed since 1965.Cariflex-TR was manufactured first in USA in 1972 [63]. Such
copolymers are added at a level of 30-40% in the HMPSA. Their polystyrene content
must be lower than 40 % in order to ensure elastic properties[64]. According to Ref.
[64], the styrene block copolymers have generally a molecular weight of 6,000-
200,000 and a styrene content of 15-45 %. The polystyrene content has a strong
effect on the stiffness of the polymer, on its holding power, tack and viscosity [61]
(see Vol.l,Chapt. 4 also ).
The synthesis methods for styrene block copolymers include [24]: sequential
monomer addition using monofunctional initiators ( I ' ) ( Eq. 1.2 and 1.3); di-block
synthesis and coupling of di-blocks with mono- or difunctional coupling agents , CAs
(Eqs. 1.4 and 1.5 ) and polymerization with difunctional initiators (' I ’ ) (Eq. 1.6). In
this case the sequential polymerization of the diene or of styrene to a di-block is
followed by a coupling reaction where a difunctional coupling agent bonds the
segments together,or the synthesis is carried out as a common sequential block
copolymerization:
T Styrene -> ( Styrene )a‘ (1.2)
(Styrene )a" + Isoprene -» ( Styrene )a —(Isoprene )b" (1.3)
Sequential monomer addition is really the anionic polymerization of styrene

followed by chain extension of the polystyrene segments with butadiene (i.e.,
copolymerization) and repeated extension with a second polystyrene end-block to
produce a linear block copolymer. This method is based principally on the
homopolymerization of styrene and copolymerization of the styrene oligomers with
butadiene or isoprene.
Coupling uses di-blocks to combine them in higher molecular weight linear or
branched products [65]:
(Styrene )a - ( Isoprene )b’ + CA + (Styrene )a - ( Isoprene )b-> (1.4)
( Styrene )a - ( Isoprene )b - CA - ( Styrene )a - ( Isoprene )b (1.5)
The best known synthesis methods of styrene block copolymers by coupling are
based on a 3 step and a 2 step procedure. In the 3 step procedure there are two
separate phases in which polystyrene and polydiene blocks are synthesized using a
monofunctional anionic initiator ( e.g., sec-butyllithium [66]):
n ( Isoprene) + T ->( Isoprene )n (1.6)
n ( Styrene) + I' -*( Styrene )n (1.7)
where I is the monofunctional initiator having an active site. In the third step, two half
molecules ( 2 di-blocks ) are coupled in the presence of a coupling agent, giving

polystyrene-polyisoprene-polystyrene copolymer.
2 ( Isoprene )n+( Styrene)n - » ( Isoprene )„ - ( Styrene )n- ( Isoprene )n (1.8)
The coupling efficiency does not attain 100 %, therefore, such products always
contain 15-20 % di-blocks:
( Isoprene )n+( Styrene )n -> ( Isoprene )n - ( Styrene )n (1.9)
Polystyrene homopolymer is formed also. The polymer synthesis by coupling

supposes the production of a living ( anionically reactive ) styrene-butadiene
copolymer (oligomer) which can be coupled with di- or polyfunctional coupling
agents to give a linear copolymer (1.10), e.g., Kraton ( Shell), Vector (Dexco ) etc., or
branched or multi-arm (radial) copolymers (1.11), e.g., Solprene ( Phillips), Kraton
(Shell), etc., grades [65] ( see Vol.2, Chapt 2)..
( 1. 10)
( 1. 11)
Difunctional initiators initiate two anionic polymerizations simultaneously. In this

procedure, two dienes are coupled first:
Isoprene + T+ Isoprene —» ' ( Isoprene )b- 1 - (Isoprene )b~—> (1.12)
Styrene + ’( Isoprene )b - 1 - ( Isoprene )b" + Styrene —> (1.13)
(Styrene )a - ( Isoprene )b - 1 - ( Isoprene )b - ( Styrene )a
This procedure ensures the simultaneous build-up of the tri-sequenced block

copolymer using di- or trifunctional initiators/catalysts which produce living
polybutadiene ( with two active sites ) where styrene can be polymerized or
polystyrene tipped.
The main characteristics of such polymers are: the degree of branching (linear or
armed, see above); the polystyrene content; the molecular weight and the
microstructure. The degree of branching is related to the molecular weight, which
influences the viscosity too. It should be stated, that both the molecular weight of
the sequences and the global molecular weight are important characteristics. The
molecular weight of the mid sequences affects chain elasticity and reactivity; the
molecular weight of the end sequences influences molecular association, i.e., material
strength.The glass transition temperature of polystyrene depends on the molecular
weight up to about 20,000. The global molecular weight determines the mechanical
and melt flow properties of the compound. As theoretically supposed, for the same
global molecular weight, branched polymers possess lower viscosities than linear
ones. Because of the determinant role of the molecular weight of the polystyrene
sequences, which must have the same magnitude as those for linear polymers, the
global molecular weight of such polymers is much higher; therefore their viscosity is
higher too.For instance, for the same molecular weight of 12,000 of the polystyrene
block in a linear or armed copolymer the total molecular weight of the polymer is
14 VoL2, Chapter 1
80,000 or 160,000 respectively and the viscosity of the linear copolymer is low, that of
the branched one is high [32].
Anionic polymerization of dienes in hydrocarbon solvents yields mainly cis
configuration , like in natural rubber. Hydrocarbon soluble difunctional initiators lead
to cis diene in the mid-block. Changes in the mid-block structure allow further
modifications of such polymers. For instance, the 1,4- trans structure crystallizes
easily [67]. Changing the macrostructure of cis-BR improves its properties. For
instance, changing the macrostructure by means of coupling reaction at the end of the
living chain produces polymers with improved characteristics [68]. Hydrogenation
provides other modification possibilities. The saturated mid-block thermoplastic
elastomers are commercially ABA type block copolymers where the polyisoprene or
polybutadiene is hydrogenated [69].The chain dimensions of hydrogenated
semicrystalline polybutadienes are in semicrystalline status about 13 % greater than
those of lineary polyethylene in the theta status [49]. The block copolymers with the
saturated mid-block segment have an Mn of about 25,000 to 300,000 [70].
Generally, the saturated polymers (Kraton-G) possess higher solution viscosity and
are harder. They display a rapid increase of the viscosity after cooling . The Kraton-
G grades exhibit 100 % elastic recovery in comparison to Cariflex ( 10-15% ). The
Cariflex and Kraton-G polymers with the highest molecular weight have the highest
styrene content too.
The cohesive strength of styrene-block copolymers is obtained by the associative
structures built-up by the polystyrene blocks.The size and morphology of the
polystyrene domains influence the cohesive strength. It depends on the polystyrene
content of the copolymer. For instance, replacing a di-block with 18 % styrene with
the tri-block with 29 % styrene up to 30 % increase of the shear resistance can be
obtained. However ,improving the cohesion by increase of the polystyrene level of
styrene block copolymers is limited because of the increase of the plateau
modulus.This makes the polymer more difficult to tackify (see Vol.l,Chapt. 4).Melt
viscosity also increases with styrene content. It should be mentioned that the ,^rigidity „
of the polymer due to its higher styrene content can be partially balanced by reduction
of the global molecular weight.
Cohesion increase is possible by changing the sequence length of the polymer, the
level of sequences having different length and the global composition of the polymer
( i.e., the copolymer/homopolymer ratio). Such regulation of die polymer composition
and structure is possible by using different synthesis methods. Copolymers with di- and
tri-blocks differ mainly in their elasticity and shear resistance. Because of the
enchanced mobility of di-blocks ( they are fixed in molecular associations on one end
only ) they improve the wetting and adhesion and make the polymer less elastic and
thus more cuttable.Di-block reduces the plateau modulus and results in softening at a
lower temperature. The di-block-ffee product exhibits higher shear strength and better
high temperature performances. It possesses better mechanical properties. For
instance, a pure tri-block copolymer shows 6.3 x 105Pa tensile strength (in comparison
with 4.2x103 Pa for SI di-block) [65].
It is evident that a higher degree of molecular association improves the shear
resistance, however, it cannot improve the temperature resistance and SAFT which
are dependent on dissociation , which is a function on the Tg of the polymer. To
improve the temperature resistance of styrene block copolymers the following
possibilities were tested: reinforcing of the polystyrene domains with high melting
point tackifier resins ( see Vol.l,Chapt. 4 also ) and change of the Tg of the end-
blocks. Therefore other styrene derivatives were studied as aromatic monomer.
Copolymers of styrene with a-methylstyrene give better temperature resistance. For
such polymers with a lower end-block molecular weight (15,000), a comonomer ratio
(styrene/a-methylstyrene) of Vi was suggested [65].
Triblock
Di-block-Triblock
Tackified Triblock
Fig.1.2 The influence o f “diluting agents” on the damain build-up in SBC ( E-aromatic units;
M-diene mid-blocks; MCT-mid-block-compatible tackifier).
As discussed earlier, block copolymers can be manufactured by coupling too.The

base segments for such coupling can be synthesized by free radicalic polymerization
also. For instance, by polymerization of styrene using a functionalized azo-derivative
(e.g., 4,4'-azo-4-cyan-rt-valeric acid. The polystyrene prepared in such a way
possesses carboxy end groups which can be transformed into more reactive acid
chlorides. Such groups can react with diols (e.g., hexanediol or decanediol).Tri-block
copolymers of styrene,a-methylstyrene and methyl methacrylate were prepared using
sodium atom induced polymerization [71]. Methyl-methacrylate block copolymers
and methylmethacrylate-styrene block copolymers can be prepared too [72]. Block
copolymers of isoprene with butylstyrene, methylstyrene and styrene were
synthesized and compared [73]. A styrene-isoprene-styrene copolymer with very high
styrene content 78 % by weight,and Mn of 90,000 was transformed with
chlorosulphonyl-isocyanate and consecutive hydrolysis in membranes with blood
compatibility [74].
As illustrated in Fig. 1.2, the plasticizing/tackifying possibilities provided by the
sequence distribution of the base polymer , together with the use of end block or
mid-block compatible ( aromatic or aliphatic ) plasticizers and tackifiers , and thus the
regulation of the degree of order (network density) of the base polymer allows the fine
regulation of the adhesion-cohesion balance of SBC-based formulations.
Multiblock Copolymers
According to their structure, styrene block copolymers can have a linear (1.14), radial-
branched (1.15), or multi-arm (1.16) structure [61]:
(1.14)
16 Vol.2, Chapter 1
(1.15)
(1.16)
Three- and four-armed, and multi-armed ( > 4) polymers are available as

commercial products. Multiblock copolymers offer new possibilities for regulation of
the molecular weight,viscosity, segregation and functionality. For instance, the
armed polymers ( Kraton D-1122X, and D-1320X and Cariflex-TR-KX139) have
lower MFR and more hardness. Such polymers can be prepared from different
chemical compounds, thus hydrocarbon based elastomers (e.g., SBC ) or heteroatom
based elastomers (e.g., polyurethanes, polyesters, halogenated compounds, silicones,
etc. have been manufactured).
Various new synthesis methods were developed to prepare star shaped, segregated
polymers. For instance, butadiene and styrene were copolymerized with maleic acid
[75]. By the reaction of such copolymers with metallic alcoxides ( Al, Mg, Zn, Na and
Ag ), metallic salts are formed . Such copolymers having 2 % ionic groups have a
star-shaped structure where the ionic interactions improve the mechanical properties
through their association. Such ionic bonds dissociate ( as showed by DSC ) between
125 and 150 °C.
Multi-block polyurethanes have been developed also. Such polymers possess the
following general formulation: -( AB )n- where n >10. In comparison with common tri
block SBCst he molecular weight of the soft sequences is very low ( 600-4,000 ).The
soft blocks are polyether or polyester with low Tg; hydroxylated polybutadienes and
polydimethylsiloxanes can be used too [76]. New (AB)n block copolymers can be
prepared by low temperature polycondensation of acylchloride-terminated
polytrimethylene terephthalate (as hard block ) and amine-terminated acryl nitryl-
butadiene rubber. The crystallinity of such copolymers is given by the hard
blocks.The copolymer behaves at 125 °C as a TPE. Above 150 °C a post crosslinking
of the residual double bonds occurs [77]. The new catalyst sytems provide control of
molecular weight and MWD, of the sequence distribution and of the geoisomeric
structure of diene units, and provide either a linear or a star molecular structure
[78].The Tables 1.2 and 1.3 present the main thermoplastic elastomers suggested as
raw material for adhesives.
Functionalized Products
Functionalization of commercial high polymers ( e.g., styrene block copolymers) or

the synthesis of functionalized oligomers (e.g., epoxidized and hydroxylated
poly(ethylene-butylene) oligomers) provide new possibilities for the build-up of
polymeric networks. Several experimental polymers have been prepared. For instance,
carboxyl terminated butadiene-acryl nitryl copolymers can be reacted with a
difunctionally brominated epoxide resin and thus a rubber component with epoxy end-
groups can be prepared [79]. Poly(acetylene-co-ethylene) was synthesized by the
isomerization of poly-1,3-butadiene. Products with up to 10 conjugated double
bonds can be prepared in such a way [80].
Table 1.2 The Main Thermoplastic Rubbers Used in Adhesives
Chemical Grade Supplier Type MW Styrene Solution DB

basis content viscosity
(%) (Pa.s)* (%) Ref.
SBS Cariflex T Shell

TR-1186 (SB)„ high 30 20 — 82
TR-1102 (SB)2 low 28-30 1.2 — 82,83
TR-KX139 (SB)2 low 40 0.6 — 82
Kraton D-1101 SBS li high 31 4.0 — 84
D-1102 SBS li low 28 1.2 — 84
D-1133 SBS li low 35 0.4 34 84
D-1300X SBSlic — 17 6.0 — 84
D -1116 (SB)„ — 21 9.0 — 84
D-1122X (SB)„ — 37 0.7 — 84
D-1135X (SB)„ — 35 0.7 — 84
D-1184 (SB)„ — 30 20.0 — 84
D-1188X (SB)„ — 35 0.9 — 84
D-1118X SB 30 0.8 80 84
Stereon-840A Firestone (SB)„ — 43 — — 56
Europrene-Sol
TE 6414 Enichem (SB)„ — 40.0 — 30 85
Vector-241 ID Dexco SBS 28.5-31.5 0 86
Vector-2518 D Dexco SBS 29.5-32.5 <1 86
Vector-8508 Dexco SBS 27.0-30.0 <1 87
Vector-4461 Dexco SBS 41.0-45.0 <1 84
Note (Tables 4.2 and 4.3): DB- di-block content; Viscosity of a 25 % solution in toluene; *Brookfield, toluene,
77°C , 25%; ( SI )n styrene isoprene multiarm ; ( SB )„ styrene butadiene multiarm; SB di-block;FU-
functionalised,l% bound functionality as succinic acid; Mi-mixed diene;li-linear; lie-linear crosslinkable
copolymer
Polymers with hydroxylated end groups can be synthesized by free radical

reactions using H20 2 as initiator for the reaction of vinylferrocene and butadiene [81].
Thermoplastic Polyurethanes
In elastomers based on diisocyanates, the urethane groups are fixed on the

crosslinking points; therefore, they cannot build reinforcing domains. Urethane groups
were built in the oligomers which are situated at a longer distance from the network
points.Such films radiation cured show better tensile strength and elongation at break
[89] . Segmented polyurethane with soft segments of butadiene with OH groups
and hard segments of butandiol and toluilenediisocyanate have been manufactured
[90]. Segmented polyurethanes with polyoxytetramethylene soft segment, and
polyether polyester as hard segment have been synthesized also [91]. Polyisobutylene-
based urethane networks were produced with tri-armed telechelic polyisobutylene triols
and 4,4'-diphenyl methanediisocyanate [92]. Polyurethane-diacetylene segmented
copolymers have been synthesized too. Such polymers have the acetylenic units as
hard segments. Hydroxyl-terminated polyethers were reacted with diphenylmethane
diisocyanate for the soft segments and with diacetylene diols for the hard segments.
18 VoL2,Chapter 1
Table 1.3 The Main Thermoplastic Rubbers Used in Adhesives.
Chemical Grade Supplier Type MW Styrene Solution DB

basis content Viscosity (%)
(%) (Pa.s) Ref.
Cariflex T R -1107 Shell (SI)2 high 15 1.6 <15 82

TR-KX83 (SI)2 high 15 0.8 40 82
TR-KX81 — high 21 — <15 82
Kraton D-1320X (SI), low 10 25 — 82
2.5 84
D-KX602 ABA — 23 — 17 85
D-1112 ABA low 14 0.9 40 83,84
D-1117 ABA low 17 0.5 40 83,84
D-1107 SIS li med 14 1.4 — 83,84
D -llll SIS li low 22 1.2 — 84
D-1113X SIS li low 16 0.6 55 84
D-1114X SIS li low 19 0.7 0 84
D-1125X SIS li low 30 0.3 — 84
Vector 4111 Dexco SIS — 18 0 60
4113 SIS — 15 18 60
4114 SIS — 15 42 60
4411 SIS 42-46.5 87
DPX-556 Exxon (SI)4 — 21 13 55
DPX-551 Exxon (SI)4 — 21 31 55
SEBS Kraton G-1652 Shell SEBSli 30 1.3 — 84,88
G -1650 SEBSli 29 8.0 — 84
G-1654X SEBSli 31 1.4 84
FG-1901X SEBSliFU 30 1.2 — 84,88
FG-1921C SEBSli FU — — — 84
G-1726X SEBSli 30 0.2 70 84,88
G-1657 SEBSli 13-14 4.2 30-35 83,84, 88
GRP-6919 MI 18 — — 5
Such polymers exhibit a two-phase structure. They can be crosslinked by the acetylenic
units in the hard segment without affecting the elastic and flexible nature of the soft
segment [93].
1.5.2. Special TPEs
Special methods of synthesis can provide special thermoplastic elastomers. For

instance, block copolymers were synthesized through difunctional initiation with an
initiator made from sec.butyllithium and 1,3-bis (phenylethenyl)benzene. In such a
way living polybutadiene was prepared and used for the manufacture of block
copolymers [94].The w-butyllithium-initiated polymerization of 2-isopropenyl
chinoline leads to high Tg polymers (475 °K ) with a molecular weight of 6,700 to
210,300. Such polymer segments can be copolymerized with living polybutadiene to
give segmented (di- and tri-block ) copolymers [95]. By the polymerization of
butadiene with butadienyl lithium oligomers and tetramethylene diamine the
amine/lithium ratio strongly influences the level of 1,2-structures [96].
The 1,4-polymerization of butadiene initiated by 6/s(r|3allyl) (trifluoroacetato)-
nickel in a living coordination system may lead to stereo di-block copolymers of
polyc/s-l^-butadiene-poly-ftm?-1,4-butadiene, or butadiene block copolymers [97].
Cationic copolymerization was developed for the synthesis of thermoplastic
elastomers also. Polymers of polyethersulphones ( PES ) and 2 ,6-dimethyl-1,4-

phenylene oxide (PPO) synthesized by cationic polymerization having reactive
endgroups ( vinylbenzyl or styryloxide ) can be used as macroinitiators for the
synthesis of ABA block copolymers or alternating copolymers such as PPO-PES-PPO
or polytetrahydrofurane-polystyrene-polytetrahydrofurane. Such macromers have a T*
of 22 °C-174 °C [98].
Other hard comonomers having heteroatoms were tested also. For instance,
butadiene-dimethylsiloxane block copolymers were prepared from butadiene,
hexamethylcyclotrisiloxane and octamethyl cyclotetrasiloxane through anionic
polymerization in tetrahydrofurane with naphthalene- sodium [99]. Segregated diene
polymers were prepared using styrene and butadiene derivatives with alkoxysilyl
groups and with silyl protective groups masked -OH,-NH2,-CHO and COOH
groups.They were polymerized or copolymerized and the polymers were hydrolyzed.
Such block copolymers show phase separation [100]. Multi-phase systems are formed
by the reaction between carboxylated butadiene and glycidyl methacrylate [ 10 1 ].
Widely spaced comb-like polymers having fluoralkyl side chains were prepared also.
Alternating copolymers of butadiene and fluoroalkyl methacrylates (with fluorinated
docecyl-octadecyl side chains ) were synthesized . Such polymers have on each sixth
carbon atom a fluorinated side chain. They exhibit the same contact angle for water
and rt-alkanes. Such polymers show crystallization of the fluoralkyl side chains
which leads to segregated structure [102]. Crosslinked polyisoprenes with domain
structure were prepared by the polymerization of isoprene with reactive
divinylbenzene-ethylvinylbenzene copolymer microgels [103].
Other comonomers and synthesis methods have been studied also.For instance,
vinyl acetate-styrene block copolymers were synthesized from polyvinyl acetate
[64] .The polymer was reacted with phthaloylperoxide and styrene. Low pressure
block copolymerization of ethylene-propylene was carried out too [104].
Polyamideimide-polyimide block copolymers were developed having excellent
thermal stability ( up to 500 °C) and melt-processibility [105]. Biologically degradable
block copolymers were tested for medical use. Such block copolymers are based on s-
caprolactone and AL-lactide [106]. Thermoplastic fluorpolymers contain a soft
fluorelastomer phase and a hard fluorinated resin phase [107]. Polyethylene
isophthalates were prepared from isophthalic acid and ethyleneglycol. Such polymers
react with carboxy terminated butadiene-acryl nitryl copolymer ( as acid chloride),
and give ABA type block copolymer [108]. Block copolymers were prepared from
epoxides and carboxylated butadiene oligomer. Such polymers exhibit a two-phase
structure. Their degree of microsegregation does not change monotonically with the
increase of the molecular weight of the hard segments [109]. Thermoplastic
elastomers can by prepared by hydrogen bonding too. Hydrogen bonding between
urazole groups on polybutadiene has been studied spectroscopically. Such bonds
disappear at higher temperatures [110]. The above examples illustrate the broad
range of potential segregated polymers. Segregated styrene-diene polymers can be
synthesized by emulsion polymerization too; in this case, segregation is obtained
through particle morphology (see later).
1.6. Alternating or Random Copolymers as Elastomers
Natural rubber was the first raw material used for PSA manufacture. Later synthetic
rubber-like polymers were produced. Some of them possess a natural rubber-like
20 Vol.2,Chapter 1
chemical composition ( i.e., they are polydienes ) and structure (cis ). For instance,
polybutadiene rubber,with high cis grades (cis made with Ti' catalysts, or Neocis made
with Nd catalysts) , and low cis types ( e.g., Intene® made with Li catalysts ) are
available also [111]. The copolymerization of the dienes with hard monomers
produced rubber-like polymers too. Different polymerization systems (e.g., peroxides,
metallocenes, etc.) were tested also [112]. Insertion of polar functional groups in the
diene-vinyl copolymer allowed the synthesis of water-based latices. The co
polymerization of dienes with special reactive monomers provided the possibility of
chemical crosslinking. Block copolymerization of dienes with monomers that build-up
ordered and segregated structures (e.g., styrene ) allowed the physical crosslinking of
synthetic elastomers.
1.6.1. Raw materials for Solvent-Based Formulations
Alternating or random styrene-diene copolymers are common raw materials for the
rubber processing industry. There are numerous commercial grades available. Some of
them are also suitable as adhesive raw materials . Such copolymers possess a low glass
transition temperature. For instance, a styrene-diene copolymer ( Dispercoll-S31)
suggested for PSAs exhibits a Tg of -64 °C [113]. Emulsion-polymerized styrene-
butadiene rubber (E-SBR), can be cold polymerized, e.g., Europrene®/In-tol® ( 1500,
1502,1507,1509, 1512, 5502 ). Solution-polymerized styrene-butadiene rubbers ( S-
SBR ) are available also.The Cariflex E-SBR hot clear types ( S-10111C,S-101 IE and
S-1013 ) are recommended for solution applications [111]. Such polymers have a
22.5-44.5 % styrene content and Mooney viscosity of 40-59 (ML 1+4 ,100 °C ).
In in the first period of the development of synthetic rubber technology, emulsion
polymerization of SBR was the primary method for producing general purpose
synthetic rubber. Polymers produced by this method have a broad range of molecular
weight and a high degree of branching. In the early 1960s, Firestone introduced
random solution styrene-butadiene rubbers ( Stereon ) on the market [114]. The
differences in the properties of emulsion and solution polymerized rubber are to some
extent the result of the contribution of resinous impurities in emulsion SBR. Solution
SBR has narrower MWD (2.10 vs 5.5), lower vinyl content ( 11 % vs 17%), lower Tg (-
69.7 °C vs -50.6 °C) for lower bound styrene (18% vs 22 %) and more cis-1,4 content.
The hot process SBR contains more styrene ( 45-80 % ) than the low temperature
process SBR (25-30%) [115].
Polar vinyl-diene copolymers have been developed too. Random copolymers of
dienes with polar vinyl monomers with heteroatoms or with dienes having heteroatom
were synthesized. The best known products are the copolymers with acryl nitryl and
with chlorbutadiene. Special polychloroprene grades having a linear, non-branched
structure do not need mastication, they can be dissolved directly. Such products can be
filled with 11% -15 % metal oxides without affecting the adhesive properties. Nitrile
rubbers display Tg values of - 48 to -1.5 °C, depending on their nitrile content.
Hydrogenated NBRs exhibit a Tg value of -25 °C, independently of the nitrile content.
Such compounds display strain induced crystallinity which ensures tensile strength
values 200 times higher than the non hydrogenated product [116]. Such products are
used mostly for special applications, e.g., where flame- or chemical resistance is
needed. For instance, self adhesive tapes for wrapping around cables to make them
less susceptible to damage in fires include 100 pts of 40/60 to 65/45 mixtures of
chlorinated polyethylene/acryl nitryl-butadiene rubber, 50-140 parts 1 /2 -2/1 mixtures of
hydrated alumina, calcium carbonate and borate salts, stibium oxide and liquid
chlorinated paraffin [117].Nitrile rubber must be masticated (20-70 °C). The masticated
rubber is blended with 25-35 % of the solvent quantity required and swollen (4-6 h).
Non-masticated or masticated old rubber builds up a highly viscous gel in the solution
[118].
1.6.2. Synthetic Rubber Dispersions
Carboxylated styrene-butadiene latices are anionic dispersions of styrene-butadiene

copolymers modified with carboxylic and heat reactive groups, they provide a wide
range of film hardness from soft to extremely hard and tough.There are numerous
commercially availablestyrene-butadiene rubber dispersions ( from BASF,
Doverstrand, Dow, Goodrich, Bayer, Metallgesellschaft, etc. ) ; most of them are
carboxylated . For instance, the Polysar Latex 3958 ( formerly Polysar actually a
BASF product) is a high cohesion latex (Tg -31 °C),which requires more tackifying
resin than the soft latex ( grade 3703 ) with a (Tg -54 °C) [119]. Revinex-31F40
(Doverstrand) is a low Tg (-59 °C ) low molecular weight CSBR suggested for deep
freezer formulations [120]. Revinex-96C40 and 97D40 CSBR dispersions are suitable
for deep freezer label adhesives. They have a butadiene content of about 63 %
[121]. Such products can differ according to their molecular weight ( e.g., the
Synthomer Latex-1338 is a low molecular weight product, the Synthomer-VL10054
possesses higher molecular weight) or to their acid comonomer (e.g., the Synthomer
Latex- VL10067 ).
Investigations on the synthesis and properties of styrene-butadiene emulsion
polymers have been carried on on a large scale. There are to be mentioned above all the
publications of Spitzer [122-125], who cleared the interdependence between the
polymerization conditions, molecular characteristics and pressure-sensitive properties
of styrene-butadiene latices. As stated by Spitzer [122], for styrene-butadiene latices
the balance of the pressure-sensitive properties decisively depends on the glass
transition temperature and molecular characteristics ( sol/gel ratio) of the polymer.
On the other hand the maximum peel strength is found to be independent of the gel
level and possibly of the glass transition temperature [123]. Latices having the same
Tg but different gel level were synthesized.These latices were blended to give
compositions with the same gel level of about 44 %. Thus, only the type of sol and gel
varied ( from „loose„ to „tight„). The more gel is synthesized, the tighter it gets.
For unblended styrene butadiene latices as the gel level decreases , the peel
resistance first increases, then the mode of failure changes from adhesive to cohesive,
while the shear is too low at below about 25 % gel level. For polymer blends with the
same gel content and Tg, the modulus increases and the damping factor decreases .
These results together with the pressure-sensitive characteristics indicate, that, for such
blends ( where only the type of the gel differs ), the tight gel fraction tends to
determine the properties .It is suggested that in such blends the tighter gel is not
readily swellable and hence the poor shear values. The presence of the „tight „gel
promotes the adhesive failure too.The strong dependence of the pressure-sensitive
properties on the rubbery network ( g e l) characteristics shows that for such polymers
the rheological ( DMA ) data alone do not allow the prediction of pressure-sensitive
formulability. On the other hand, for such copolymers a high polymer blending-based
formulation ( like for the acrylics ) is limited too.
Generally styrene-butadiene latices are modified with an antioxidant, pH adjuster,
chelating agent and preservative [126]. For SBR latices without carboxy groups
poststabilizing with surface active agents ( e.g., sodium lauryl sulphate, sodium
dodecyl diphenyloxide disulphonate and non-ionic alkylphenol derivatives) was
suggested. The common vinyl acids used for carboxylation are: acrylic, itaconic, and
fumaricacid (1.0-3.0 % ).
22 VoL2,Chapter 1
Carboxylated neoprene latex is preferred because of its better specific adhesion

on metals and good colloidal stability. Carboxy group-containing chloroprene rubbers
are prepared by emulsion polymerization of chloroprene with 1.5 % methacrylic acid
using alkali metal salts of C6-i8 alkylbenzenesulphonic acid and HCHO-(3-naphthalene
sulphonic acid condensates in a specially defined ratio. Such emulsions show less
than 2 viscosity deviations in 5 runs [127]. The oil resistance of chloroprene can be
improved by copolymerization with acryl nitryl. Most polychloroprene latices are
anionic and possess a high pH value necessary for their stabilization. The HC1 formed
from the polymer may destroy the surface active agent [67]. Polychloprene latices
have 40-60 % solids and a viscosity of 300-400 mPa.s. Neoprene Latex 102 (from
Du Pont) has an average particle size of 3 pm.
Nitrile rubber dispersions are used in the tape industry for masking tapes. Such
PSAs contain low molecular nitrile rubber.Such a product possesses a shelf life of 12
months .The special rubber is tackified with colophonium derivatives. Such adhesives
are used for tapes or for items employed as contact adhesive ( PSA on PSA ) also, and
exhibit readherability [128].
Segmented polymers have been prepared using the emulsion polymerization
technology also. In this case, phase separated morphologies are produced using
multistage emulsion polymerization. Such approaches usually involve a sequential
polymerization of a hard phase and a soft phase within a single polymer particle in a
batch or a continuous process . Such polymerization processes are termed often „core
shell,, or latex interpenetrating networks. Spitzer and Zosel [124 ] designed a two-
stage process , in which the first stage yields a low Tg polymer, and the second stage
yields a high Tg low molecular weight polymer, using styrene and butadiene as the
main monomers. In this processes the chain transfer process is the predominant
molecular weight determining mechanism; they use the term polytelomerization and
polytelomers for the two stage polymerization process. Some of the synthesized
compositions can exhibit multi-phase morphology, having segregated styrene rich
domains surrounded by butadiene-rich phase, both of these phases being embedded in
a honeycomb carboxyl rich phase.The most important parameters that control the
properties of the final compositions are the weight ratio of the polymeric and
telomeric stages,the Tg and molecular weight of each stage,the level of carboxylation
and the degree of conversion of the polymeric stage. Some of such polymers exhibit
special properties, e.g., higher peel resistance at lower peeling rates, which can be
explaned supposing the deformation of the styrene segments also.Because of their
multi-phase structure with hard and soft segments, such polymers behave like tackified
ones. Thus it can be concluded that random styrene-diene polymers offer new
possibilities for off-line formulation,given by the control of the gel/sol ratio and by the
synthesis of polymer particles having multiple morphology.
Polymeric Alkene Derivatives
Polymers and copolymers of C3 and C4 alkenes include a broad range of plastomers,

elastomers, viscoelastomers and viscous compounds which can be used as various
components of pressure-sensitive products. Such compounds are employed in
processing of plastics and in classic adhesives too. The best known of them are
butene ( isobutene) oligomers or polymers and propylene polymers.
1.7.1. Poly(butenes/isobutenes)
Alkenes and isoalkenes with C4 constitute the raw material basis for a range of
macromolecular hydrocarbons which exhibit viscous or elastic properties depending
mainly on their molecular weight. Such compounds are known as polybutenes or
polyisobutenes. The polymerization of butene and isobutene and their
copolymerization with dienes or functionalized monomers made possible the synthesis
of new rubber-like, viscoelastic or viscous, hydrocarbon-based polymers. Polybutenes
are obtained by the polymerization of a C4 fraction containing a high proportion of
isobutene. A wide range of polymers with different molecular weight ( 440-5,900) is
produced having a viscosity of 13 to 40,500 m2/s ( at 100 °C , ASTM D445) [129].
High molecular weight , rubber-like polyisobutene was synthesized first in 1934
[130]. The properties of polyisobutene were described in detail by Jordan [131].
Butylrubber is a copolymer of isobutene with isoprene (with less than 3% isoprene)
having a molecular weight of 300,000-400,000. It is manufactured as latex also. In
butylrubber,a chain segment of about 100 isobutene molecules contains about 3
isoprene molecules [132]. In butyl rubber ( as determined by 13C-NMR ) the butene
and isoprene units are inserted in head to tail position [133].
Polyisobutenes are liquids ( having a molecular weight of 36,000-58,000 ) or
solids (having a molecular weight of 800,000-2,600,000 ). Polyisobutenes exist as oily
liquids having a low molecular weight ( 300-4000 ), highly viscous, tacky liquids
with a molecular weight of 40,000-120,000 and elastomer-like solids with a
molecular weight of more than 300,000. They possess a low Tg of about -50 °C to -60
°C. The low molecular products are known ( specially in USA ) as polybutenes also.
Polybutene ( e.g., Parapol from Exxon ) can be used as plasticizer [134] ( see
Vol.l,Chapt.4 ). Polybutenes are liquidshaving a high degree of tack. They can be
used as tackifier and modifier.Their properties were studied as main tackifier for
butyl rubber (with a molecular weight of 450,000 ) and polyisobutene ( with a
molecular weight of 2 , 100 ,000 ).
The main commercial products are the low molecular weight Indopol (Amoco),
Oppanol-B (BASF) and Napvis (BP), the medium molecular weight Oppanol (BASF)
and Vistanex grades ( Exxon ) and the rubber-like Oppanol-B and Vistanex grades
[135].The mechano-thermal degradation of polyisobutenes can be accelerated by using
peroxides (e.g., butylperoxide). In such procedure ( with 0.25 % di-f-butyl-peroxide)
the molecular weight decreases from 81,400 to 19,000 (mastication) [136].
Polyisobutenes are used for tapes, medical plasters and labels [137].
Polybutenes display the following advantages: compatibility with aliphatic
resins,compatibility with atactic PP and SBC, high filler level tolerance, formulation
latitude to balance the adhesive properties, optimization of low temperature properties
( by Tg ),optimization of high temperature properties (through the Tm ) and of the level
of crystallinity [138].High molecular weight polybutenes (with 85-98 % monoolefins)
were supplied as modifier for thermoplastic elastomers (e.g., Amoco Polybutenes).The
tackiness of such polymers increases with the molecular weight. Such polybutenes
have viscosities of 27 m2/s at 38 °C (grade L-14) and about 600 m2/s (grade H-300)
and 3400 m2/s at 99°C (grade H-1500) [139]. High molecular polybutene is suggested
as tackifier/plasticizer for special (e.g., medical, insulating,masking and electric),
packaging and general use tapes based on adhesives with hydrocarbon rubbers.
High molecular polybutene is miscible with most hydrocarbon rubbers.
Pelletized, partially crosslinked butyl rubber is suggested for 100 % solids butyl tapes
[140] . Halogenated phenolic resins can be added at high temperature to butyl rubber
[141] . Secondary rubber dispersions were proposed as filler for water-based adhesives
in order to improve their plasticizer stability,solids content and temperature stability.
Such dispersions have particles of 20-30 pm and are based mostly on butyl rubber
[142] .
24 Vol.2, Chapter 1
1.7.2. Amorphous Polyalphaolefins
Amorphous polyalphaolefins (APAO) are usually low molecular weight polyolefins

with melt viscosities in the range of 100-10,000 mPa.s, which are obtained in Ziegler-
Natta polymerization as a byproduct or specially tailored product [143].
There are three product typesipolypropylene homopolymers, ethylene-propylene
copolymers and 1-butene-propylene copolymers. The adequate choice of the catalyst
and comonomers leads to products which have well defined properties such as melt
viscosity, softening point, needle penetration, embrittlement temperature and open
time [143]. Special products are known too. For instance, silane modified amorphous
polyalphaolefins ( e.g., Vestoplast-206 from Hiils ) form strong chemical bonds
between the silane groups and O-H groups of the substrate surface and crosslink
under the influence of moisture [144]. Atactic polypropylene obtained as byproduct in
the synthesis of polypropylene was first used as raw material for hot-melt pressure-
sensitive adhesives [145]. So-called „on purpose,, polypropylenes were synthesized
at the beginning of the 1970s. First ethylene-propylene copolymers were
manufactured. Such polymers cannot be used as raw materials for hot-melt pressure-
sensitive adhesives. Their tackifying leads to softening, but such products do not
have the required viscoelasticity. The copolymerization of propene with long chain
olefins leads to amorphous and tacky products. The best results have been obtained
with hexene and octene as comonomer. Such C3/Q copolymers have intrinsic pressure
sensitivity, but they cannot compete with SIS copolymers concerning their price
and adhesive properties. Various amorphous co- and terpolymers of a-olefins have
been developed [146]. Such products exibit the following characteristics: they possess
a Tg of -10 to -40 °C,tensile strength of lxlO 3 -3xl0 5Pa; viscosity of 0.20 to 10 Pa.s (at
190 °C ), R&B softening point of 80- 150 °C, amorphous content ( hexane index ) of
0-50 % ,( probe) tack of 0 - 800 g and shear (static ) of 1-30 h.
Such amorphous polyalphaolefins are pressure-sensitive in the neat form, i.e., they
do not need tackifiers. Because of their low viscosity , the viscosity of the polymer can
be tailored to the adhesive so that low viscosity components are required only to
provide better performances , not lower viscosity. They offer the following advantages
over typical styrene block copolymer/tackifier/oil blends : contain no oils, therefore no
bleeding; contain no resin, therefore cause less skin sensitizing; possess good thermal
stability (tested as less than 10 % viscosity break after 100 h at 177 °C in a forced
draft oven ); exhibit low colour and odour; are reactive and can be modified. They
are compatible with most olefin-compatible ingredients and possess lower density than
conventional rubber-based hot-melt pressure-sensitive adhesives.
There are propene rich and butene rich copolymers. There are pressure-sensitive and
semi-pressure-sensitive products.The semi-pressure-sensitive products display limited
pressure sensitivity in time [145].They are lose their pressure sensitivity due to their
crystallization.Their crystallization strongly depends on the composition of the
adhesive.Various semi-pressure-sensitive adhesives were formulated with amorphous
polyalphaolefins. Such adhesives have softening point of about 210-300 °F, application
temperatures of 170-375 °F , and viscosities of 500-10,000 mPa.s .
According to Ref. [147], hot-melt pressure-sensitive adhesives are based on
atactic polypropyene ( with a molecular weight of 15,000-60,000 ) and small
quantities of terpene resins ( with a molecular weight of 1200 ). Low viscosity
polyolefin hot melt adhesives are based on mixtures of amorphous polymers, e.g.,
polypropylene and propylene-butene copolymer having more than 50 % propylene,
45-55% hydrocarbon tackifiers with a R&B softening point of 70-130 °C ,15-25 %
rosin tackifiers with R&B softening point of 70-100 °C, and polyethylene wax [148].
A possible APAO type hot-melt pressure-sensitive adhesive formulation contains the
following ingredients [140]: 75 pts,Vestoplast-508 ( a hard C3/C8polymer with an open

time of 15 min, from Hiils), 15 pts Arkon- P90, lOpts Ondina-Gl7 ( from Shell)
and 0.2 pts Irganox-1010 ( from Ciba-Geigy).
Heteropolymers
Special polymers include products having elastomer , viscoelastomer or viscomer

properties. Such characteristics may be provided by different chemical composition
and macromolecular build-up.
1.8.1. Silicones
Silicone-based PSAs were developed in 1953 [149]. Such adhesives were prepared by
mixing of a silicone polymer gum with a siloxane resin ( see Vol.l,Chapt. 4
also).They have principally two components: a highly flexible, linear siloxane
rubber and an extensively branched siloxane resin. Industrially, polydimethylsiloxane
and polydimethyl -diphenylsiloxane are the main polymers for the production of
silicone PSAs [149]. For elevated thermal stability phenylsilicones , for better
adhesion characteristics and improved filler loading capability methylsilicones were
suggested. Such polymers can be crosslinked with benzoyl peroxide. The MQ resin
is a highly branched siloxane polymer, where M is trimethylsiloxy and Q is Si02.
Such MQ resin is a hard glassy material with a broad Tg above room temperature.
Amoroux et al. [150] investigated the adhesion of a silicone elastomer made of
polydimethylsiloxane (PDMS) crosslinked with a silicone MQ resin.The resines had
the following chemical formula MDV1Q, with M=Me3SiOi/2, Dvl =Me(CH2=CH)Si02 /2,
Q= Si04/i and Mn= 4300 g/mol, Mn/Mw= 1.8.
Polydimethylsiloxanes exhibit a Tg of about -120 °C. In comparison acrylics show
a glass transition temperature of about -65 to -40 °C. Therefore, the peel resistance of
both adhesives increases with decreasing the temperature (as the polymer stiffens), but
the peel increase of acrylics is followed by a sharp decrease at temperatures below -
20°C. The peel force of silicones continues to increase at lower temperatures.
Therefore, the silicone is a better adhesive for lower temperatures. Thus silicones are
functioning as PSAs from at least -73 °C up to 250 °C. Acrylics work between -25
and +150 °C. At room temperature, acrylics have a slightly higher ( about 20 %) shear
resistance than silicones, but below -20 °C the shear resistance of acrylics decreases
while the silicone reaches a plateau between -50 and -73 °C.The silicone maintains
100 % of its room temperature resistance when laminated at -20 °C, while the acrylic
exhibits only 61 % of its original peel resistance. Such silicone based product provides
a shelf life of 12 months.
Silicone rubbers are resistant to moisture, UV light, ozone, weathering,corona
discharge and radiation. Silicone rubbers exhibit excellent electrical properties,
bacterial resistance and physiological inertness. They show excellent release and
antistatic characteristics.
Silicones display good chemical resistance.As mentioned above, such rubbers are
mainly based on dimethylsiloxane polymers, but vinyl, phenyl and trifluoropropyl
groups can be introduced to replace methyl groups on the silicon atom.The presence of
vinyl groups improves vulcanization and phenyl groups improve low temperature
resistance, while trifluoropropyl groups are added to increase resistance to solvents
[151]. Silicone rubbers have a broad service temperature ( -100 °C to +316 °C ) and
good flame retardancy. They show low smoke density and toxicity and high chemical
26 VoL2,Chapter 1
and environmental resistance [152]. For instance, a cured self-bonding silicone tape
withstands temperature extremes of -10 °C to +180 °C. Silicone rubber displays
spontaneous adhesion on itself or on polar substrates. Its autoadhesion is improved
by temperature, humidity and ammonia. Silicone adhesive chemistry is based on
curing of such compounds. Curing may have different mechanisms.
Because of the higher reactivity of the polar groups on silicone in comparison
with hydrocarbons, low temperature crosslinking (e.g., condensation crosslinking) can
be carried out. First low-solids silicone adhesives with 60 % solids were manufactured.
Such adhesives were used for splicing, electrical and masking tapes. For such
applications they must be cured (see Vol.l,Chapt. 4, Crosslinking also).
New silicone PSAs are based on a silylvinyl-silylhydride addition reaction
(hydrosilylation) [144]. Such reaction is catalyzed by platinum. The addition- based
crosslinking of silicones in the presence of Pt catalysts occurs as illustrated by scheme
1.17 [144].
For adhesive manufacture, silicone polymers with vinyl and hydride groups are
prepared and compounded with tackfying MQ resins . Such polymers can be cured at
temperatures as low as 110 °C. As the Si-H/Si-vinyl ratio increases from 1.12 to 2.17,
the curing temperature can be reduced from 136°C to 93°C. Such formulations possess
80-90 % silicone solids.They need no diluting agent to be coated. The first generation
of high solids silicones had a viscosity of about 50,000 mPa.s.The lack of sufficient
cohesive strength ( shear at high temperatures, e.g., 260 °C ) has been a limitation for
such adhesives. In industrial practice, new addition-cure high-solids silicone PSAs
are multi-component systems and possess four components as follows: an adhesive
polymer;a tackifying resin and two separate crosslinkers. The level of the crosslinker
and the ratio between the two crosslinkers influence the properties of the silicone
PSA. Such compounds display low, shear-dependent viscosity.Typically a coater-ready
blend should have a viscosity of 4,000-8,000 mPa.s for reverse roll applications and
10,000-40,000 mPa.s for knife-over-roll applications [149].
According to Ref. [153], siloxane adhesives comprise siloxanes, hydrodiene-
siloxane, accelerators and fillers. Dimethylsiloxane from trimethylsilyl-terminated
dimethyl siloxane and methylvinysiloxane (100 pts), trimethylsiloxy-terminated
polymethylhydrodiene siloxane ( 5 pts) dicumylperoxide ( 3 pts) and hexamethyl
disilazane-treated silica were mixed to give an adhesive [154]. Some silicone pressure-
sensitive adhesives are dispersions (in organic solvents ) of polydimethyl siloxane gum
and resin, diluted with xylene [155]. A common silicone pressure-sensitive adhesive
contains 600-700 ppm silanol. It can provide sites for crosslinking and sites for
hydrogen bonding with a drug if used for medical applications [156]
(1.18)
(see schema 1.18). By endcapping the adhesive polymer and resin, the silanol groups
can be eliminated.
The manufacture of such silicone PSA begins with the reaction of silanol end-
blocked polydimethylsiloxane and silicone resin dissolved in organic solvent in the
presence of ammonia. Such PSAs have a high content of silanols. Reacting silazane
with the product, gives a trimethylsilyl end-capped, non-reactive siloxane [157].
Reactive silicone groups can be built into common polymers too. For instance, a
pressure-sensitive adhesive for tapes and label comprises a polyether containing at least
one reactive silicone-containing group (100 pts bw ), a resin compatible with the
polyether (10-140 pts), a curing catalyst (0.1-10 pts), and 0-150 pts other
components.The resin is an aromatic petroleum resin,a low molecular weight
polystyrene resin, an alicyclic petroleum resin and a coumarone resin [158].
Poly(imide-siloxane) segmented copolymers were prepared also [159].
Polydimethylsiloxane-polyamide block copolymers were synthesized [160]. Vinyl-
terminated polydimethylsiloxanes can be reacted with silicone polymers having
mercaptoisobutyl groups, and can be cured in the presence of photoinitiators (e.g.,
benzopheno-1,2 -hydroxymethyl- 1 -phenylpropane- 1 -one and 2 ,2 -diethoxy-aceto-
phenone) and UV light [161]. Photoiniated-polymerization using acrylic groups is
possible too [162]. Amine-compatible silicone PSAs were developed for transdermal
drug delivery systems [157]. Medical grade silicone PSAs introduced in the 1970s
contained high molecular weight polydimethylsiloxane and an amorphous silicone
resine [166]. From these components an interpenetrating polymer network results,
having excellent cohesion properties. Acrylated silicone medical products are
segmented polymers with sequences of silicone chains and acrylate chains. The
soft silicone acrylates are elastomeric and non-tacky.
It should be mentioned that MQ resins are used for release control (i.e., increase of
the release force) for silicone release layers also. In this case it is supposed that the
resins mixed in the silicone release layer do not migrate into the adhesive and „divide
themselves between the silicone phase and the silicone adhesive interface,, [163].
Guyot and Vergelati [162] use molecular modelling ( low molecular silicones) to
prove the above hypothesis. The working mechanism of such resin release control
agents can be compared with their tackification effect in adhesives. Table 5.4 presents
some screening formulations for silicone PSAs.
1.8.2. Polyurethanes
Polyurethane adhesives are used for special applications. The high polarity of
polyurethanes ensures good adhesion; their partially crystalline structure allows
excellent mechanical properties [168]. The main technical polyurethanes are two-
component and one-component ( humidity-curable and heat-curable) compounds [169].
The raw materials employed in formulating polyurethanes include isocyanates,
polyols, chain extenders, catalysts, solvents and additives . The most used aromatic
isocyanates are toluene diisocyanate (TDI), methylene-4,4 '-di (phenylisocyanate)
(MDI) and polymeric MDI (PMDI) with NCO functionalities varying from 2.2 -3, and
4,4',4“-triphenylmethane - triisocyanate (TTI). To avoid the use of monomeric
28 VoL2,Chapter 1
Table 1.4 Screening Formulations for Silicone PSA
Components Concentration (pts bw)
Chemical nature R ef
164 165 166 167
Methyl siloxane 55 — — 94.7

Vinyl terminated siloxane 45 — — 0.3
Methyl-H-siloxane — — — —
Dimethyl siloxane or — OP — —
dimethyl-diphenylsiloxane
copolymer gum
Phenylsiloxane 5
Polyorganodisiloxane with — — OP —
monovalent hydrocarbon groups
Vinylsiloxane
Organopolysiloxane with R '3S i0 4-S i0 2 OP
units with R '= alkyl, alkenyl or OH,
(0.6-0.9)/l mol ratio
Organohydrogenpolysiloxane
with > 2H per mol
Resin with R3Sio.5 units OP
R= C<6 hydrocarbyl, with > 95% being
methyl and SiO units
Hexachloroplatinate lOOppm OP
Toluene 15
OP-optionally
isocyanates with high vapour pressure, NCO-terminated adducts or prepolymers of

diisocyanates with hydroxyl containing polyester, polyethers or polybutadienes are
utilized [170]. Such compounds are available with various compositions. For
instance, a foamed adhesive for tapes was manufactured from a mixture containing a
TPE, a tackifying resin, an isocyanate-terminated monomer or oligomer and a polymer
comprising a backbone of polymers like polybutadiene,polyester and polyether which
must contain at least two active hydrogens capable of reacting with the isocyanate-
terminated monomer, and expandable fillers [171].The raw materials for thermoplastic
polyurethanes are choosen in such way to lead to soft and hard polymer parts. For
instance, the softsegment may be a polytetramethyleneoxide (PTMO), with a
molecular weight of 2000, the hard segment may be a diisocyanatecyclohexane (CDDI,
99 % trans ). As chain extender, 1,4-butanediol and trymethylolpropane are suggested
[172]. The hard segment is made from diisocyanate and a polyol , e.g., MDI , HDI,
isophorone diisocyanate ( IPDI) and 1,4-butanediol, the soft segment includes polyols
e.g., butanediol-1,4-polyadipate or ethanediol-butanediol-1,4-polyadipate). Poly-
tetramethylene etherdiol and polyoxypropylene diol prepolymer, and TDI were
proposed as raw materials for polyurethanes also [173].
Two-component-based reactive polyurethanes are 100 % -solids systems
resulting from the combination of polyol-polyisocyanate or an isocyanate terminated
prepolymer cured with polyamines or polyols ( 1.19 ). Single-part polyurethane
adhesives are polymers of low molecular weight whose chains are terminated with
isocyanate groups. These NCO groups are free to react with moisture either present
already on the web or added as water fog at the nip station [174] (1.20):
(U 9 )
( 1.20)
Special polyurethanes contain vinyl unsaturation as reactive site. For instance,

urethane acrylics are functionalized polyurethanes, with acryl functional groups. They
are manufactured by functionalization of polyurethane units . The synthesis of
urethane acrylics is schematically presented as follows ( 1 .2 1 - 1 .22 ):
( 1.21)
( 1.22)
By suitable choice of the starting polyisocyanate, polyol and acrylate, the desired
substitution,functionality and molecular weight can be achieved [175]. Using such
oligomers, block copolymers with distinct properties can be synthesized.The
crosslinking density and molecular weight of the polymer control the mechanical and
adhesive properties. Generally, the isocyanate can be regarded as a stiff component of
the copolymer,while the polyol may be regarded as a relative flexible component.The
stiff segments tend to form laterally ordered groups through intermolecular bonding
occurs. Flexible groups are disordered and randomly oriented. They are necessary to
provide toughness and flexibiliy. If the flexible backbone is sufficiently long,a certain
amount of coiling occurs giving rise to rubbery domains. Flexible groups influence
peel strength and cleavage strength. The soft segments can contain various
heteroatoms. For instance, segmented , UV-light-curable polyurethane-acrylates
based on hydroxyl-terminated dimethylsiloxane (PDMS ) soft segments with a
molecular weight of 1800 and 2,4 TDI-2-hydroxyethyl methacrylate hard segments
were synthesized too [176].
Polyurethanes modified with acrylate derivatives can be crosslinked by free radical
mechanism [177]. For instance, a polyurethane prepolymer with free -NCO groups
was mixed with a polyol and zinc organic catalysts, and than reacted with
dicyclopentadienyl oxyethyl acrylate in the presence of an UV-catalyst. The acrylic
derivative polymerizes and builds-up an interpenetrating network.The urethane-
acrylate oligomer may be a viscous material which has to be diluted with a reactive
diluting agent. Such diluting agent can be an acrylate monomer. Its influence on the
properties of the adhesive film is considerable. It improves the cohesion but reduces
the adhesion. A tackifier resin can be added too [178]. For instance, dicyclopentenyl
methacrylate, air curing-monomer is polymerized through its methacrylate group to
produce polymers with pendant, reactive double bonds capable of being crosslinked
30 Vol.2,Chapter 1
by free radical mechanism , thermally or by radiation, in solution or emulsion [179].

Non-isocyanate low volatile organic content urethane resins were developed for
lacquers. Such compounds contain acrylic backbone resins, acrylated urethane
crosslinker resin and catalyst. The base acrylics include an acetoacetyl functional
group which undergoes Michael addition reaction with the unsaturated vinylic end
group of the urethane crosslinker. The catalyst is an organic base [180].
The lower viscosity of solventless polyurethane adhesives is achieved using lower
molecular weight and higher -NCO -content [181,182]. Solvent-based PUR
formulations can contain other base elastomers also. For instance, a solvent-based glue
stick adhesive contains a solution of linear /branched-chain polyurethane rubber, a
carboxylated butadiene-acryl nitryl rubber containing at least 50 % bw butadiene and
the reaction product of sorbitol and benzaldehyde in a non-aqueous solvent system
[183].
Polyurethane dispersions were developed also. Water-bom polyurethane adhesives
contain linear thermoplastic elastomers , which can be dispersed in water due to the
presence of ionic groups in their structure ( polyurethan ionomer) which act as internal
emulsifiers. Principally emulsifier-free and emulsifier-containing polyurethane
dispersions can be manufactured [184]. The base prepolymers can contain ionic
groups or hydrophilic groups. According to the nature of the surface active agent, the
dispersion can be cationic, anionic or non-ionic. The polymers having ionic groups
are self-emulsifying. Surface active agent free dispersions, called ionomer dispersions
are more important. They can be cationic anionic or non ionic. The surface active
agent-free anionic PUR dispersions are prepared fom urethane prepolymers solved in
acetone according to the following schema (1.23-1.25) [185]:
Polyether ( Polyester) + Diisocyanate —►Urethane prepolymer ( in acetone ) (1.23)
Urethane prepolymer + Alkalisalt of a diaminocarboxylic acid -» PUR (1.24)
PUR + Water —» PUR Dispersion (with acetone) —» PUR Dispersion (1.25)
The cationic dispersions are prepared in a similar manner . In this case, the chain
extension agent is bears amino groups. Non-ionic PUR dispersions contain chain
extension agent with hydrophilic polyether chains. Polyurethane ionomer dispersions
are synthesized without supplemental emulsifiers because the negative influence of
the wetting agents on the adhesion. They are based on high molecular polyether or
polyester with a molecular weight of 2000. Such polymers react with diisocyanates (in
acetone) and chain extension agents having ionic (anionic COO', S03‘ or cationic -
NR 3 ,PR3+ ) groups which stabilize the (secondary) polymer dispersion [186]. The
influence of the hard segments was studied in Ref. [187]. As stated, decrease of the
NCO/OH ratio of the polyurethane dispersion (PUD) produced an increase of the
average particle size, decrease in the molecular weight due to an increase of the
average particle size, lower thermal resistance, lower elastic modulus, an increase vin
the thermal degradation stability due to the highre sioft segment content, an increase in
the polyurethane crystalllinity, an improvement of the adhesion to PVC.
The prepolymers are hot dispersed in water ( triethylamine aqueous solution) and
chain extender hydrazine wis added to inhibit the reaction between the -NCO groups
and the water, due to the preferential reactivity of -NCO gropus with amine groups.
Pressure-Sensitive Adhesion as Process 31
Figure 2.3 Idealized plot o f the storage modulus, G \ loss modulus, G” , and tan 8 for a typical
pressure-sensitive adhesive as a function o f temperature [16]. coref = 1 Hz.
Figure 2.4. Temperature dependence o f dynamic shear moduli G ’, G ” and tan 8 for PVP-PEG
PSA at a reference deformation frequency o f 1 Hz [14].
PVP-PEG adhesive is more in the range of 3-5 MPa (Fig. 2.4), a value clearly
incompatible with the Dahlquist’s criterion for tackiness, which specifies that an
adhesive loses its tack if its elastic modulus at 1 Hz is higher than about 0.1 MPa. Also
typical PSAs are used in a temperature range corresponding to the beginning of the
high-temperature rubbery plateau or the end of the transition region (Fig. 2.3), while
the PVP-PEG blend has been found to be tacky in a region corresponding to the center
of the transition region [26]. Typical values of tan 5 for conventional PSAs range from
0.1 to 0.7. For the PVP - PEG adhesive hydrogel at 20° C the value of tan S is about
1.25 (Fig. 2.4).
32 Vol. 2, Chapter 1
with acrylates exhibit an improved balance of the adhesive properties but they also
display a non-aggressive type of tack [195]. They have a broad range of applications
from pressure-sensitive adhesives (as hot-melts and water-based dispersions), non
pressure-sensitive hot-melt adhesives, adhesiveless self-adhesive films, coatings and
blends to general moulding and extrusion of non adhesive films, profiles, etc.
Ethylene-vinylacetate copolymers were used as heat-activated adhesives also [196].
Ethylene-vinyl acetate copolymers with more than 70% vinyl acetate have been
proposed as polymeric plasticizer for cellulose derivatives [197]. Ethylene-vinyl
acetate based formulations for primers are known too [198]. Cold-seal coatings are
based mainly on NRL and a vinyl acetate copolymer [199].Ethylene-vinyl acetate
copolymers can be used in cellulose microcapsules for drug release as coacervation-
inducing agent [200]. Flame-retardant non corosive ( FRNC ) elastomers based on
EVAc were prepared also [201]. They can be crosslinked peroxidically.Ethylene-
vinyacetate copolymers have been suggested as detackifiers, antiblocking and release
agents also. Such agents are added (0.5-1.5 %) to lacquers.Increase of the vinyl
acetate content increases elongation and flexibility, impact strength,low temperature
resistance; polarity and adhesion, solubility; crosslinkability blocking; tensile
strength ( up to 30 % viny lacetate level ) and gas permeability, and decreases the
stiffness, water resistance, slip, specific resistance and chemical resistance [202 ].
The main ethylene-vinyl acetate copolymers preferred for adhesives contain 14-40%
vinylacetate and have an MFI value of 25-2500 [203].
The modulus of ethylene-vinyl acetate copolymers depends on their
manufacturing method. Ethylene-vinyl acetate copolymers obtained by partially
saponification of the vinyl acetate groups differ from those obtained by partially
esterification of PVA. Partially hydrolysed ethylene-vinyl acetate copolymers have
hydroxy sequences as block. Their modulus is lower than the modulus of partially
acetylated products. Such low modulus causes higher peel resistance [204]. For
high-pressure synthesized ethylene-vinyl acetate copolymers , the maximum of the
branching depends only slightly on the composition of the copolymer. Increase of
the vinyl acetate content of the copolymer increases the distribution of the branched
chain lengths [205].
Ethylene-vinyl acetate copolymers suffer photodegradation caused by UV radiation.
In this process hydroperoxy groups are formed . Their number incresases with the
vinyl acetatecontent of the polymer. The degradation reaction occurs with splitting off
of acetic acid ( by ring formation) [206]. Ethylene-vinyl acetate copolymers can be
crosslinked between 120 °C and 160 °C ( 10-15 min, curing time ) [207]. Ethylene-
vinyl acetate copolymers cannot be steam sterilized. However, radiation ( such as
from Cobalt 60 ) may be used at the normal sterilization level of 2.5 megarads,
without causing significant degradation. Ethylene-vinyl acetate copolymers are
stable up to 230 °C; ethylene-acrylate copolymers are stable up to 320 °C [208].
As mentioned above, terpolymers of ethylene, vinyl acetate and acrylates exhibit
improved adhesive properties. Ethylene-vinyl acetate-acrylate copolymers as water-
based dispersions show acrylate-like tack and peel and good adhesion on polyolefins.
They need no tackification and hence they are ageing and plasticizer resistant.
Therefore they can be suggested for flooring adhesives also [209]. ( For instance, an
ethylene-vinyl acetate copolymer with a Tg of -23 °C is used for flooring adhesive
[210] ). However their use is limited to paper label and decorative film application
because of their low shear resistance and pronounced water sensitivity [145]. Such
copolymers can work as tackifier.
Ethylene-vinyl acetate copolymers synthesized in high pressure procedure are raw
materials for PSAs . They possess better adhesive properties than common EVAc
copolymers. For instance, a conventional pressureless vinyl acetate copolymer having a
Tg of -30 °C exhibits a looptack of 7.0 N/10 mm in comparison with 2.6 N/10 mm for
a high pressure ethylene-vinyl acetate copolymer (Vinnapas-EAF 60 ), a peel
resistance of 10.5 N/10 mm in comparison with 5.3 N/10 mm (for Vinnapas-EAF 60)
and shear resistance of 0.2 h in comparison with more than 500 h for the high pressure
copolymer [211]. High shear pressure-sensitive water-based adhesives based on
ethylene-vinyl acetate-acrylate were prepared and used for labels, flooring and
ceramics. Such adhesives can be tackified and plasticized [212]. Vinnapas-EAF 60
(Wacker ) was the first (high pressure made) pressure-sensitive ethylene-vinyl acetate
dispersion synthesized in Europe. It exhibits pronounced plasticizer and shrinkage
resistance and cohesion. It can be used as tackifier for other dispersions , for flooring
adhesives or as PSA for tapes, labels and insulation materials [213,214]. For instance,
the Vinnapas-EAF 60 dispersion can be used as tackifier and flexibilizer for flooring
adhesives [215].
Such adhesives contain a pressure-sensitive adhesive on ethylene-vinyl acetate
basis, a non pressure-sensitive ethylene-vinyl-acetate dispersion, resins, fillers
andadditives. They can be applied as one-side flooring adhesives after an about 20
min drying time, and display excellent thermal stability ( important for floor heating).
So-called legging adhesives are prepared too. In this case the addition of a resin
allows the regulation of the legging. Removable flooring adhesives are required also.
These are removable with or without water. In this case an ethylene-vinyl acetate
copolymer-based primer is applied on the substrate to allow removability.
Various reactive comonomers were tested in ter- and multipolymer with ethylene-
vinyl acetate. For instance, such copolymer contains vinyl esters or aliphatic carbonic
acids ( C3 -Ci g), esters of acrylic or methacrylic acid, and of maleic acid with aliphatic
Ci-Cig alcohols, in the presence of 0.05 to 0.05 % a,P-unsaturated carbonic acids
and 0 % to 0.95 % epoxydized or hydroxy methacrylic or acrylic acid ester and 1.5 -
20% celluloseether. The copolymer diplays a Tg of -40 to 0°C [216].
Secondary ethylene-vinyl acetate dispersions can be manufactured too.Their
properties were compared with those of ethylene-vinyl acetate dispersions in [217].
Vinyl acetate copolymers can be used for water-soluble compositions too. Water-
soluble HMPSAs are based on a water-sensitive polar copolymer and a solubilizing
component [218]. As base polymer, N-vinyl pyrrolidone-vinyl acetate copolymers
were suggested. Such compounds have to be tackified, and their melt viscosity has to
be reduced. The composition includes 35-65 % polymer and 35-50 % solubilizing
component. As solubilizing component, free monobasic saturated fatty acid with an
acid number higher than 137 was suggested . A special composition for water-
activatable hot-melt includes vinyl pyrrolidone-vinyl acetate copolymer with vinyl
pyrrolidone/vinyl acetate ratio of 3/1 to 1/3 and an ethylene-vinyl acetate copolymer
with 17-40 % vinyl acetate [219]. In this case, the role of EVAc copolymers
(preferably with 40%, 33 % and 28 % vinyl acetate level) is to increase cohesive
strength and flexibility and to lower the penetration into substrates.
Polypropylene and ethylene-vinyl acetate copolymers are used in blends as
thermoplastic elastomers [220]. A segmented ethylene-vinyl acetate copolymer
possesses higher vinyl acetate content (36 %) and better thermal, oxidation and UV
radiation resistance and good anchorage on PVC [221].The crosslinking of TPEs
based on ethylene-vinyl acetate improves their physical properties [222 ].
The base ethylene-vinyl-acetate copolymers for hot-melts contain 28 % vinyl
acetate [223]. Such polymers have good oxydation resistance, compatibility with
resins, fillers and waxes ( excepting paraffin ). Because of their low tack such
polymers were not used for HMPSAs. Elvax-170 (a segmented ethylene-vinyl acetate
copolymer from Du Pont) was manufactured for HMPSAs. Such polymer possesses
alternating segments with low and high vinyl acetate content. It has higher vinyl
34 VoL 2,Chapter 1
acetate content than common EVAcs and much higher ( R&B) softening temperature
( 220 °C ). Such copolymer is designed to be used for hot- melts because of its low
viscosity ( of 15,000-50,000 mPa.s at 150 °C ) and good oxidation resistance and
excellent UV light-resistance [210]. Such polymers are compatible with aromatic
and alkyl - aromatic resins, colophonium derivatives and phatalate plasticizer.
Water white systems are needed for hygienic articles [223]. The plasticizer resistance
of ethylene-vinyl acetate copolymers allows their use as adhesive on PVC carrier
[212].For both applications EVAc copolymers are recommended. Formulations for
hygienic articles can contain up to 20 % plasticizer.
The above listed formulations and practical applications illustrate the excellent
versatility of vinyl acetate copolymers for carrier materials and adhesive or non
adhesive coatings. Unfortunately such copolymers are not suitable for high
performance pressure-sensitive use. Because of its macromolecular characteristics
polyvinyl acetate does not exhibit pressure-sensitive properties. First plasticizing of
PVAc was tried toachieve such pressure sensitivity; later, its copolymerization was
perfected. As demonstrated in Ref.[224], and discussed in Ref.[225], a decade ago, in
a comparative study of acrylates, CSBR and EVACs, ethylene vinyl acetate
copolymers do not possess balanced adhesive properties. Their adhesion is low and
heir tackification is difficult.
Later, multipolymers with acrylates and maleic derivatives were developed.
Although the properties of acrylic terpolymers are better, they do not reach the level of
common acrylates and their tackification remains difficult. The copolymers with
maleinates show better tack and specific peel but (unfortunately) very low cohesion.
1.9.2. Vinyl Acetate-Vinyl Pyrrolidone Copolymers
The copolymers of vinyl acetate with N-vinyl pyrrolidone are used mainly in water-
dispersible or soluble formulations as base elasto-mer (see above).As is shown,a water
soluble hot-melt pressure-sensitive adhesive is based on a water-sensitive polar
copolymer and solubilizing components. As base polymer vinyl pyrrolidone-vinyl
acetate copolymers are preferred. Due to their pronounced hydrophilic character
vinyl pyrrolidone polymers are preferred for special, for example medical applications.
For instance, for drug releasing medical devices a crosslinked hydroxyethyl
methacrylate-N-vinyl-2-pyrrolidone copolymer hydrogel was proposed [226]. Water-
soluble adhesive compositions based on vinyl pyrrolidone copolymers will be
discussed in the Sect., 1.13.2 .
1.10. Acrylates
The copolymerization of acrylates was studied as solution polymerization. Therefore,

acrylate solutions were first used as adhesives. Later the emulsion polymerisation was
developed also and acrylate dispersions from BASF have been marketed in Europe
since 1930. The grade Acronal-500 D was patented in 1931 and Acronal-4 D was
patented in 1943. According to Ref. [227], acrylates were introduced for PSAs in
the 1950s, and have been widely used in the 1970-1980s. Acrylate-vinylacetate
copolymers are manufactured mainly on economic considerations.
1.10.1. Pure Acrylates
Acrylates offer the following advantages [228]: pressure sensitivitywithout low

molecular additives which can migrate or oxidize, optical clarity due to compatibility,
non-yellowing, oxidation resistance and chemical resistance, excellent water
resistance,adhesion to various substrate surfaces, broad service temperature and
versatility for different coating methods.As illustrated by the data of Table 1.4,
acrylates can be supplied as solvent-based, water-based and 100 % solids materials and
they display a broad range of adhesive properties which allows their use for various
PSPs.The molecular weight of acrylates polymerized in solution is about 5,000-
150,000 [229]. Their viscosity increases with their molecular weight. In order to
limit their viscosity and to achieve excellent mechanical properties, thermally
crosslinkable acrylates are used.
Table 1.4 Adhesive Properties of Pressure-sensitive Products Based on Acrylic Raw

Material
Adhesive /End use Peel Tack SAFT/

resistance Shear
(N/25mm) RB Loop Polyken resistance
(cm) N/25mm (g) (°C,h) Ref.
Acrylic -WB
Label MF* >22.0 — — >180 230

8.9AF 8.0 — — >180 230
11.0 11.0** 0.8
Packaging tape 11-12 1.4 4.5-6.2 _ 231
25.0AF 3.7 — — — 232
8.0 — — — — 233
Protective film 0.7-5.0 >20.0 — — — 234
1.7 14.0 — — — 235
Permanent label 10.0 3.0 — — — 236
Permanent PSP 10.0 — 14.0 700 — 236
Semipermanent PSP 6.5 6.0 — — — 234
Removable PSP 1.5 — 2.5 — — 237
Removable film 3.5 6.0 — — — 234
Repositionable PSP 1.0 5.0 — — 234
2.1-3.0 — — — — 238
Medical PSP 12.0 5.0 — — — 236
Medical tape 8 — 8.0 — — 234
Acrylic -SB
Protective film 6.0 11.0 __ __ __ 235

Medical tape 17.0 1.0 — — — 239
10.0 — 11.0 — — 240
Transfer tape 2.8 — — 400 — 241
Double sided foam tape 15.0 — 15.0 — — 242
Acrylic -HM
UV-curable
Label MF 23.0 — >180 230
MF-material failure;AF-Adhe sive failure; * to Mylar; **N/in2

Another random document with
no related content on Scribd:
CHAPTER XV
TIMELY HELP
Lavish Gifts for the Soldiers—The Times Fund—The Times

Commissioner Visits Scutari—His Description of Miss Nightingale
—Arrival of M. Soyer, the Famous Chef—He Describes Miss
Nightingale.
This is true philanthropy, that buries not its gold in ostentatious

charity, but builds its hospital in the human heart.—G. D. Harley.
M ISS NIGHTINGALE’S personal efforts for the sick and wounded

soldiery were nobly and most generously seconded by
sympathisers at home. Ladies were continually arriving at the
Admiralty Office in carriages piled with huge boxes and chests
labelled “Miss Nightingale,” and such large cargoes reached Scutari
that it was said at the time the officials might fancy that the Indian
mail had been landed by mistake.
The Queen in her palace, assisted by the young princesses, in
common with women of all degrees throughout the land, were
making lint and bandages, sewing shirts and knitting socks, for the
poor soldiers. Nothing indeed was deemed too good for the suffering
heroes. Sister Mary Aloysius relates that when she first began to sort
the stores in the sheds at Scutari, she thought that the “English
nobility must have emptied their wardrobes and linen stores to send
out bandages for the wounded. There was the most beautiful
underclothing, and the finest cambric sheets, with merely a scissors
run here and there through them, to ensure their being used for no
other purpose, some from the Queen’s palace, with the Royal
monogram beautifully worked.” Amongst these delicate things the
rats had a fine time, and on the woollen goods they feasted
sumptuously ere the sisters could get them sorted and distributed
from their temporary resting-place in the sheds outside the
hospitals.
While private charity was sending its promiscuous bales of
goods, The Times, to which belonged the honour of having first
aroused public interest in the suffering soldiery, had organised a
fund for the relief of the wounded which met with the most
generous support. The great journal undertook to distribute the
fund, and for this purpose appointed Mr. Macdonald, a man of high
character and endowed with good sense and discrimination, to
proceed to the East and ascertain on the spot the manner in which
the money could be best applied for the relief of the distressed army.
Before setting forth Mr. Macdonald called on the Duke of
Newcastle, Secretary of State for War, also on Dr. Andrew Smith, the
Inspector-General, and was assured by both that such ample
measures had been taken by Government that The Times fund was
really scarcely needed for the relief of the sick and wounded.
However, Mr. Macdonald proceeded on his way, for there was at least
one man connected with the War Office—Sidney Herbert—who knew
from Florence Nightingale’s letters what the true state of affairs was.
When The Times commissioner reached the Bosphorus, he again
had cold water thrown on his mission. Officialdom laughed amiably
over “bringing coals to Newcastle.” Mr. Macdonald found, however,
that the men of the 39th Regiment on their way to the seat of war
were going to face the rigours of a Crimean winter in the trenches
before Sebastopol in the light and airy garments which they had
been wearing at Gibraltar, and he got rid of some of his Times gold
by going into the markets of Constantinople and purchasing suits of
flannels for the men.
When Mr. Macdonald at length reached the hospitals at Scutari—
those hospitals the deficient and insanitary state of which had
moved the heart of the country to its core—he must have felt
dumfounded when Dr. Menzies, the chief medical officer, in answer
to his offer of help, told him that “nothing was wanted.” It seemed
that officialdom was leagued together to deny the existence of
wants which the Government ought to have met. In a higher quarter
still, Kinglake relates that The Times commissioner was met with the
astounding proposal that as the fund was wholly unneeded, he
might disembarrass himself of it by building an Episcopal Church at
Pera!
However, there was one person to whom Mr. Macdonald had not
yet offered his money-bags, and he forthwith proceeded to the
Barrack Hospital and sought an interview with the Lady-in-Chief and
related his experiences.
“Help not needed! the soldiers provided with all necessaries! the
proffered money thrown back on the donors!” Florence Nightingale
must have taken a long gasp when she heard that. She marshalled
the excellent Mr. Macdonald and his superfluous cash away to her
office in the Nurses’ Tower, where he could see for himself the daily
demands on her private stores made by the sick and wounded
soldiers, and how impossible it was, despite the generous gifts
already received from the charitable at home, to meet all
requirements.
The Lady-in-Chief could tell of men arriving by hundreds without
a shred of decent clothing on their backs, of the lack of hospital
furniture, of beds, pillows, sheets, and sanitary appliances, even of
drugs, to say nothing of materials for invalid food. Before the
narration was concluded Mr. Macdonald must have come to the
conclusion that there would be no church built at Pera just yet.
The Times almoner now found his days fully taken up in visits of
investigation to the wards, under the guidance of the Lady-in-Chief,
and many hours of each day were spent in her office in the Nurses’
Tower, taking down in his notebook the things which were pressingly
needed and dispatching orders to the storekeepers of
Constantinople. Miss Nightingale had now found the kind of help
really needed. Here was English gold to replenish her stores at
discretion, and she was no longer left to depend on promiscuous
charity, which sent embroidered cambric when good stout calico
would have been more useful, or fancy mufflers to men who needed
shirts. On the eve of his return to England Mr. Macdonald wrote of
the Lady-in-Chief:—
“Wherever there is disease in its most dangerous form, and the
hand of the spoiler distressingly nigh, there is this incomparable
woman sure to be seen. Her benignant presence is an influence for
good comfort even among the struggles of expiring nature. She is a
‘ministering angel’ without any exaggeration in these hospitals, and
as her slender form glides quietly along each corridor, every poor
fellow’s face softens with gratitude at the sight of her. When all the
medical officers have retired for the night, and silence and darkness
have settled down upon those miles of prostrate sick, she may be
observed alone, with a little lamp in her hands, making her solitary
rounds.
“The popular instinct was not mistaken which, when she had set
out from England on the mission of mercy, hailed her as a heroine; I
trust she may not earn her title to a higher though sadder
appellation. No one who has observed her fragile figure and delicate
health can avoid misgivings lest these should fail. With the heart of a
true woman and the manners of a lady, accomplished and refined
beyond most of her sex, she combines a surprising calmness of
judgment and promptitude and decision of character.
MISS NIGHTINGALE AND THE DYING SOLDIER—A SCENE AT SCUTARI
HOSPITAL WITNESSED BY M. SOYER.
[To face p. 176
“I have hesitated to speak of her hitherto as she deserves,

because I well knew that no praise of mine could do justice to her
merits, while it might have tended to embarrass the frankness with
which she has always accepted the aid furnished her through the
fund. As that source of supply is now nearly exhausted and my
mission approaches its close, I can express myself with more
freedom on this subject, and I confidently assert that but for Miss
Nightingale the people of England would scarcely, with all their
solicitude, have been spared the additional pang of knowing, which
they must have done sooner or later, that their soldiers, even in the
hospital, had found scanty refuge and relief from the unparelleled
miseries with which this war has hitherto been attended.”
After the departure of Mr. Macdonald, Miss Nightingale received
another welcome and also an entertaining visitor in the person of M.
Soyer, an expert in cooking and culinary matters generally, to offer
his services at the hospitals. M. Soyer’s “campaign” was initiated in
February, 1855, by the following letter to the editor of The Times:—
“Sir,—
“After carefully perusing the letter of your
correspondent, dated Scutari, in your impression of Wednesday
last, I perceive that, although the kitchen under the
superintendence of Miss Nightingale affords so much relief, the
system of management at the large one in the Barrack Hospital
is far from being perfect. I propose offering my services
gratuitously, and proceeding direct to Scutari at my own
personal expense, to regulate that important department, if the
Government will honour me with their confidence, and grant me
the full power of acting according to my knowledge and
experience in such matters.
“I have the honour to remain, sir,
“Your obedient servant,
“A. Soyer.”
The services of M. Soyer having been accepted, he in due course

sailed for the East and arrived at Scutari in April. The gallant
Frenchman was all anxiety to pay his respects to “Mademoiselle
Nightingale,” and was gratified to hear that she had heard of his
arrival and would be much pleased to see him. As soon as he
reached the Barrack Hospital he inquired for Miss Nightingale’s
apartment, and was immediately shown into what he terms “a
sanctuary of benevolence.”
Upon entering the room, M. Soyer was received by the Lady-in-
Chief, to whom, after the inevitable complimentary speech, he
presented parcels and letters from Mr. Stafford, who had been such
an indefatigable helper to Miss Nightingale in the past winter, and
other friends, among them one from Harriet, Duchess of Sutherland,
who strongly commended M. Soyer to Miss Nightingale as likely to
be of service in the kitchen department. The Lady-in-Chief arranged
to accompany her visitor in a tour of inspection, and M. Soyer thus
records his impressions:—
“On my arrival I first visited, in company with Miss Nightingale
and one of the medical officers, all the store-rooms, cook-houses,
kitchens, and provision departments, to glean an idea of the rules,
regulations, and allowances made by the authorities. Instead of
there being no appropriate kitchen, as was represented by several
Government employees prior to my embarkation for the East, I
found ample room and space adapted for culinary purposes even
upon the most elaborate and extensive scale.
“I must especially express my gratitude to Miss Nightingale, who
from her extraordinary intelligence and the good organisation of her
kitchen procured me every material for making a commencement,
and thus saved me at least one week’s sheer loss of time, as my
model kitchen did not arrive until Saturday last.”
The Lady-in-Chief found a very valuable ally in M. Soyer, who
was eagerly ready to carry out her suggestions for the furtherance of
various schemes for the better dietary arrangements for the sick,
and who introduced new stoves and fuel and many other reforms of
which she had hardly dared to dream in the first months of her
work. To these new arrangements Lord William Paulet, the military
Commandant, and Drs. Cummings, Menzies and Macgregor the
principal medical officers, gave their entire approval, and Miss
Nightingale had at length the satisfaction of seeing the culinary
arrangements of the Scutari hospitals arranged on a model plan.
During his stay M. Soyer obtained a glimpse into the “ministering
angel” side of the lady whose excellent business faculty had filled
him with admiration as he inspected stoves and boilers and
discussed rations and diets in their rounds of the kitchens. He had
been spending a jovial evening in the doctors’ quarters, and in
making his way at two o’clock in the morning to his own apartment,
he saw, at an angle of one of the long corridors filled with sick and
wounded, a group revealed in silhouette by a faint light. A dying
soldier was half reclining upon his bed, at the side of which sat
Florence Nightingale pencilling down his last wishes home. A sister
stood at her back holding a lighted candle. The group thus outlined,
like a sombre study of Rembrandt, drew M. Soyer to the spot, and
for a time unseen he observed the dying man pass his watch and
trinkets into those tender womanly hands of the Lady-in-Chief, and
heard the laboured gasp of the man to articulate the last message to
wife and children. Then approaching Miss Nightingale, M. Soyer
inquired as to the complaint of her patient, when she replied in
French that the poor fellow had been given up by the doctors and
was not likely to last many hours, and she was noting down his last
wishes for his relatives. The incident enables one to realise how
manifold were Miss Nightingale’s duties and how after laborious days
she gave up hours of needed rest in order to comfort the dying.
Soon after the opening of his model kitchen, M. Soyer received a
visit from General Vivian, and while the General was there Miss
Nightingale entered the kitchen, and an animated conversation
ensued regarding hospital treatment. At the conclusion, M. Soyer
relates that the General said, “M. Soyer, Miss Nightingale’s name and
your own will be for ever associated in the archives of this
memorable war.”
One can understand the ecstasy of the volatile Frenchman at
finding himself coupled in such distinguished company and forgive
his little conceit, for he was an enthusiastic admirer of our heroine,
and has left one of the best pen portraits of her extant. “She is
rather high in stature,” he writes, “fair in complexion and slim in
person; her hair is brown, and is worn quite plain; her physiognomy
is most pleasing; her eyes, of a bluish tint, speak volumes, and are
always sparkling with intelligence; her mouth is small and well
formed, while her lips act in unison, and make known the impression
of her heart—one seems the reflex of the other. Her visage, as
regards expression, is very remarkable, and one can almost
anticipate by her countenance what she is about to say: alternately,
with matters of the most grave import, a gentle smile passes
radiantly over her countenance, thus proving her evenness of
temper; at other times, when wit or a pleasantry prevails, the
heroine is lost in the happy, good-natured smile which pervades her
face, and you recognise only the charming woman.
“Her dress is generally of a greyish or black tint; she wears a
simple white cap, and often a rough apron. In a word, her whole
appearance is religiously simple and unsophisticated. In conversation
no member of the fair sex can be more amiable and gentle than Miss
Nightingale. Removed from her arduous and cavalier-like duties,
which require the nerve of a Hercules—and she possesses it when
required—she is Rachel on the stage in both tragedy and comedy.”
CHAPTER XVI
THE ANGEL OF DEATH
Death of Seven Surgeons at Scutari—The First of the “Angel

Band” Stricken—Deaths of Miss Smythe, Sister Winifred, and
Sister Mary Elizabeth—Touching Verses by an Orderly.
Sleep that no pain shall wake,

Night that no morn shall break,
Till joy shall overtake
Her perfect calm.
Christina Rossetti.
It is the cause, and not the death, that makes the martyr.—Napoleon.
T HROUGHOUT the spring of 1855 disease continued its ravages

amongst the soldiers in the Crimea without abatement, and
there was an increase of typhus fever in its worst form. The
constitutions of the men were so undermined by the privations
through which they had passed that they were unable to fight
against the disease.
The “men with the spades” had no cessation from their
melancholy toil at Scutari. Deaths occurred daily in the hospitals,
and the stricken took the places of the dead only themselves to die
before another day had dawned.
The fever also attacked the hospital staff. Eight of the surgeons
were prostrated, and of these seven died. Miss Nightingale herself
tended Dr. Newton and Dr. Struthers in their last moments, a matter
of inexpressible comfort to their friends. For a time there was only
one medical attendant in a fit state of health to wait on the sick in
the Barrack Hospital, and his services were needed in twenty-four
wards. Three of the nurses were also attacked by the fever. With the
medical staff prostrated and fever threatening her own band, the
duties and responsibilities of the Lady-in-Chief became more
formidable. She bore the strain in a marvellous manner, and there is
no record that throughout this terrible winter at Scutari she was
once unable to discharge her duties. An inflexible will and iron nerve
carried her over all difficulties, and it seemed as though Florence
Nightingale led a charmed life.
Hitherto she had been spared the sorrow of seeing any of her
own band stricken by death, but just when the sweet spring-time
was lifting the gloom of this winter of terrible experiences the call
came to one of the best beloved of her nurses, Miss Elizabeth Anne
Smythe. She had accompanied Miss Nightingale to Scutari, was a
personal friend, and had been trained by her. Miss Smythe’s beautiful
character and her capabilities as a nurse made her very valuable to
her chief, who with great regret consented that she should go from
Scutari to the hospital at Kullali, where help seemed more urgently
needed. Miss Nightingale had hoped that they might have continued
to work side by side until the end of the campaign, but the young
sister felt a call to go to Kullali, where help was needed.
Shortly after her arrival she wrote to her friends in excellent
spirits with every indication of being in good health, and said how
glad she was to have had the courage to come. The presence of
such a bright, well-qualified nurse was a great acquisition to the
hospital staff, and she soon became a favourite with the patients. In
a few days, however, she was stricken with the malignant fever. It
was hoped against hope that her youth and good constitution would
enable her to resist the attack, and for eight days she lay between
life and death, anxiously watched by doctors and nurses. Then
peacefully she fell asleep and passed to her martyr’s crown.
She was the first of the “Angel Band” to be stricken by death,
and her loss cast a gloom over those that remained, but as Miss
Nightingale has herself said, “Martyrs there must be in every cause.”
The funeral of the beloved young sister took place at Easter-time
under bright azure skies, when Nature was decking that Eastern land
in a fresh garb of loveliness. The simple coffin, covered with a white
pall, emblematic of the youthful purity of her who slept beneath,
was conveyed through the streets of Smyrna to the English burying-
ground, a route of two miles, through crowds of sympathetic
spectators. The coffin was preceded by a detachment of fifty
soldiers, marching sorrowfully with arms reversed. Immediately in
front of the coffin walked two chaplains, and on either side were
sisters and nurses. Military and medical officers followed the cortège,
which passed through the silent streets, a touching and pathetic
spectacle. Christian and Moslem alike joined in paying a tribute of
homage to one whose deeds of mercy lifted her above the strife of
creeds.
The first young Christian martyr

Is carried to the tomb,
And busy marts and crowded streets
Are wrapt alike in gloom.
And men who loathe the Cross and name

Which she was proud to own,
Yet pay their homage, meet and due,
To her good deeds alone.
Before many weeks had passed by, Miss Nightingale was again
called to mourn the loss of another of her helpers. The next claimed
by death was Sister Winifred, a Sister of Charity, who, with other
nuns from Ireland, was tending the Irish soldiers in the hospital at
Balaclava, to which they had recently come from Scutari and Kullali.
Only a few days after her arrival Sister Winifred was attacked by
cholera, which had broken out afresh at Balaclava.
Very touching is the account which Sister Mary Aloysius gives of
the death of her comrade: “Our third day in Balaclava was a very
sad one for us. One of our dear band, Sister Winifred, got very ill
during the night with cholera. She was a most angelic sister, and we
were all deeply grieved. She was attacked at about three o’clock in
the morning with the symptoms which were now so well known to
us; every remedy was applied; our beloved Rev. Mother never left
her. She was attended by Father Unsworth, from whom she received
the last rites of our holy religion; and she calmly breathed her last
on the evening of the same day. A hut was arranged in which to
place the remains; and so alarming were the rats—and such huge
animals were they—that we had to watch during the night so that
they should not touch her. She, the first to go of our little band (viz.
the Roman Catholic sisters), had been full of life and energy the day
before. We were all very sad, and we wondered who would be the
next.”
A burial-place was found for Sister Winifred on a piece of ground
between two rocks, on the hills of Balaclava, where her remains
could repose without fear of desecration. The funeral formed a
contrast to that of the Protestant sister at Smyrna, but was equally
impressive. We can picture the sad cavalcade, distinguished by the
symbols of the Roman Catholic faith, wending its way up the hillside
to the lonely spot in the rocks above the Black Sea. Two priests
preceded the coffin, chanting the prayers, and the black-robed nuns
came closely behind, while soldiers and military and medical officers
followed.
Amongst the mourning band walked one tall, slight figure
dressed simply in black whose presence arrested attention. It was
Florence Nightingale, who had come to pay her tribute of love and
honour to the sister who, if divided by faith, had been united with
her in holy work and deeds of mercy.
A tribute was paid to the memory of Sister Winifred in a poem
by a friend, from which we quote the following verses:—
They laid her in her lonely grave upon a foreign strand,
Far from her own dear island home, far from her native land.
They bore her to her long last home amid the clash of arms,
And the hymn they sang seemed sadly sweet amid war’s fierce
alarms.
They heeded not the cannon’s roar, the rifle’s deadly shot,
But onward still they sadly went to gain that lowly spot;
And there, with many a fervent prayer and many a word of love,
They left her in her lowly grave with a simple cross above.
* * * * *
Yet far away from her convent grey, and far from her lowly cell,
And far from the soft and silvery tone of the sweet convent bell,
And far from the home she loved so well, and far from her native
sky,
’Mid the cannon’s roar on a hostile shore she laid her down to die.
* * * * *
She went not forth to gain applause, she sought not empty fame;
E’en those she tended might not know her history or her name;
No honours waited on her path, no flattering voice was nigh;
For she only sought to toil and love, and ’mid her toil to die.
They raise no trophy to her name, they rear no stately bust,

To tell the stranger where she rests, co-mingling with the dust;
They leave her in her lowly grave, beneath that foreign sky,
Where she had taught them how to live, and taught them how to
die.
The grave of Sister Winifred was, unhappily, not destined to

remain solitary. In the early spring of 1856—to anticipate the
sequence of our narrative a little—another funeral was seen wending
its way, to the chanting of priests, up the hills of Balaclava. It was
the body of Sister Mary Elizabeth, who had died of fever, caught
amongst the patients of her ward. Our informant, Sister Mary
Aloysius, thus describes the death scene as it occurred amid a storm
which threatened to unroof the wooden hut where the dying sister
lay: “It was a wild, wild night. The storm and wind penetrated the
chinks so as to extinguish the lights, and evoked many a prayer that
the death-bed might not be left roofless. It was awful beyond
description to kneel beside her during these hours of her passage
and to hear the solemn prayers for the dead and dying mingling with
the howling of the winds and the creaking of the frail wooden hut.
Oh, never, never can any of us forget that night: the storm disturbed
all but her, that happy being for whom earth’s joys and sorrows were
at an end, and whose summons home had not cost her one pang or
one regret.”
They buried Sister Mary Elizabeth beside Sister Winifred, and the
89th Regiment requested the honour of carrying the coffin.
Hundreds of soldiers lined the way in triple lines from the hospital to
the hut where the body lay, and a procession of various nationalities
and differing faiths followed the body to its lonely resting place on
the rocky ledge of Balaclava heights.
Later, when the graves of the two sisters were visited, it was
found that flowers and evergreens were growing in that lonely spot,
planted by the hands of the soldiers they had tended. On the white
cross of Sister Winifred’s grave was found a paper, on which were
written the following lines:—
Still green be the willow that grows on the mountain,

And weeps o’er the grave of the sister that’s gone;
* * * * *
And most glorious its lot to point out to the stranger,
The hallowed remains of the sainted and blest;
For those angels of mercy that dared every danger
To bring to the soldier sweet comfort and rest.
It was discovered that these lines had been composed and

placed there by one of Sister Winifred’s orderlies.
CHAPTER XVII
SAILS FOR THE CRIMEA AND GOES UNDER
FIRE
On Board the Robert Lowe—Story of a Sick Soldier—Visit to the

Camp Hospitals—Sees Sebastopol from the Trenches—
Recognised and Cheered by the Soldiers—Adventurous Ride
Back.
The walls grew weak; and fast and hot

Against them pour’d the ceaseless shot,
With unabating fury sent,
From battery to battlement;
And thunder-like the pealing din
Rose from each heated culverin:
And here and there some crackling dome
Was fired before th’ exploding bomb.
Byron.
O N May 2nd, 1855, Florence Nightingale, having completed six

months’ continuous labour in establishing a system of good
administration in the hospitals at Scutari, set out for Balaclava. She
was anxious to see how the sick and wounded were faring at the
actual seat of war, and it was also her duty as Superintendent of the
Nursing Staff in the East to inspect the hospitals in the Crimea.
LADY HERBERT OF LEA.
[To face p. 192.
There were some sad good-byes to say before she quitted the
scene of her work at Scutari, for death would have claimed many
brave fellows ere she returned to her old post. Sorrowful eyes
followed the gleam of the familiar lamp as she went her final rounds
on the night before her departure, and heads were pathetically
turned to catch a last look at her shadow as it passed on the
whitened wall.
Rarely has any human being had such a retrospect of harrowing
experience and of insuperable difficulties overcome as passed
through Florence Nightingale’s mind when she reviewed the past six
months. The Barrack Hospital as she had found it, crowded with
suffering humanity in the most appalling state of loathsome neglect,
seemed like a hideous nightmare, scarcely to be realised in
comparison with the order, comfort, and cleanliness which now
prevailed.
It was with a heart of thankfulness to the Giver of all Good that
she had been permitted to accomplish this great work that Florence
Nightingale on a bright May morning stepped aboard the good ship
Robert Lowe and set sail for the Crimea. She was accompanied by a
staff of nurses and her friend Mr. Bracebridge, and by M. Soyer, the
celebrated chef, who was going to reform culinary matters at the
“front,” and attended by her boy Thomas, a young drummer who
had abandoned his “instruments and sticks,” as he called them, to
devote himself to the Lady-in-Chief. No general in the field had a
more devoted aide-de-camp than Florence Nightingale had in
Thomas. He was a lad of twelve, full of life, fun, and activity and of
amusing importance, but such was his devotion that he would have
been cut to bits ere harm came near his beloved mistress.
The short voyage was made in lovely weather, when the spring
air was redolent with perfume and freshness, and scarcely a ripple
moved the blue waters of the Bosphorus. Miss Nightingale greatly
enjoyed being on deck as the vessel glided past some of the most
beautiful scenes in that Eastern land. There rose the mosques and
minarets of Constantinople, enveloped, as it seemed, in golden
vapour, then the Golden Horn was passed, and the European and
Asiatic shores opened out in a scene of Oriental beauty. The
picturesque caiques skimmed the waters like magic craft, and Miss
Nightingale was fortunate in seeing the gorgeous flotilla of the
Sultan, consisting of large caiques brilliantly decorated with gilded
and rich silken hangings, and manned by gaily dressed oarsmen,
leave the marble staircase of the Dolmabatchke Palace to convey the
Sultan and his suite to the Mosque of Sultan Mahomet, for it was
Friday, the Turkish Sunday. Fifty guns proclaimed the departure of
the nautical procession. Then Kullali was passed, and the voyagers
thought sadly of the young sister who had recently died there at her
post in the hospital. On went the vessel, past the Sweet Waters of
Asia, where the Turks hold high festival, and the resorts of Therapia
and Buyukdére, until at length the dazzling Oriental coast was
almost lost to view as the ship entered the Black Sea.
However, Miss Nightingale’s delight in the sights and scenes
through which she was passing did not render her oblivious to her
fellow-passengers. There were six hundred soldiers on board and
many officers and Government officials. The second day of the
voyage, being Sunday, Miss Nightingale, accompanied by the
captain, visited the lower deck and talked with the soldiers, and
having heard that there were some invalids on board, asked to see
them. In passing from sufferer to sufferer, she at length came to a
fever patient who had refused to take his medicine.
“Why will you not take the medicine?” asked Miss Nightingale.
“Because I took some once,” the man replied, “and it made me
sick; and I haven’t liked physic ever since.”
“But if I give it to you myself,” said the Queen of Nurses with a
pleasant smile, “you will take it, won’t you?”
The poor fellow looked very hard at her and replied, “Well, sure
enough, ma’am, it will make me sick just the same.” However, he
took the draught and forgot the anticipated consequence as Miss
Nightingale chatted to him about the last engagement he was in.
The distant booming of the cannon in Sebastopol intimated to
the travellers that they were nearing their destination, and on one of
the high peaked mountains they could plainly see the Russian picket
mounting guard. An hour later the vessel reached the harbour of
Balaclava, which presented a wonderful sight with the numerous
great ships lying at anchor. The news had spread that Miss
Nightingale was expected to arrive that day, and the decks of the
vessels in harbour were crowded with people anxious to get a
glimpse of her. Immediately the Robert Lowe came to anchor, the
chief medical officer of the Balaclava Hospital and other doctors and
officials came on board to welcome Miss Nightingale, and for an
hour she held what her fellow-voyager, M. Soyer, facetiously termed
“a floating drawing-room.” Later, Lord Raglan, Commander-in-Chief
of the British forces, came to welcome the illustrious heroine, but
only to find that she had already landed and begun her work of
hospital inspection.
Next day, Miss Nightingale, accompanied by Mr. Bracebridge, M.
Soyer, and an escort of other friends, set out for the camp to return
Lord Raglan’s visit. She “was attired simply in a genteel amazone, or
riding-habit,” relates M. Soyer, “and had quite a martial air. She was
mounted upon a very pretty mare, of a golden colour, which, by its
gambols and caracoling, seemed proud to carry its noble charge.
The weather was very fine. Our cavalcade produced an extraordinary
effect upon the motley crowd of all nations assembled at Balaclava,
who were astonished at seeing a lady so well escorted.”
The people did not, however, know how illustrious the lady was,
for Miss Nightingale preserved an incognito on her way to the camp.
At that time there were only four ladies in the Crimea, excepting the
sisters of mercy, who were never seen out, so there was great
curiosity as the cavalcade approached headquarters to know who
the lady was, and Mr. Bracebridge had to give evasive replies to
enquiring officers.
Florence Nightingale’s ride to camp proved an adventurous one.
The road was bad and not nearly wide enough for all the traffic.
Crowds of many nationalities, together with a ceaseless stream of
mules, horses, oxen, artillery waggons, cannon, infantry, and cavalry
struggled over the uneven muddy road, drivers and officers
shouting, horses kicking, sometimes a waggon overturned, and
everybody in a state of turmoil. Miss Nightingale’s horse kicked and
pranced in company with the horses of her escort, and but for a cool
nerve and steady hand she would certainly have come to grief. But
the skill in horsemanship which she had acquired as a girl amongst
the hills and dales of Derbyshire now served her in good stead, and
the ride was accomplished in safety.
The first halt was made at the hospital in a small Greek church
at the village of Kadikoi. After a little tour of inspection Miss
Nightingale and her party galloped up to the top of a high hill from
which was visible a panorama of the camp, with its myriads of white
tents dotted over the landscape. Now, indeed, she was in touch with
that great bivouac of warfare which the wounded at the Barrack
Hospital in Scutari had raved about in their fever wanderings. Upon
the air came the roar of the cannon from Sebastopol, the sound of
trumpets, the beating of drums, and the general din of military
manœuvres. Around the martial plain rose the rugged heights of
Balaclava with that valley of death sacred to the “noble six
hundred”:—
Stormed at with shot and shell,

Boldly they rode and well,
Into the jaws of Death,
Into the mouth of Hell
Rode the six hundred.
Florence Nightingale sat long on her horse, gazing afar at the

stirring scene and then turned sadly away. She knew that hundreds
of poor fellows away in yonder trenches were doomed to swell the
ranks of the dead and wounded ere the siege of Sebastopol was
ended.
Proceeding on her way to headquarters, Miss Nightingale called
to inspect several of the small regimental hospitals. When at length
the vicinity of Lord Raglan’s house was reached, Mr. Bracebridge,
acting as advance guard, galloped forward, to announce the
approach of the Lady-in-Chief, only to find, however, that the
Commander-in-Chief, who had not received intimation of her
coming, was away. Miss Nightingale having left a message of thanks
to Lord Raglan for his visit of the previous day, now proceeded to
the General Hospital before Sebastopol.
This hospital contained some hundreds of sick and wounded,
and great was the joy of the poor fellows at receiving a visit from
the “good lady of Scutari,” as they called Miss Nightingale. When she
went out past the huts to the cooking encampment, some of the
men who had been patients at the Barrack Hospital recognised Miss
Nightingale and gave her three hearty cheers, followed by three
times three. She was much affected by such an unexpected
demonstration, and being on horseback could only bow to the men
by way of thanks. The shouts grew so vociferous that Miss
Nightingale’s horse turned restive, and one of her friends was
obliged to dismount and lead it by the bridle until the men’s
enthusiasm had abated.
The party now proceeded through the French and English camps
which surrounded Sebastopol. Miss Nightingale expressed a wish to
have a peep into the besieged stronghold, and a column was formed
to escort her to a convenient point. Some sharp firing was going on,
and as the visitors approached a sentry in much trepidation begged
them to dismount, pointing to the shot and shell lying around, and
remarking that a group of people would attract the enemy to fire in
their direction. Miss Nightingale laughingly consented to seek the
shelter of a stone redoubt where she could view Sebastopol through
a telescope. From this vantage ground she obtained an excellent
sight of the doomed city, being able to discern the principal buildings
and to see the duel of shot proceeding between the allied armies
and the enemy.
Miss Nightingale was in an adventurous mood, and proposed to
go still farther into the trenches up to the Three-Mortar Battery. Her
friends Mr. Bracebridge, Dr. Anderson, and M. Soyer were favourable
to her wish, but the sentry was in a great state of consternation.
“Madam,” said he, “if anything happens I call on these
gentlemen to witness that I did not fail to warn you of the danger.”
“My good young man,” replied Miss Nightingale, “more dead and
wounded have passed through my hands than I hope you will ever
see in the battlefield during the whole of your military career;
believe me, I have no fear of death.”
The party proceeded and, arrived at the battery, obtained a near
view of Sebastopol. M. Soyer was in his most volatile mood, and
relates that the following incident occurred: “Before leaving the
battery, I begged Miss Nightingale as a favour to give me her hand,
which she did. I then requested her to ascend the stone rampart
next the wooden gun carriage, and lastly to sit upon the centre
mortar, to which requests she very gracefully and kindly acceded.”
Having thus unsuspectedly beguiled Miss Nightingale into this
position, the irrepressible Frenchman boldly exclaimed:
“Gentlemen, behold this amiable lady sitting fearlessly upon that
terrible instrument of war! Behold the heroic daughter of England—
the soldier’s friend!” All present shouted “Bravo! Hurrah! hurrah!
Long live the daughter of England.”
When later Lord Raglan was told of this incident, he remarked
that the battery mortar ought to be called “the Nightingale mortar.”
While in that elevated position the heroine was recognised by
the 39th Regiment, and the men set up such ringing cheers as
wakened echoes in the caves of Inkerman and startled the Russians
in Sebastopol.
The sun was beginning to sink below the horizon and shadows
to gather over the trenches and fortifications of the besieged city
when Miss Nightingale started on the return journey. She and her
party, proceeding at a sharp gallop through the camps, were
overtaken by darkness when only half-way back to Balaclava, and
losing their way, found themselves in a Zouave camp, where the
men were drinking coffee and singing their favourite African song.
They informed the travellers that brigands were roaming about, and
that it was dangerous to take the road after nightfall. However,
brigands or not, there was nothing for it but to push on down the
deep ravine which now faced them. The road was so steep and
slippery that one of the gentlemen dismounted to lead Miss
Nightingale’s horse by the bridle. When they halted to water the
horses, this gentleman received a severe blow in the face by coming
in sharp contact in the dark with the head of Miss Nightingale’s
steed. He concealed the injury, though his face was streaming with
blood and his eyes blackened, until they reached Balaclava hospital,
when the Queen of Nurses returned his kind attention by helping to
dress his wounds. Proceeding to the harbour, she retired to her state
cabin on the Robert Lowe, and so ended Florence Nightingale’s
adventurous visit to the camp hospitals before Sebastopol.
CHAPTER XVIII
STRICKEN BY FEVER
Continued Visitation of Hospitals—Sudden Illness—Conveyed to

Sanatorium—Visit of Lord Raglan—Convalescence—Accepts Offer
of Lord Ward’s Yacht—Returns to Scutari—Memorial to Fallen
Heroes.
Know how sublime a thing it is

To suffer and be strong.
Longfellow.
N OTHING daunted by the fatiguing journey to the camp hospitals

at headquarters related in the last chapter, Miss Nightingale,
although she was feeling indisposed, set out the next morning to
visit the General Hospital at Balaclava and the Sanatorium. She was
accompanied by the ubiquitous M. Soyer, who was carrying out his
culinary campaign at the Crimean hospitals, and attended by her
faithful boy Thomas.
After spending several hours inspecting the wards of the General
Hospital, Miss Nightingale proceeded to the Sanatorium, a collection
of huts perched on the Genoese heights nearly eight hundred feet
above the sea. She was escorted by Mr. Bracebridge, Dr. Sutherland,
and a sergeant’s guard. The weather was intensely hot, as is usual
in the Crimea during the month of May, and the journey, following
on the fatigue of the previous day, proved a trying one. Half-way up
the heights, Miss Nightingale stopped to visit a sick officer in one of
the doctor’s huts, and afterwards proceeded to inspect the
Sanatorium.
She returned to Balaclava, and next day went to install three
nurses in the Sanatorium; and on her way up again visited the
invalid officer in his lonely hut. During the succeeding days she
continued her inspection of the hospitals in Balaclava, and also
removed her quarters to the London, as the Robert Lowe, in which
she sailed, was ordered home.
It was when on board the London, while she was transacting
business with one of her nursing staff, that Miss Nightingale was
suddenly seized with alarming illness. The doctors pronounced it to
be the worst form of Crimean fever, and ordered that she should be
immediately taken up to the Sanatorium. She was laid on a stretcher,
and tenderly carried by sad-eyed soldiers through Balaclava and up
the mountain side amid general consternation. Her own private
nurse, Mrs. Roberts, attended her, a friend held a large white
umbrella to protect her face from the glaring sun, and poor Thomas,
the page-boy, who had proudly called himself “Miss Nightingale’s
man,” followed his mistress, crying piteously. So great was the
lamenting crowd that it took an hour to get the precious burden up
to the heights. A hut was selected near a small stream, the banks of
which were gay with spring flowers, and there for the next few days
Florence Nightingale lay in a most critical condition, assiduously
nursed by Mrs. Roberts and attended by Drs. Henderson and Hadley.
It seemed strange to every one that Miss Nightingale, after
passing unscathed through her hard labours at Scutari, when she
had been in daily contact with cholera and fever, should have
succumbed to disease at Balaclava, but the fatigues of the past
days, undertaken during excessive heat, accounted largely for the
seizure, and some of her friends thought also that she had caught
infection when visiting the sick officer on her way up to the
Sanatorium.
Alarmist reports quickly spread, and at Balaclava it was currently
reported that Florence Nightingale was dying. The sad tidings were
told at the Barrack Hospital at Scutari amidst the most pathetic
scenes. The sick men turned their faces to the wall and cried like
children. The news in due time reached London, and the leading
articles in the papers of the time show that the public regarded the
possible death of our heroine as a great national calamity. Happily
the suspense was brief, and following quickly on the mournful tidings
came the glad news that the worst symptoms were passed, and that
in all human probability the precious life would be spared.
Miss Nightingale, in a touching bit of autobiography, attributes
her first step towards convalescence to the joy caused on receiving a
bunch of wild-flowers.
During the time that Miss Nightingale lay in her hut on the
Genoese heights, some very sharp skirmishes were taking place
between the allied troops and the enemy, and it was reported that
the Russians were likely to attack Balaclava by the Kamara side. Miss
Nightingale’s hut being the nearest to that point, would, in the event
of such a plan being carried out, have been the first to be attacked.
Thomas, the page boy, constituted himself guard of his beloved
mistress and was ready to die valiantly in her defence. It would,
however, be an injustice to the Russian troops to imply that they
would knowingly have harmed even a hair of Florence Nightingale’s
head. Her person was sacred to friend and foe alike.
Lord Raglan was deeply concerned at Miss Nightingale’s illness,
and as soon as he heard from the doctors in attendance that he
might visit her, rode over from headquarters for the purpose. Mrs.
Roberts, the nurse, thus related to M. Soyer the account of the
Commander-in-Chief’s unexpected call:—
“It was about five o’clock in the afternoon when he came. Miss
Nightingale was dozing, after a very restless night. We had a storm
that day, and it was very wet. I was in my room sewing when two
men on horseback, wrapped in large gutta-percha cloaks and
dripping wet, knocked at the door. I went out, and one inquired in
which hut Miss Nightingale resided.
“He spoke so loud that I said, ‘Hist! Hist! don’t make such a
horrible noise as that, my man,’ at the same time making a sign with
both hands for him to be quiet. He then repeated his question, but
not in so loud a tone. I told him this was the hut.
“‘All right,’ said he, jumping from his horse, and he was walking
straight in when I pushed him back, asking what he meant and
whom he wanted.
“‘Miss Nightingale,’ said he.
“‘And pray who are you?’
“‘Oh, only a soldier,’ was the reply; ‘but I must see her—I have
come a long way—my name is Raglan—she knows me very well.’
FLORENCE NIGHTINGALE AS A GIRL.
(From the drawing by her sister, Lady Verney.)

Full Pressure Sensitive Design and Formulation Application First Edition Benedek Ebook All Chapters

Uploaded by

Copyright:

Available Formats

Full Pressure Sensitive Design and Formulation Application First Edition Benedek Ebook All Chapters

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Full Pressure Sensitive Design and Formulation Application First Edition Benedek Ebook All Chapters

Uploaded by

Copyright:

Available Formats

Full download ebook at ebookgate.

Pressure sensitive design and formulation

Download more ebook from https://ebookgate.com

Technology of Pressure Sensitive Adhesives and Products

Fundamentals of Pressure Sensitivity 1st Edition Istvan

Pressure Vessel Design Manual Illustrated procedures

JavaScript Application Design A Build First Approach

Mobility protocols and handover optimization design

Affinity Electrophoresis Principles and Clinical

Recent Advances in Design and Usage of Pressure Vessels

Fatigue of Materials and Structures Application to

Boca Raton London New York

CRC Press is an imprint of the

Published 20 I 8 by CRC Press

© 2006 by Taylor & Francis Group, LLC

No claim to original U.S. Government works

ISBN 13: 978-90-6764-440-2 (hbk)

Visit the Taylor & Francis Web site at

and the CRC Press Web site at

1.1 Raw Materials as a Function of the End-Use 1

2 FORMULATION EQUIPMENT 106

2. 1 Blending Equipment 106

2.2 Manufacturing Equipment 117

1 HOT-MELT PRESSURE- SENSITIVE ADHESIVES 141

2 STYRENIC BLOCK COPOLYMER 143

3 TACKIFIERS FOR SBC-BASED HOT-MELT PSAs 149

3.1 Rosin Resins 151

4 ADHESION PERFORMANCE OF SBC-BASED HMPSAs 157

4.1 Viscoelastic Behavior of Hot-melt PSAs 157

1 MOLECULAR NATURE OF PRESSURE-SENSITIVE 181

2 BASIC TYPES OF INTERPOLYMER COMPLEXES 183

3 THERMODYNAMIC PRINCIPLES OF INTERPOLYMER 184

3.1 Ladder- Like Complexes 185

4 ADHESIVES BASED ON LADDER- LIKE COMPLEXES 188

4.1 Factors Providing the Preparation 188

6 ADHESIVES BASED ON THE COMBINATION OF 210

6.1 Mechanical Properties 211

7 CORPLEX™ ADHESIVES OF CONROLLED WATER­ 222

7.1 Classification of Corplex™ Adhesives in Terms of Their 223

2 REMOVABLE AND REPOSITIONABLE PRESSURE- 232

2.1 Mixture of Pressure-Sensitive Adhesives with 232

3 INFLUENCE OF THE COATING WEIGHT ON TACK 245

4.1 Removability 246

5 PROSPECTS FOR REMOVABLE AND 248

1 WHAT ISUV? 251

1.1 Principles of Photocuring 252

2 UV-CURABLE PRESSURE-SENSITIVE- ADHESIVES 256

2.1 Techniques in UV-Polymerizable PSAs 258

3 ADHESION PROPERTIES OF UV-CURABLE PSAs 270

3.1 UV-Polymerizable PSAs 271

4 KINETICS OF UV-CURABLE PSAs 284

1 DESIGN AND FORMULATION FOR ADHESIVE 291

1.1 Design and Formulation of Permanent Adhesives 291

2 DESIGN AND FORMULATION FOR PRESSURE- 315

2.1 Design and Formulation of Labels 315

Abbreviations and Acronyms 367

Chapter 1 Design- and Formulation Basis

Chapter 2 Hot-Melt PSAs Based on Styrenic Polymer

Chapter 3 Pressure-Sensitive Adhesives of

7 CORPLEX™ ADHESIVES OF CONROLLED WATER 222