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Colorants and auxiliaries

ORGANIC CHEMISTRY AND APPLICATION PROPERTIES

Second Edition

Volume 2 – Auxiliaries

Edited by John Shore

Formerly of BTTG/Shirley and ICI Dyes (now DyStar), Manchester, UK

2002

Society of Dyers and Colourists

iii

Copyright © 2002 Society of Dyers and Colourists. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means without the prior permission of the copyright owners.

Published by the Society of Dyers and Colourists, PO Box 244, Perkin House, 82 Grattan Road, Bradford, West Yorkshire BD1 2JB, England, on behalf of the Dyers’ Company Publications Trust.

This book was produced under the auspices of the Dyers’ Company Publications Trust. The Trust was instituted by the Worshipful Company of Dyers of the City of London in 1971 to encourage the publication of textbooks and other aids to learning in the science and technology of colour and coloration and related fields. The Society of Dyers and Colourists acts as trustee to the fund.

Typeset by the Society of Dyers and Colourists and printed by Hobbs The Printers, Hampshire, UK.

ISBN 0 901956 78 3

iv

Contributors

John Shore Formerly of BTTG/Shirley and ICI Dyes (now DyStar), Manchester, UK

Terence M Baldwinson Formerly Dye & Information Service Manager, Yorkshire Chemicals plc, Leeds, UK

v

Contents

Preface

ix

CHAPTER 8

Functions and properties of dyeing and printing auxiliaries

471

8.1

The need for auxiliaries 471

8.2

The general types and characteristics of auxiliaries 474 References 476

CHAPTER 9

The chemistry and properties of surfactants

477

9.1

Introduction 477

9.2

Hydrophiles 477

9.3

Hydrophobes 477

9.4

Anionic surfactants 479

9.5

Cationic surfactants 485

9.6

Nonionic surfactants 486

9.7

Amphoteric surfactants 489

9.8

The general properties of surfactants 490 References 496

CHAPTER 10

Classification of dyeing and printing auxiliaries by function

497

10.1

Electrolytes and pH control 497

10.2

Sequestering agents 505

10.3

Macromolecular complexing agents 519

10.4

Enzymes 539

10.5

Preparation of substrates 553

10.6

Dispersing and solubilising agents 636

10.7

Levelling and retarding agents 642

10.8

Thickening agents, migration inhibitors and hydrotropic agents used in printing and continuous dyeing 645

10.9

Treatments to alter dyeing properties or enhance fastness 664

10.10

Agents for fibre lubrication, softening, antistatic effects, soil release, soil repellency and bactericidal activity 705

10.11

Foaming and defoaming agents 744 References 750

vi

CHAPTER 11

Fluorescent brightening agents

760

11.1

Introduction 760

11.2

Mode of action of a fluorescent brightener 761

11.3

Evaluation of FBAs: measurement of whiteness 765

11.4

General factors influencing FBA performance 768

11.5

Chemistry and applications of FBAs 770

11.6

Brighteners for cellulosic substrates 770

11.7

Brighteners for cellulose acetate and triacetate fibres 781

11.8

Brighteners for nylon 784

11.9

Brighteners for wool 788

11.10

Brighteners for polyester fibres 790

11.11

Brighteners for acrylic fibres 799

11.12

Brighteners in detergent formulations 803

11.13

Analysis of FBAs 809 References 811

CHAPTER 12

Auxiliaries associated with main dye classes

813

12.1

Introduction 813

12.2

Acid dyes 813

12.3

Azoic components 820

12.4

Basic dyes 824

12.5

Direct dyes 832

12.6

Disperse dyes 837

12.7

Reactive dyes 856

12.8

Sulphur dyes 882

12.9

Vat dyes 893 References 913

vii

Preface to Volume 2

This Second Edition of a textbook first published in 1990 forms part of a series on colour and coloration technology initiated by the Textbooks Committee of the Society of Dyers and Colourists under the aegis of the Dyers’ Company Publications Trust Management Committee, which administers the trust fund generously provided by the Worshipful Company of Dyers. The initial objective of this series of books has been to establish a coherent body of explanatory information on the principles and application technology of relevance for students preparing to take the Associateship examinations of the Society. This particular book has been directed specifically to the subject areas covered by Section A of Paper B: the organic chemistry and application of dyes and pigments and of the auxiliaries used with them in textile coloration processes. However, many qualified chemists and colourists interested in the properties of colorants and their auxiliaries have found the First Edition useful as a work of reference. For several reasons it has been convenient to divide the material into two separate volumes: 1. Colorants, 2. Auxiliaries. Although fluorescent brighteners share some features in common with colorants, they have been treated as auxiliary products in this book. This second volume of the book collects together a remarkable quantity and variety of factual information linking the application properties of auxiliary products in textile coloration and related processes to as much as is known of the chemical structure of these agents. The environmental impact of auxiliary products has become of major importance and developments during the 1990s have necessitated substantial modification and expansion of the text of this volume. The opportunity has also been taken to highlight novel chemical types of auxiliaries that are under evaluation to overcome or avoid many of the drawbacks shown by traditional products. Thus the two volumes of this Second Edition are now approximately equal in size, whereas in the 1990 edition Volume 2 was only about half as big as its sibling. Virtually all of this development and improvement of Volume 2, especially in the much expanded Chapters 10 and 12, is thanks to the thorough and painstaking work of Terry Baldwinson, who has carefully sifted through an extensive yet scattered range of primary sources. Our grateful thanks are due to John Holmes and Catherine Whitehouse for their patient copy editing and to the publications staff of the Society, especially Carol Davies, who have prepared all the material in this new edition for publication.

ix

JOHN SHORE

Chapters in Volume 1

Chapter 1

Classification and general properties of colorants

Chapter 2

Organic and inorganic pigments; solvent dyes

Chapter 3

Dye structure and application properties

Chapter 4

Chemistry of azo colorants

Chapter 5

Chemistry and properties of metal-complex and mordant dyes

Chapter 6

Chemistry of anthraquinonoid, polycyclic and miscellaneous colorants

Chapter 7

Chemistry of reactive dyes

x

471

CHAPTER 8

Functions and properties of dyeing and printing auxiliaries

Terence M Baldwinson

8.1 THE NEED FOR AUXILIARIES

There is hardly a dyeing or printing process of commercial importance that can be adequately operated by the use of dyes and water alone. Practically every colorant–substrate system requires the use of additional products, known as auxiliaries, to ensure its reliable functioning and control. This was the case even centuries ago, when the use of natural vat and mordant dyes depended entirely on the proper, albeit rule of thumb, use of additives. These controlled pH, reduction, oxidation and mordanting to enable the dyes to be applied to the natural fibres of those days. Many of the auxiliaries, like the dyes and fibres, were of natural origin. Dung and urine [1] were among the agents used, and soap was clearly the first surfactant to be employed. Indeed, from the standpoint of today, one can only wonder at the degree of purely empirical expertise so successfully developed and applied by the ancient dyers and printers. Our current level of understanding is clearly a phenomenal advance on the ancient arts, yet our need for auxiliaries remains. For example, even before dyeing or printing the substrate must be cleaned and wetted. Products are needed to convert non-substantive vat and sulphur dyes to substantive forms, to help stabilise the conditions that bring about the substantivity, and then to reconvert the dyes to their insoluble forms in the substrate (sections 1.6.1 and 1.6.2). Mordant dyes still require the appropriate chelating agents, as well as other agents to create and maintain the optimum chelating conditions (section 5.8). Printers still need thickening agents to facilitate the localised application of dyes. Inevitably, however, the present-day plethora of dyes, fibres and coloration processes has created additional reasons for the use of auxiliaries, whilst the concurrent evolution of the chemical industry has satisfied these needs as they arose. Moreover, a vastly more comprehensive understanding of the physico–chemical processes involved has enabled auxiliaries to be precisely engineered for specific purposes. Hand in hand with this theoretical knowledge, practical evaluation has become increasingly sophisticated. Nevertheless, it is often difficult to differentiate between auxiliaries promoted purely for commercial reasons and those that serve a definite technical need. Dye manufacturers are acutely aware of the positive part played by auxiliaries in helping to sell dyes, and dyers today are under constant pressure to use more of them. Some additives offer cost savings by improving reproducibility and minimising reprocessing; nevertheless it is all too tempting to incorporate too many products without critically evaluating their efficacy, thus inevitably and unnecessarily increasing processing costs. Consequently it is more important than ever that the dyer or printer understands the

471

472 FUNCTIONS AND PROPERTIES OF DYEING AND PRINTING AUXILIARIES

functions of auxiliary products and is equipped to evaluate their use realistically and to monitor it continually. As has been implied already, functional demands for auxiliaries continue to grow, with each dye–fibre system and dyeing or printing process having particular needs. The primary functions of auxiliaries are:

(a)

to prepare or improve the substrate in readiness for coloration by

– scouring, bleaching and desizing

– wetting

– enhancing the whiteness by a fluorescent brightening effect

(b)

to modify the sorption characteristics of colorants by

– acceleration

– retardation

– creating a blocking or resist effect

– providing sites for sorption

– unifying otherwise divergent rates of sorption

– improving or resisting the migration of dyes

(c)

to stabilise the application medium by

– improving dye solubility

– stabilising a dispersion or solution

– thickening a print paste or pad liquor

– inhibiting or promoting foaming

– forming an emulsion

– scavenging or minimising the effects of impurities

– preventing or promoting oxidation or reduction

(d)

to protect or modify the substrate by

– creating or resisting dyeability

– lubricating the substrate

– protecting against the effects of temperature and other processing conditions

(e)

to improve the fastness of dyeings, as in

– the aftertreatment of direct or reactive dyes

– the aftertreatment of acid dyes on nylon

– the chroming of mordant dyes on wool or nylon

– giving protection against atmospheric influences, as in UV absorbers or inhibitors of gas-fume fading

– back-scouring or reduction clearing

(f)

to enhance the properties of laundering formulations (fluorescent brightening agents).

Some auxiliaries fulfil more than one of the above functions. For example, an auxiliary to improve dye solubility may also accelerate (or retard) a coloration process, or an emulsifying agent may also act as a thickening agent; pH-control agents may both stabilise a system and also affect the rate of dye sorption. Thus the range of auxiliaries available is very large indeed, covering a multiplicity of uses for all stages of textile processing. However, a factor which has assumed great importance regarding the use of auxiliaries in recent years is that of their effects on the environment. In view of the extensive portfolio of products and processes, it is not surprising that good

THE NEED FOR AUXILIARIES

473

environmental management is complex. Undesirable effects from the use of auxiliaries may become evident during handling, through effluent discharge to surface waters, through discharge to the atmosphere (e.g. via stenter gases), through consumer contact with the finished product (e.g. skin sensitivity) or during the eventual disposal of solid wastes (e.g. incineration or landfill). All these factors need careful consideration in the selection of auxiliaries at all stages of processing. Compliance with good environmental practice may be voluntary (preferably) or enforced by legislation, some countries having introduced quite extensive and stringent requirements [2,3]. Many factors need to be considered: acute toxicity to mammals, toxicity to aquatic organisms (fish, daphniae, algae) and waste water bacteria, biodegradability (aerobic or anaerobic), abiotic degradability (hydrolysis, photolysis, oxidation), ground mobility, bioaccumulation, carcinogenicity, mutagenicity and teratogenicity. The textile wet processing industry produces particularly heavy discharges of effluent; hence the responsibility placed on it for environmentally good behaviour is indeed an onerous one, both technically and financially [4]. The preparation processes of desizing, scouring and bleaching, together with their associated wash-off processes, inevitably produce a heavy biological oxygen demand in the effluent [5]. Hence there has been, and continues to be, much research effort to improve the environmental performance of these areas. There are two general approaches to good environmental practice. The first, termed ‘end- of-pipe’ solutions, requires all unacceptable matter to be removed from the effluent, or at least to be reduced to acceptable levels. This is relatively difficult and expensive, requiring the appropriate treatment facilities. The second attempts to minimise the need for end-of- pipe treatments by reducing the hazardous nature of the effluent in the first place. This can be achieved, for example, by recycling and reusing useful constituents, especially reducing water volumes through the use of low liquor ratios, and reducing the toxicity of the effluent by selecting ‘green’ chemicals and processing methods. In some cases, the volume of effluent can be reduced by combining some processes, e.g. desizing, scouring and bleaching. The possibilities inherent in the second approach have stimulated much research work amongst manufacturers and suppliers of auxiliaries, in terms of finding ‘greener’ products and more acceptable processes for their use. These efforts will continue for the foreseeable future. It is important to remember that auxiliaries nowadays are most frequently supplied as more or less complex mixtures. It is essential from an environmental point of view to consider the influence of the subsidiary components in the branded product as well as of the main substances. For example, even a small amount of solvent added to improve the stability of an auxiliary may pose problems of flammability or toxic vapours, necessitating careful storage and labelling. Constant monitoring of products and processes is necessary, since environmental requirements are continually changing as more information, matched by increasing awareness of hazards, becomes available. It has been suggested that the main concerns to date have been in response to controlling listed substances rather than in tackling fundamental environmental problems [5]. Wragg [6] has provided the following basic environmental check-list for textile wet processing:

(1) Is the product free from species and/or by-products that are on the various control lists? Lists of controlled chemicals are being continually extended, together with controls on their use. Usage of heavy metals, solvents and AOX-containing products will gradually decrease.

474 FUNCTIONS AND PROPERTIES OF DYEING AND PRINTING AUXILIARIES

(2) Is the manufacturing process suitable for safety and environmental controls? Processing cycles are being placed under greater control in terms of machine operation. Auxiliary usage will be more specific and accurate to avoid over-consumption and to minimise waste. (3) Has the product or its components been assessed at any time for acute toxicity, carcinogenicity or irritant properties? (4) Are the materials easily dealt with in waste treatment systems? (5) Has the product or its components been assessed at any time for toxicity to aquatic species?

The overall result of environmental awareness has been to increase the interplay of devolution and evolution. Devolution has seen increasing restrictions, sometimes amounting to a complete ban, on the use of certain substances (e.g. alkylphenolethoxylates, which were once widely used) and a corresponding evolution of new products which, at least for the present, are environmentally acceptable. This interplay between devolution and evolution is likely to continue indefinitely. Environmental factors as they affect specific types of auxiliary will be dealt with under the relevant sections of this volume.

8.2 THE GENERAL TYPES AND CHARACTERISTICS OF AUXILIARIES

An auxiliary has been defined [7] as ‘a chemical or formulated chemical product which enables a processing operation in preparation, dyeing, printing or finishing to be carried out more effectively, or which is essential if a given effect is to be obtained’. It is much harder to devise a classification system for auxiliaries than it is for dyes. This is undoubtedly one of the main reasons why there has been no incentive to produce an auxiliaries index comparable with the Colour Index. It is difficult enough to put together a comprehensive yet manageable list of general application types; it becomes even more difficult to classify them chemically, especially as many of them are more or less complex mixtures, are of imprecisely known structure or are the subject of a good deal of trade confidentiality. Although the Society of Dyers and Colourists has shown reluctance to be involved in this area, a very useful biennial trade publication [8] has made considerable progress in the ordered listing of currently available commercial products. This first appeared in 1967. The seventeenth edition (2000) lists currently available products by trade name, application and suppliers. Unfortunately this publication does not include a listing by chemical type. Although the first section does give whatever chemical detail the manufacturers are prepared to divulge, these tend to be bland, broadly based descriptions such as ‘nonionic aqueous emulsion of modified wax’ or ‘quaternary ammonium compound, cationic’. In spite of these shortcomings it remains an indispensable guide to the vast range of products on the market today. The broadest classification of auxiliaries is achieved simply by dividing them into non- surfactants and surfactants, as detailed below. Non-surfactants include simple electrolytes, acids and bases, both inorganic and organic. Examples include sodium chloride, sodium acetate, sulphuric acid, acetic acid and sodium carbonate, together with complex salts (such as sodium dichromate, copper(II) sulphate, sodium ethylenediaminetetra-acetate, sodium hexametaphosphate), oxidising agents (hydrogen peroxide, sodium chlorite) and reducing agents (sodium dithionite, sodium sulphide). Anionic polyelectrolytes such as sodium alginate or carboxymethylcellulose, used

THE GENERAL TYPES AND CHARACTERISTICS OF AUXILIARIES

475

mainly as thickening agents and migration inhibitors, also fall within the class of non- surfactants; so too do sorption accelerants such as o-phenylphenol, butanol and methylnaphthalene, although they normally require an emulsifier to stabilise them in aqueous media. Fluorescent brightening agents (FBAs) form another large class of non- surfactant auxiliaries (see Chapter 11). Surfactants are, in general, substantially organic in nature and structurally more complex than most non-surfactants. It is difficult to define surfactants in a manner sufficiently precise to satisfy everyone. However, for the purposes of this book an adequate definition of a surfactant is given by the Society’s Terms and Definitions Committee [7]: ‘an agent, soluble or dispersible in a liquid, which reduces the surface tension of the liquid’. In coloration processes this reduction in surface tension usually takes place at a liquid/liquid or liquid/solid interface, although liquid/gas interfaces are also occasionally important. In general, a dramatic lowering of surface tension can be brought about by a relatively small amount of surfactant; as little as 0.2 g/l of a soap such as sodium oleate will more than halve the surface tension of water. This physical effect in solution is attributed to the molecular orientation potential of a relatively small hydrophilic moiety (a hydrophile) having strong polar forces, juxtaposed with a relatively large (usually linear) hydrophobic moiety (a hydrophobe) having relatively weak electrostatic forces (Figure 8.1). In aqueous solution or dispersion the polar hydrophile tends to be oriented into the body of the aqueous phase, whilst the hydrophobe, by nature subjected to forces of repulsion by the aqueous phase, is oriented towards (or at) the interfacial boundary, which may be that between the solution and air or between the solution and a fibrous (or other) substrate. The surfactants used as textile auxiliaries can be divided into four major groups, depending on the type and distribution of the polar forces, an arrangement broadly resembling the ionic classification of dyes. The general scheme is shown in Table 8.1.

of dyes. The general scheme is shown in Table 8.1. Strongly polar hydrophile Weakly polar hydrophobe

Strongly

polar

hydrophile

Weakly polar hydrophobe
Weakly polar hydrophobe
Weakly polar hydrophobe

Weakly polar hydrophobe

Figure 8.1 Schematic diagram of surfactant

Table 8.1 General classification of surfactants

Degree of ionic charge on the

 

Hydrophile

Class of surfactant

Hydrophobe

(associated ion)

Anionic

Weakly negative

Strongly positive

Cationic

Weakly positive

Strongly negative

Nonionic

Uncharged

Uncharged

Amphoteric

These possess balanced negative and positive charges, one or other of which dominates in solution depending on the pH

476 FUNCTIONS AND PROPERTIES OF DYEING AND PRINTING AUXILIARIES

REFERENCES

1. H T Pratt, Text. Chem. Colorist, 19 (1987) 23.

2. S Helman, Melliand Textilber., 72 (1991) 567.

3. W Baumann, U Engler,. W Keller and W Schefer, Textilverediung, 27 (1992) 392.

4. M Lomas, J.S.D.C., 109 (1993) 10.

5. J Park and J Shore, J.S.D.C., 100 (1984) 383.

6. P Wragg, J.S.D.C., 110 (1994) 137

7. Colour terms and definitions (Bradford: SDC, 1988).

8. Index to textile auxiliaries, 17th Edn (Bradford: World Textile Publications, 2000).

CHAPTER 9

477

The chemistry and properties of surfactants

Terence M Baldwinson

9.1 INTRODUCTION

A surfactant was defined in Chapter 8 as: ‘an agent, soluble or dispersible in a liquid, which

reduces the surface tension of the liquid’ [1]. It is helpful to visualise surfactant molecules as

being composed of opposing solubility tendencies. Thus, those effective in aqueous media typically contain an oil-soluble hydrocarbon-based chain (the hydrophobe) and a smaller water-solubilising moiety which may or may not confer ionic character (the hydrophile).

The limitations of space do not permit a comprehensive detailed treatment of the chemistry

of

surfactants. The emphasis is therefore on a broad-brush discussion of the principal types

of

surfactant encountered in textile preparation and coloration processes. Comprehensive

accounts of the chemistry and properties of surfactants are available [2–13]. A useful and lucid account of the chemistry and technology of surfactant manufacturing processes is given by Davidsohn and Milwidsky [14].

9.2 HYDROPHILES

The basic purpose of the hydrophile is to confer solubility (aqueous solubility is always to be understood unless otherwise stated). The simple moieties most often employed are as follows:

(a)

in anionic surfactants: sodium, potassium or ammonium cations, associated with negatively charged groups on the hydrophobe such as carboxylate, sulphonate, sulphate or phosphate

(b)

in cationic surfactants: chloride, bromide or methosulphate ions, juxtaposed with, for example, positively charged quaternary nitrogen atoms

(c)

in nonionic surfactants: ethylene oxide or propylene oxide moieties.

More complex hydrophilic moieties are sometimes encountered, however, such as mono-, di- and tri-ethanolamine and the corresponding isopropanolamines in anionic surfactants. Morpholine, once employed, is now obsolete owing to its toxicity.

9.3 HYDROPHOBES

There is a much wider choice of hydrophobes. Most are based on substantially linear long- chain alkanes, either saturated or unsaturated. These were originally obtained from naturally occurring fats and oils such as castor, fish, olive, sperm, coconut and tallow oils, but these sources were later superseded by petroleum products which at that time were cheaper. More recently, not only has the price of crude oil escalated, but there has also been a growing

477

478 THE CHEMISTRY AND PROPERTIES OF SURFACTANTS

awareness of the finite and diminishing nature of this resource. In 1995, some 75% fossil- sourced raw materials were used in the production of synthetic anionic surfactants (90% if lignosulphonates are excluded) [8], but it is foreseen that more biological materials will be used in the future. It is evident that for some time there has been a systematic and large expansion of vegetable oil production, especially in South East Asia [8]. Typical vegetable oils include: tallow, coconut, palm kernel, palm, soybean, linseed, cotton, rape and sunflower. Most cationic surfactants are still obtained from petrochemical olefins, alcohols, paraffins and aromatics, although some are derived from fatty acids [9]. The most common hydrophobes used as the basis for surfactants are those containing eight to eighteen carbon atoms, such as those listed as carboxylates in Table 9.1. Some hydrophobes are aromatic (benzene or naphthalene) moieties, often containing lower alkyl substituents; dodecylbenzene (9.1) is a common example. Alkyl-substituted toluenes, xylenes and phenols, and mono- and di-alkylated naphthalenes (9.2 and 9.3), are also used.

Table 9.1 Examples of hydrophobes

No. of

carbon

Chemical

atoms

name

Trivial name and formula

8

Octanoate

Caprylate CH 3 (CH 2 ) 6 COO

10

Decanoate

Caprate CH 3 (CH 2 ) 8 COO

12

Dodecanoate

Laurate CH 3 (CH 2 ) 10 COO

12

9-Dodecenoate

Lauroleate CH 3 CH 2 CH=CH(CH 2 ) 7 COO

14

Tetradecanoate

Myristate CH 3 (CH 2 ) 12 COO

14

9-Tetradecenoate

Myristoleate CH 3 (CH 2 ) 3 CH=CH(CH 2 ) 7 COO

15

Pentadecanoate

Isocetate CH 3 (CH 2 ) 13 Palmitate CH 3 (CH 2 ) 14

 
 

COO

16

Hexadecanoate

 

COO

16

9-Hexadecenoate

Palmitoleate CH 3 (CH 2 ) 5 CH=CH(CH 2 ) 7 COO

17

Heptadecanoate

Margarate CH 3 (CH 2 ) 15

COO

18

Octadecanoate

Stearate CH 3 (CH 2 ) 16

COO

18

9-Octadecenoate

Oleate CH 3 (CH 2 ) 7 CH=CH(CH 2 ) 7 COO

18

9,12-Octadecadienoate

Linoleate CH 3 (CH 2 ) 4 (CH=CHCH 2 ) 2 (CH 2 ) 6 COO

18

9,12,15-Octadecatrienoate

Linolenate CH 3 CH 2 (CH=CHCH 2 ) 3 (CH 2 ) 6 COO

18

12-Hydroxy-9-octadecenoate

Ricinoleate CH 3 (CH 2 ) 5 CH(OH)CH 2 CH=CH(CH 2 ) 7 COO

C 12 H 25 C 8 H 17
C 12 H 25
C 8 H 17

9.1

9.2

ANIONIC SURFACTANTS C 4 H 9 H 9 C 4
ANIONIC SURFACTANTS
C 4 H 9
H 9 C 4

9.3

479

The hydrophobes are usually, though not always, used in the form of acids, alcohols, esters or amines. Commercial products rarely contain a single pure hydrophobe, however; most are mixtures containing a range of hydrophobes, since the raw materials from which they are made are generally themselves mixtures of homologues. For example, a batch of coconut oil, a rich source of the lauric hydrophobe, may have the approximate composition shown in Table 9.2, although the proportions of the individual components may vary by 1–3% between batches. As is the general rule in naturally occurring fats and waxes, only even-numbered carbon compounds are present; odd-numbered ones have to be made by synthesis. Clearly, a surfactant produced from such a mixture will contain a very large, and variable, number of homologues and isomers. Hence two products with the same nominal constitution, but from different manufacturers, often differ in details of composition and properties. This is one fundamental reason why a chemical classification of auxiliaries, analogous to that for dyes in the Colour Index, would be extremely difficult to devise.

Table 9.2

Approximate hydrophobe composition of

coconut oil

Trivial

No. of

Amount

name

carbon atoms

(%)

Caproate

6

0.5

Caprylate

8

7.0

Caprate

10

6.5

Laurate

12

49.5

Myristate

14

17.0

Palmitate

16

8.5

Stearate

18

2.5

Oleate

18

6.5

Linoleate

18

2.0

Any hydrophobe can yield each of the main (i.e. anionic, cationic, nonionic or amphoteric) types of surfactant in much the same way as the same chromogenic system can be used in anionic, basic or disperse dyes. This will be demonstrated in the following sections, dealing with each class of surfactant, using the cetyl-containing (C 16 H 33 ) hydrophobe.

9.4 ANIONIC SURFACTANTS

Until recently this class accounted for by far the largest number of surfactants used in preparation and coloration processes. This dominance is now challenged by the much increased use of nonionic types. The essential feature of the class is a long-chain

480 THE CHEMISTRY AND PROPERTIES OF SURFACTANTS

hydrophobe linked through an anionic grouping – usually carboxylate, sulphate (sulphuric ester) or sulphonate, but occasionally phosphate, carboxymethyl or other group – to a relatively small cation, generally sodium, although ammonium, potassium and other cations are also used. Carboxylates (9.4, where R is the long-chain hydrophobe and X the cation) represent the oldest type of surfactants, since they could be obtained from naturally occurring fats and oils long before the advent of the petrochemical industry; sodium heptadecanoate (9.5), for example, incorporates the cetyl group as hydrophobe. Sodium stearate, sodium palmitate and sodium oleate are the simplest carboxylates generally used as surfactants. Alkylaryl compounds (9.6) are also known.

R

COO

9.4

_ +

X

C

16

H 33 COO

9.5

_
+

Na

_ + H COO Na 25 C 12
_ +
H
COO
Na
25 C 12

9.6

Many carboxylates are used in the form of soaps, obtained by alkaline saponification of triglyceride fats and waxes of general formula 9.7. The three carboxylic ester groups (RCOO) may carry the same or different hydrophobes, generally containing eight to 22 carbon atoms, the most common being laurate, palmitate and stearate among the saturated types, and oleate and linoleate among the unsaturated ones. At ambient temperatures the unsaturated fats tend to be liquids and the saturated ones solids.

R 1

CH 2 COO CH
CH
2
COO
CH

9.7

CH

2

OOC OOC
OOC
OOC

R 2

R 3

R HC CH _ CH COO _ CH 2 COO
R
HC
CH
_
CH
COO
_
CH 2
COO

9.8

Na

+

Na

+

Particularly important as wetting agents are the disodium alkenylsuccinates (9.8), in which the saturated R group may contain from three to fourteen carbon atoms. The surfactant properties of these carboxylates, as with other types of surfactant, are dependent on the number of carbon atoms in the hydrophobe. Significant surfactant properties begin to appear in the C 8 compounds, although the C 8 –C 12 carboxylates are wetting agents rather than detergents. Better detergency and emulsifying properties become evident with C 12 –C 18 alkyl groups. Solubility decreases with increasing length of the alkyl group; the solubility of soaps, for example, reaches its useful limit with the C 22 compounds. The major disadvantage of the carboxylates is that they tend to be precipitated by acids and hard water, since the free acids and the calcium and magnesium salts of the carboxylates are insoluble. This disadvantage provided the main technical reason for finding alternative products that showed tolerance to a wider range of processing conditions. Modified carboxylates, in which the carboxylate moiety forms part of a carboxymethoxy group, are also available. These are made by reaction of selected nonionic surfactants with chloroacetic acid. The result is a useful hybrid range, lacking the sensitivity of simple

ANIONIC SURFACTANTS

481

carboxylates to calcium and magnesium whilst retaining excellent detergency; these compounds are more stable to electrolytes than are the conventional nonionics and more suitable for use at high temperatures as they are not susceptible to cloud point problems (section 9.8.2). Sulphates or sulphuric esters of the long-chain fatty acids were the first alternative to the carboxylates. They are essentially the half esters of sulphuric acid (9.9); the ester incorporating the cetyl hydrophobe (9.10) belongs to the important class of fatty alcohol sulphates. Such sulphates, using C 8 –C 18 hydrophobes, are common.

R

_

OSO 3

9.9

Na

+

_

C 16 H 33 OSO 3

9.10

Na

+

Just as there are mono-, di- and tri-carboxylate surfactants, the sulphates can also be prepared from products bearing mono-, di- and tri-hydrophobes. Indeed, the first sulphates

to be used were analogous to soaps in that they were the sulphation products of triglycerides. Although their chemistry can be represented in simple terms, it is worth re-stating that most commercial products are highly complex mixtures. For example, a sulphated triglyceride may contain the following:

– the sulphated glyceride proper

– sulphated free fatty acid

– unsulphated glyceride

– unsulphated fatty acid

– inorganic salts

– traces of glycerol.

The range of hydrophobes present may also be unexpectedly broad, since the raw materials often consist of mixtures of symmetrical and/or mixed glycerides. As little as 60% of an oil may be sulphatable; sulphation is never carried to theoretical completion and is often far below 100%. With these provisos in mind, the chemistry of the sulphated oils can be considered. Many oils are used as starting materials: olive, castor, tallow, neatsfoot, cotton seed, rape seed and corn oils are examples. Sulphated olive oil was the first sulphated oil to be produced and was used as a mordant in dyeing as long ago as 1834. Sulphation usually occurs at the double bonds of any unsaturated fatty acids in the glyceride (Scheme 9.1). On the other hand, in the preparation of the best-known of these products, Turkey Red Oil or sulphated (often wrongly termed ‘sulphonated’) castor oil, sulphation of the main component, the glyceride of ricinoleic acid (12-hydroxy-9-octadecenoic acid), takes place preferentially at the hydroxy group rather than at the double bond (Scheme 9.2). Such products possess useful wetting, emulsifying and dye-levelling properties.

CH CH CH 2 CH + H 2 SO 4 _ OSO 3 H
CH
CH
CH 2
CH
+ H 2 SO 4
_
OSO 3
H

+

482 THE CHEMISTRY AND PROPERTIES OF SURFACTANTS

CH CH 2 CH CH CH CH 2 CH CH + H 2 SO 4
CH
CH 2
CH
CH
CH
CH 2
CH
CH
+ H 2 SO 4
_
+
OH
OSO 3
H

Scheme 9.2

At the present time, however, the long-chain alcohol sulphates already mentioned, such as structure 9.10, and particularly the sulphated ethers are of greater importance. The stability of the sulphates to mildly acidic conditions and to hard water is much better than that of the carboxylates and is sufficient for most purposes. Under more stringent acidic conditions, however, hydrolysis may take place. Another type of sulphated product, an ester sulphate, can be prepared by esterifying a fatty acid such as ricinoleic or oleic acid with a short-chain (C 3 –C 5 ) alcohol and then sulphating. Such products are particularly useful foaming, wetting and emulsifying agents; an example is sulphated butyl ricinoleate (9.11).

CH 3 (CH 2 ) 5 CHCH 2 CH + OSO 3 H
CH 3 (CH 2 ) 5 CHCH 2 CH
+
OSO 3 H

CH(CH 2 ) 7 COO(CH 2 ) 3 CH 3

9.11

More recent developments amongst anionic surfactants are the sulphated polyethers or alcohol poly(oxyethylene) sulphates (9.12, 9.13), prepared by ethoxylating the fatty alcohol to give a polyether containing a terminal hydroxy group that is then sulphated. Aromatic hydrophobes may also be used to produce, for example, alkylphenol poly(oxyethylene) sulphates. In a general sense, a poly(oxyethylene) sulphate can be viewed as a partly anionic and partly nonionic surfactant, although the degree of ethloxylation of these products is generally much lower than that of the purely nonionic surfactants. Hence they are sometimes referred to as ‘lightly ethoxylated alcohol sulphates’; again, their actual composition may be a good deal more complex than indicated by their nominal structural formulae. There has been increasing use of these derivatives in domestic detergents.

R

(OCH 2 CH 2 ) x

9.12

_

OSO 3

Na

+

C 16 H 33

(OCH 2 CH 2 ) x

9.13

OSO 3

_ +

Na

Sulphonated anionic surfactants have the general structure 9.14, which should be compared with that of the sulphates (9.9). As well as the simple alkyl derivatives such as structure 9.15, aromatic and particularly alkylated aromatic (alkylaryl) types are technically and commercially important. Indeed, sodium dodecylbenzenesulphonate (9.16) has long been of great importance in domestic washing powders. Although it is no longer the only surfactant used in domestic washing powders, its economy, efficacy and environmental properties are such that it is likely to remain the dominant anionic surfactant in heavy-duty concentrated powder detergents for some time [15]. Environmental studies have shown that 90% of such linear alkylbenzenesulphonates are removed by conventional sewage treatment, the remainder being virtually completely biodegradable in topsoil with half-life values varying from 3 to 25 days [16,17].

_

RSO 3 Na +

9.14

C 16 H 33 SO 3

_ +

Na

9.15

H 25 C 12

ANIONIC SURFACTANTS _ + SO 3 Na
ANIONIC SURFACTANTS
_ +
SO 3
Na

9.16

483

Nowadays these compounds are usually blended with other surfactants, including nonionic types (section 9.6). In 1990 a typical low- or non-phosphate domestic detergent contained 7% linear alkylbenzenesulphonate and 6% nonionic fatty alcohol ethoxylate [16]. There is increasing use of the long-chain fatty alcohol poly(oxyethylene) sulphates previously described (e.g. 9.12) as a partial or complete replacement for linear alkylbenzenesulphonates [15] since they are made from renewable feedstocks such as tallow and palm oil [16]. Naphthalene and other aromatic hydrophobes are also used to produce sulphonates, such as structure 9.17. Of greater importance, however, are the more complex condensation products that form the basis of many excellent dispersing, resist and aftertreating (syntan) agents. Typical examples are the condensation products of naphthalenesulphonates with formaldehyde, and the lignosulphonates derived from pulping processes; these are described in more detail in section 10.6.1.

C 3 H 7 9.17
C 3 H 7
9.17

SO 3

_ +

Na

Sulphosuccinates are of particular interest not only for their technical properties but also because structurally they combine the two hydrophile functions described earlier – the sulphonate and carboxylate moieties – in a single molecule (9.18). The sulphosuccinate diesters, however, are probably of greater commercial importance in textile processing than are the monoesters. The most important example is sodium dioctylsulphosuccinate (9.19), but the dinonyl, dimethylamyl and di-isobutyl analogues are also used commercially. As usual, a wide choice of hydrophobes is available and includes alcohols, lightly ethoxylated alcohols, alkanolamides and combinations of these.

COOR COOC 8 H 17 H 2 C H 2 C _ + _ +
COOR
COOC 8 H 17
H 2 C
H 2 C
_ +
_ +
CH
SO 3
Na
CH
SO 3
Na
_
COO
Na +
COOC 8 H 17
9.18
9.19

Phosphate esters (9.20) represent a different class of hydrophile-characterised anionic surfactants; mono- or di-esters can be formed depending on whether one or two alkyl groups are present. Most phosphate esters are based on alcohols and especially their ethoxylates,

484 THE CHEMISTRY AND PROPERTIES OF SURFACTANTS

including aliphatic and alkylaryl types. Whereas the sulphates tend to be based on lightly ethoxylated alcohols, the phosphate esters are also made from more highly ethoxylated products. Commercial products are complex mixtures (9.21) of monoester, diester, free phosphoric acid and free nonionic surfactant [18].

O O R O P OH ROPO R OH OH
O
O
R
O
P
OH
ROPO
R
OH
OH

9.20

O O R(OCH 2 CH 2 ) x O P OH R(OCH 2 CH 2
O
O
R(OCH 2 CH 2 ) x O
P
OH
R(OCH 2 CH 2 ) x O
P
O(CH 2 CH 2 O) x R
OH
OH
Monoester surfactant
Diester surfactant
9.21
O
HO
P
OH
R(OCH 2 CH 2 ) x OH
OH
Free phosphoric
Free nonionic
acid
surfactant

Phosphate esters are particularly useful for their alkali stability and wettability. It has been shown [18] that a certain amount of ethoxylation of the hydrophobe is required to obtain alkali resistance, and that as the relative molecular mass (M r ) of the hydrophobe increases, the proportion of ethylene oxide required also increases. The greater the degree of ethoxylation, the greater the degree of alkali resistance, few materials showing good alkali resistance with less than six moles of ethylene oxide per mole of hydrophobe. The same study [18] showed that wetting power decreased with increasing M r of the hydrophobe. Incorporating 2–3 moles of ethylene oxide per mole of hydrophobe seems to give optimum wetting. It appears that as one attempts to increase the rate of wetting, alkali tolerance decreases. Other anionic surfactant types include the alkylisethionates (9.22), N-acylsarcosides (9.23), N-acyltaurides (9.24) and perfluorinated carboxylates, sulphonates (e.g. 9.25), sulphates and phosphates [13].

R

O

CH 2 CH 2 SO 3

9.22

_ +

Na

R

O

C N
C
N

CH 3

9.23

CH 2 COO

_

Na

+

R 1

O

CH 2 CH 2 SO 3 2 CH 2 SO 3

_

R 2

9.24

+

Na

CATIONIC SURFACTANTS CF 3 CF 2 F 3 C F C C C O 3
CATIONIC SURFACTANTS
CF 3
CF 2
F 3 C
F
C
C
C
O
3 C
_
F 3 C
CF 2
SO 3
CF 3

9.25

485

Na

+

9.5 CATIONIC SURFACTANTS

By far the most important types of cationic surfactant used in textile processing are the quaternary ammonium salts (9.26), in which R is usually a long-chain hydrophobe and R 1 , R 2 , R 3 are lower alkyl groups. The most common anions in these and other cationic surfactants are chloride and bromide: thus cetyltrimethylammonium chloride (9.27) is typical of this class of cationic surfactants. In fact, however, all four alkyl groups on the nitrogen atom can be varied to alter the balance of properties of the products. In the alkyldimethylmethallylammonium chlorides (9.28), an unsaturated aliphatic group is used. Aromatic components are also used, as in the important alkyldimethylbenzylammonium chlorides (9.29), and both the aromatic nucleus and the alkyl groups in such products may contain substituents (9.30 and 9.31). As important as the quaternary ammonium surfactants are the pyridinium salts (9.32; R is a long-chain alkyl group), such as cetylpyridinium chloride (9.33).

+ R 1 CH 3 _ RNR 2 X N CH 3 H 33 C
+
R 1
CH 3
_
RNR 2
X
N
CH 3
H 33 C 16
R 3
CH 3
9.26
9.27
+
CH
3
_
R
N
CH 2
Cl
CH 3
9.29 CH 3 R N CH 2 CH 2 OH CH 3
9.29
CH 3
R
N
CH 2 CH 2 OH
CH 3

+

Cl

_

+ CH 3 _ R N CH 2 C CH 3 Cl CH 3 CH
+
CH 3
_
R
N
CH 2
C
CH 3
Cl
CH 3
CH
2
9.28
+
Cl
CH 3
_
R
N
CH 2
Cl
CH 3

9.30

N C 16 H 33 + _ Cl
N
C
16 H 33
+
_
Cl
N R + _ X
N
R
+
_
X

9.32

9.33

9.31

+

Cl

_

486 THE CHEMISTRY AND PROPERTIES OF SURFACTANTS

Imidazoles can be quaternised to yield cationic surfactants (such as structures 9.34 and 9.35). Long-chain alkyl primary, secondary and tertiary amines can also be used as cationic surfactants, but their use in textile processing is limited as a result of their insolubility in other than acidic aqueous media. The range of products available as cationic surfactants is truly enormous, including, for example, such complex products as alkylated mono- and di- guanidines and polyamines (9.36) containing more than one basic nitrogen atom.

CH 3 H N 2 C _ + C R 1 Cl H N 2
CH 3
H
N
2 C
_
+
C
R 1
Cl
H
N
2 C
NHCO
CH 2 CH 2
R 2
9.34
R
(NHCH 2 CH 2 ) x NH 2
CH 2 CH 3 N + C R N CH 2
CH 2 CH 3
N
+
C
R
N
CH 2

9.35

Cl

_

9.36

Many of these cationic products, including the quaternary amines and imidazoles, can be ethoxylated (9.37, 9.38), forming cationic analogues of the ethoxysulphates and ethoxyphosphates in the anionic series. They are essentially cationic/nonionic hybrid surfactants, variously described in manufacturers’ promotional literature as ‘modified cationic’, ‘weakly cationic’ or even ‘modified nonionic’. Their value lies in the fact that the cationic nature can be controlled by varying not only the alkyl substituents but also the degree of ethoxylation. In addition the ethoxylate moiety confers useful emulsifying properties. Fluoro-containing cationic surfactants (9.39) can also be obtained [13].

+ CH 3 _ R N (CH 2 CH 2 O) x H Cl (CH
+
CH 3
_
R
N
(CH 2 CH 2 O) x H
Cl
(CH 2 CH 2 O) x H
9.37
CH 3
C
CONH
(CH 2 ) 3
N
7 F 15
+
CH
3
CH 3 H N 2 C + C R H N 2 C (CH 2
CH 3
H
N
2 C
+ C
R
H
N
2 C
(CH 2 CH 2 O) x H
9.38

CH 3

_

9.39 I

_

Cl

9.6 NONIONIC SURFACTANTS

Nearly all nonionic surfactants contain the same type of hydrophobes as do anionic and cationic surfactants, with solubilisation and surfactant properties arising from the addition of ethylene oxide to give a product having the general formula 9.40. Usually, depending on the

NONIONIC SURFACTANTS

487

hydrophobe, aqueous solubility and detergent properties begin to be evident when x = 6, but in theory the degree of ethoxylation can be continued almost indefinitely. Optimal surfactant properties are generally found when x = 10–15, although higher homologues (for example, x = 50) are known. The ‘lightly ethoxylated’ sulphates mentioned earlier usually contain only 2–4 oxyethylene units per molecule. Thus a typical nonionic surfactant can be represented by structure 9.41.

R

(OCH 2 CH 2 ) x OH

9.40

H 33 C 16

(OCH 2 CH 2 ) 12 OH

9.41

Although there are other types of nonionic surfactant, the great majority are adducts of ethylene oxide with hydrophobes derived from three sources:

– fatty alcohols and alkylphenols

– fatty acids

– fatty amines and amides.

For many years the most common of these have been adducts with p-nonyl- and p-octylphenol, and to a lesser extent 2,4-dinonylphenol, p-dodecylphenol and 1-alkylnaphthols. Since the hydrophobes used may be variable products conforming to an average nominal structure, and since the quoted degree of ethoxylation can also only be regarded as an average value, products having the same name (such as, for example, p-nonylphenol dodecaoxyethylene) may in fact differ in detailed composition and properties when obtained from different manufacturers. These provisos should be borne in mind when considering the examples below, even though there is a trend in some cases towards the manufacture of narrower fractions. An example of an alcohol-based nonionic (9.41) has already been given. An alkylphenol adduct (9.42) is essentially similar; both alcohols and phenols give rise to the relatively strong and stable ether link, a valuable property of this type of product. Analogues based on alkylthiols (9.43) may also be used.

H 19 C 9

on alkylthiols (9.43) may also be used. H 1 9 C 9 9.42 (OCH 2 CH

9.42

(OCH 2 CH 2 ) x OH

H 17 C 8

S

(CH 2 CH 2 O) x H

9.43

(OCH 2 CH 2 ) x OH

R
R

(OCH 2 CH 2 ) x OH

9.44

Polyfunctional alcohols of varying complexity, such as polyethylene glycols (9.44) and polypropylene glycols of varying chain length, also provide useful nonionic agents. A polypropylene glycol molecule has a hydroxy group at each end to which ethylene oxide can be added, forming random segments of poly(oxyethylene) and poly(oxypropylene). This results in block copolymers, which can be engineered by control of starting materials and processing conditions to give products specifically suited to a wide variety of purposes by virtue of wide variations in segment length and degree of polymerisation. Whereas the alcohol and phenol derivatives are characterised by ether linkages, adducts of ethylene oxide with fatty acids give rise to both monoesters (9.45) and diesters. These are

488 THE CHEMISTRY AND PROPERTIES OF SURFACTANTS

H 33 C 16 CO(OCH 2 CH 2 ) x OH

9.45

H 23 C 11

(CH 2 CH 2 O) x H

N
N

(CH 2 CH 2 O) x H

9.47

H 23 C 11

C
C

O

H 23 C 11 NH(CH 2 CH 2

9.46

H 23

NH(CH 2 CH 2 O) x H

9.48

O) x H (CH 2 CH 2 O) x H C N C 11 O
O) x H
(CH 2 CH 2 O) x H
C
N
C 11
O (CH 2 CH 2 O) x H

9.49

less stable than the ethers in strongly acidic or alkaline media, however, hydrolysing to the original fatty acid and polyethylene glycol. Adducts of ethylene oxide with fatty amines can yield mono- (9.46) or di-substituted (9.47) products, as can the adducts with fatty amides (9.48, 9.49). In practice the products formed are far from being as simple or as symmetrical as represented by these formulae since, amongst other things, the ethylene oxide addition takes place randomly. A recent introduction in the area of nonionic surfactants is the alkylglycoside series. These are long-chain acetals of saccharides (9.50). Commercial products currently have an average alkyl chain length of 10–12 carbon atoms. These are manufactured from non- petroleum sources, being synthesised from glucose and fatty alcohols. Such acetals are regarded as eco-friendly, being said to be completely biodegradable [19] and having low skin irritancy. These surfactants possess wetting, foaming and detergency properties similar to those of the corresponding alcohol ethoxylates but with higher solubility in water and in solutions of electrolytes. They are soluble and stable in sodium hydroxide solutions and show no inverse solubility characteristics.

HO

CH 2 OH CH O CH CH O CH CH OH OH
CH 2 OH
CH
O
CH
CH
O
CH
CH
OH
OH

9.50

C n H 2n+1

The nonionic types so far discussed form the great majority used in textile processing. Of course, a great many more can be synthesised, as the possible range of permutations and combinations is truly enormous. Given appropriate conditions, ethylene oxide will react with almost any proton-donating compound, but the choice in practice is restricted by economic factors. Not all nonionic surfactants are ethoxylates, however. Analogous propylene oxide adducts are known; rather more different products include sucrose and sorbitan esters, alkanolamides and fatty amine oxides. The fatty acid esters of compounds such as sucrose and sorbitol exhibit surfactant properties. Some, such as the sorbitan fatty esters, are insoluble in water but being oil-soluble they can be used as emulsifiers in oil-based systems, or they can be ethoxylated to render them water-soluble. Mention has already been made of fatty amide poly(oxyethylene) adducts formed by condensation of a fatty acid with an alkanolamine which is then ethoxylated; some complex alkanolamides have in themselves (i.e. without ethoxylation) some surfactant properties, however. They are made by the

AMPHOTERIC SURFACTANTS

489

reaction of a fatty acid (such as lauric acid or a coconut fatty acid) with a secondary alkanolamine (such as diethanolamine) to yield an amide, which then reacts further with diethanolamine to give the water-soluble alkanolamide surfactant. Typical fatty amine oxides (9.51 and 9.52) are derived, for example, from the peroxide oxidation of tertiary amines containing at least one fatty-chain group.

H 25 C 12

9.51

CH 3 N CH 3
CH 3
N
CH 3

O

O N 9.52
O
N
9.52

O

C

12 H 25

9.7 AMPHOTERIC SURFACTANTS

As mentioned in Table 8.1, amphoteric surfactants contain both an anionic and a cationic group. In acidic media they tend to behave as cationic agents and in alkaline media as anionic agents. Somewhere between these extremes lies what is known as the isoelectric point (not necessarily, or even commonly, at pH 7), at which the anionic and cationic properties are counterbalanced. At this point the molecule is said to be zwitterionic and its surfactant properties and solubility tend to be at their lowest. These products have acquired a degree of importance as auxiliaries in certain ways [20–25], particularly as levelling agents in the application of reactive dyes to wool. The simplest type is represented by the higher alkylaminoacids, such as compound 9.53; disubstituted amines can also be synthesised (9.54). Ethoxylated products can also feature as amphoteric surfactants; an example is compound 9.55, an alkylamine poly(oxyethylene) sulphate. Of particular interest in textile processing are the trisubstituted alkylamino acids known as betaines; N-alkylbetaines (9.56; R = C 8 –C 16 alkyl) and acylaminoalkylbetaines (9.57; R = C 10 –C 16 alkyl) are typical [30]. Sulphate and sulphonate analogues of the carboxylates, such as the sulphobetaine 9.58, can also be used as amphoteric agents.

R

H 33 C

CH 3 + N CH 3
CH 3
+
N
CH 3

+

16 NH 2 CH 2 COO

9.53

_

CH 2 COO

9.56

_

CH 2 COOH + H 33 C 16 HN _
CH 2 COOH
+
H 33 C 16 HN
_

R

CH 2 COO

9.54

CH 3 + CONHCH 2 CH 2 CH 2 N
CH 3
+
CONHCH 2 CH 2 CH 2
N

9.57

CH 3

H 33 C 16

(CH 2 CH 2 O) x H

+ HN
+
HN

_

(CH 2 CH 2 O) x CH 2 CH 2 OSO 3

_

CH 2 COO

R

9.55

CH 3 + N CH 3
CH 3
+
N
CH 3

_

CH 2 CH 2 CH 2 SO 3

490 THE CHEMISTRY AND PROPERTIES OF SURFACTANTS

9.8 THE GENERAL PROPERTIES OF SURFACTANTS

9.8.1 Effects on the environment

The widespread use of these products focused attention on their environmental properties long ago, owing to the persistent foam-creating tendency of many surfactants when discharged. However, the surfactants industry has a very good track record of responding to environmental problems, stretching back as long ago as the 1960s; that is, quite some time before the present environmental bandwagon began to roll. Karsa has provided a pointed reminder of this: ‘The most significant development in the West in the 1960s was the growing environmental awareness and concern for biodegradable components to overcome problems at sewage treatment plants and foam in watercourses. The result was an under- publicised and often forgotten fact that industry on both sides of the Atlantic voluntarily changed from branched-chain alkylbenzenesulphonates’. Since then, ‘detergents have been based on biodegradable components, contrary to the impression given with some of the information supplied with today’s ‘green’ detergents, which would have one believe biodegradability is something new and exclusive to these products. This was among the first major environmental moves by any industry and was ten years ahead of any UK or EEC legislation’ [16]. Major works dealing with environmental aspects of surfactants are available [26–30]. The excellent biodegradability of the linear alkylarylsulphonates has already been mentioned (section 9.4). The alcohol sulphates have low toxicity and alcohol poly(oxyethylene) sulphates are even less toxic. Alkane sulphonates have high COD, BOD and an MBAS degradation rate of 90%. Polyether carboxylates have excellent environmental properties and are non-toxic to the extent that they are used in cosmetics and household detergents. Sodium- α -olefin sulphonates show rapid biodegradation due to their linear structures. The α -sulphomonocarboxylic esters show good to excellent environmental properties and are also used in cosmetics and household detergents. Sulphosuccinates generally show 90% biodegradation after seven days and have a long history of safe use, being ranked as relatively non-toxic. Phosphorus-containing anionics are very mild to the skin and are used in cosmetics, shampoos and lotions. The toxicology of perfluorinated surfactants varies greatly; most are harmless, whilst some are amongst the most toxic non-proteins known, the structural differences between the two often being relatively slight. Hence caution is needed in their use, even though they are so strongly surface-active that they can be used in much smaller quantities than other surfactants. Cationic alkylammonium surfactants have shown 94% biodegradability [27]. Amongst the nonionics, the use of linear primary alcohol ethoxylates has grown rapidly since the 1970s, due in very large measure to their high degree of biodegradability under most test procedures, both rapid primary and ultimate degradation [28]. Biodegradation of such products is retarded by branching of the alkyl chain, this being cumulative. It is also retarded in secondary alcohol structures, by the addition of about 3 equivalents of propylene oxide to the ethoxylate moiety and by an ethoxylate chain of more than 20 units. However, as Talmage points out [28], products containing these features are not present in the simple alcohol ethoxylates most commonly used in detergent formulations. In contrast to the above trends, during the 1980s and 1990s there has been considerable environmental concern over the alleged effects of the nonionic nonylphenol ethoxylates.

THE GENERAL PROPERTIES OF SURFACTANTS

491

The concern seemed to be centred around possible bioaccumulation and the properties of nonylphenol itself, potentially one of the major metabolites (products of biodegradation) released during the environmental breakdown of nonylphenol ethoxylates. The incomplete biodegradation was attributed to branching in the nonyl group and the presence of the aromatic phenyl ring. In the 1980s, particularly in Europe, there were calls for restrictions and bans on the use of nonylphenol ethoxylates. This concern, not surprisingly, led to much careful and detailed research from which has evolved a clarified and much less alarmist picture. This research has been excellently reported by Naylor [31], who pointed out the limitations of laboratory methods (the extent of biodegradation of nonylphenol ethoxylates has been variously reported from 0% to 100%!) and the critical importance of determining biodegradability in conventional waste water plants using improved and streamlined analytical methods. This work, on American rivers and treatment plants, showed that nonylphenol ethoxylates exhibited high treatability under conditions of extremely high loadings on waste water treatment plants. It was confirmed that nonylphenol is indeed the metabolite of highest toxicity but it is not a significant metabolite except under anaerobic conditions. It was shown that nonylphenol ethoxylates are extensively biodegraded (92.5– 99.8% removal rates) in secondary treatment. Re-aeration studies have shown that nonylphenol and nonylphenol ethoxylates contained in sewage sludge degrade when the sludge is applied to soil. Thus there is a strong basis for the conclusion that nonylphenol ethoxylates are highly biodegradable, do not accumulate in water, sediment or aquatic organisms and do not pose a credible threat to the environment. Hence, in 1995, Naylor [31] was able to say that, in America, nonylphenol ethoxylates were by far the most important alkylphenol ethoxylates, accounting for 80% of the total volume and commonly found in formulations for fibre sizing, spinning, weaving, scouring and dyeing, as well as for water-based paints, inks, adhesives and many institutional and household cleaning products. Finally, in considering the environmental properties of surface-active auxiliaries generally, it should be borne in mind that they are more or less complex mixtures and hence the presence of other components, such as solvents, electrolytes or sequestrants, needs to be considered in addition to the surfactants present.

9.8.2 Application properties

Anionic and cationic products generally tend to interact with each other, usually diminishing the surface-active properties of both and often resulting in precipitation of the complex formed. Amphoteric compounds can also be incompatible with anionics in acid solution but are generally compatible with cationics and nonionics. Interaction between anionic and cationic agents can sometimes be prevented by addition of a nonionic. In some cases, if an ethoxylated sulphate or phosphate is used as the anionic component a cationic compound produces no obvious precipitation, since the oxyethylene chain acts as dispersant for any complex that may be formed. The main disadvantages of the carboxylates are their tendency to react with calcium and magnesium ions in hard water to give insoluble precipitates and their insolubility in acidic media, although they generally have good wetting and detergent properties. The acylsarcosides are less affected by calcium and magnesium ions, however, whilst the

492 THE CHEMISTRY AND PROPERTIES OF SURFACTANTS

carboxymethyl surfactants are unaffected. The sulphates were specifically developed to overcome the drawbacks of the carboxylates and, like the phosphates, are stable towards calcium and magnesium ions. As well as being outstanding detergents, the sulphonates are also unaffected by strongly acidic or alkaline conditions, and the higher-alkyl members have useful lubricating properties. On the other hand, the sulphates can be hydrolysed by acid and sulphated monoglycerides can also be hydrolysed by alkali. Their wetting properties tend to be inferior to those of the sulphonates but they are particularly valuable as emulsifying agents, especially in combination with nonionics. The sulphosuccinates have a high propensity to foaming and their solubility is not generally good, but the monoesters have good detergency properties and the diesters are particularly rapid wetting agents. As a group, the phosphates have good stability to acid and alkali for most purposes, have low foaming and good detergency properties and are biodegradable. They tend to be better wetting agents than the sulphates and their solubility in organic solvents makes them useful in, for example, dry cleaning. The perfluoroalkyl anionic surfactants are very expensive, but are powerful surfactants at very low concentrations and are stable in chemically hostile environments; they also exhibit surface activity in organic solvents. Cationic agents generally are less useful than anionics as detergents but they have useful properties as softeners, germicides and emulsifiers. Nonionic agents are generally compatible with both anionic and cationic types. They are also stable to calcium and magnesium ions. With the exception of the fatty acid esters, which are readily hydrolysed by acid and alkali, they are stable and effective over a wide range of pH values. A particular characteristic of nonionic surfactants is their inverse solubility: as the temperature rises the solubility decreases, until a point is reached at which the surfactant

attains its limiting solubility and therefore begins to precipitate out, causing cloudiness of the solution. The temperature at which this occurs, known as the cloud point, depends on the number of oxyethylene units in the nonionic molecule in relation to the length of the hydrophobe. Thus, for any given hydrophobe, the cloud point increases with the increasing degree of ethoxylation; for example, dodecanol heptaoxyethylene C 12 H 25 (OCH 2 CH 2 ) 7 OH has

a cloud point of 59 °C, while that of the undecaoxyethylene homologue is 100 °C. Conversely,

for a fixed number of oxyethylene units, the cloud point decreases with increasing size of the hydrophobe. The cloud points of nonionic agents are also generally lowered by the presence of electrolytes, the effect varying with the electrolyte and its concentration. It is important to bear this in mind when choosing nonionic agents for use in electrolyte-containing processes. This inverse solubility arises from the solubilisation of the nonionic molecules by hydrogen bonding of water with the ether oxygen atoms (9.59). As the temperature rises, the energy

within these bonds becomes insufficient to maintain their cohesion and dehydration takes place, with a consequent decrease in solubility. A knowledge of the cloud point of a surfactant

is useful, not only because of solubility effects but also because the surface activity tends to be

optimal just below the cloud point.

O H O H H O CH 2 CH 2 O CH 2 O CH
O
H
O
H H
O CH 2
CH 2
O
CH 2
O
CH 2
n
H
O
H

9.59

H

THE GENERAL PROPERTIES OF SURFACTANTS

493

The tendency of nonionics to produce foam varies. Some, such as the block copolymers, are even used as defoamers. Their wetting, detergency and emulsifying properties also vary widely, depending to a large extent on the balance between the hydrophobic and hydrophilic (oxyethylene) portions. The amphoteric agents exhibit excellent compatibility with inorganic electrolytes and with acids and alkalis. Such is their stability in strongly acidic solution that they are even used in cleaning compositions based on hydrofluoric acid [14].

9.8.3 The theory of surface activity

The physico-chemical theory of surface activity is a vast field and no more than broad principles can be touched on here; major reference sources exist for those who require more detail of the relationship between chemical structure and the various surfactant properties such as wetting, detergency and emulsification-solubilisation [32–36]. Surface activity is generally related to the balance between the hydrophobic and hydrophilic portions of the molecule. For example, among the anionic surfactants C 8 –C 12 alkyl hydrophobes tend to be predominantly wetting agents, whilst the C 12 –C 18 homologues exhibit better detergency and emulsifying properties. The alkylsuccinates and sulphosuccinates are particularly powerful wetting agents. Clearly, as the hydrophobic character of the surfactant is increased, aqueous solubility decreases and oil solubility increases. Thus the balance between the hydrophobic and hydrophilic moieties of a surfactant is a critical factor in determining its major characteristics. This is referred to as the hydrophile–lipophile balance, or HLB (the term ‘lipophile’, of course, being analogous to ‘hydrophobe’). Whilst the HLB value is of general use in expressing the characteristics of a surfactant, it is of particular value in describing the formation of emulsions. For some general purposes the HLB can be used qualitatively (referring, for instance, to low, medium or high HLB), but for more precise work it is preferable to use a quantifying scale. Such a scale, put forward in the 1940s [37], covers a range of values from zero (the lipophilic or hydrophobic extreme) to a hydrophilic extreme of 20 or higher, with a value of 10 approximately representing the point at which the hydrophilic and hydrophobic portions are in balance. This scale is especially useful in describing the properties of the nonionic ethoxylates. For example, a low HLB value (4–6) signifies a predominance of hydrophobic groups, indicating that the surfactant is lipophilic and should be suited for preparing water- in-oil emulsions. A value in the 7–9 range indicates good wetting properties. As the value shifts towards increased hydrophilicity other properties predominate, values of 8–18 being typical for surfactants that will give oil-in-water emulsions, and values of 13–15 for surfactants that show useful detergency. The HLB values required for solubilising properties are generally in the range 10–18. The HLB of a relatively pure poly(oxyethylene) adduct can be calculated from theoretical data [37]. For these agents the HLB is an indication of percentage by mass of the hydrophilic portion, divided by five to give a conveniently small number. For example, if the hydrophilic portion of a purely hypothetical nonionic agent accounted for 100% of the molecule (such a product cannot, of course, exist), its HLB is 20. Similarly, a more plausible product in which 85% of the molecule is accounted for by the hydrophilic portion has an HLB of 85/5 = 17. The ICI Americas Inc. method of calculating the theoretical HLB of a sorbitan monolaurate nonionic having 20 oxyethylene units per molecule is given in

494 THE CHEMISTRY AND PROPERTIES OF SURFACTANTS

Equation 9.1 (total relative molecular mass = 1226, of which 1044 is contributed by the hydrophilic portion) [37].

HLB

1044

1

100

1226 5

17.0

(9.1)

As explained earlier, however, the actual constitution of a surfactant rarely conforms to its nominal structure. Consequently the theoretical method of calculation is of limited utility, practical methods being more reliable. The HLB value may be determined directly by analysis or by comparison with a range of surfactants of known HLB values. An analytical method for the sorbitan monolaurate described above uses Equation 9.2 [37].

HLB

20

S

45.5

1

A

276

20

1

16.7

(9.2)

where S is the saponification number of the ester and A is the acid number of the recovered acid. The saponification value of a product is the mass in milligrams of potassium hydroxide required to saponify one gram of the product; it can be found by saponification of the product with an excess of potassium hydroxide, followed by back-titration of the remaining alkali with hydrochloric acid. The acid value of an acid is the number of milligrams of potassium hydroxide required to neutralise a standard quantity, and can again be found by titration. The comparative methods should always be used for the nonionic surfactants that are not based on ethylene oxide, and also for ionic surfactants since the hydrophilic influence of the ionic group exceeds that indicated by the mass percentage basis (this can lead to apparent HLB values higher than 20). Once the HLB values of a range of surfactants are known it is an easy matter to calculate the HLB value of a mixture as follows:

Individual HLB

Fractional HLB

 

45% of surfactant A

16.7

0.45 × 16.7

=

7.52

35% of surfactant B

4.0

0.35 × 4.0

=

1.40

20% of surfactant C

9.6

0.20 × 9.6

=

1.92

 

Total HLB

= 10.84

When preparing an emulsion, emulsification tends to be most efficient when the HLB of the agent matches that of the oil phase. Often a mixture of surfactants makes a more efficient emulsifying agent than a single product having the same HLB value as the mixture; similarly, if the oil phase to be emulsified is itself a mixture, its components will each contribute to the effective HLB value. It is this effective HLB that is the main criterion in designing a suitable emulsifying system. The effective HLB value can be found by carrying out preliminary emulsification tests with agents of known HLB values. A useful procedure [37] uses two such emulsifying agents of widely differing HLB values mixed in various proportions so as to give a range of intermediate HLB values. The HLB value of the mixture that gives the best emulsion of the oil phase under test then corresponds to the effective

Surface tension/N m 1

THE GENERAL PROPERTIES OF SURFACTANTS

495

HLB value of the oil phase. Further tests can then be carried out with different chemical types of agents around this effective HLB value in order to find the optimum emulsifying system.

9.8.4 Micelle formation

All surfactants in solution tend to form more or less ordered agglomerates of molecules, known as micelles. Pure water has a surface tension of about 72 × 10 3 N/m. As surfactant is added gradually to it, the surface tension falls quite rapidly (Figure 9.1) until, at a certain concentration of surfactant, it begins to level off more or less sharply. At the point at which this levelling out takes place, the critical micelle concentration (CMC in Figure 9.1), the surfactant molecules begin to orient themselves in clusters within the body of the solution, these clusters being more or less lamellar or spherical (Figure 9.2).

being more or less lamellar or spherical (Figure 9.2). CMC Concentration of surfactant/g l – 1
being more or less lamellar or spherical (Figure 9.2). CMC Concentration of surfactant/g l – 1
being more or less lamellar or spherical (Figure 9.2). CMC Concentration of surfactant/g l – 1
being more or less lamellar or spherical (Figure 9.2). CMC Concentration of surfactant/g l – 1

CMC

Concentration of surfactant/g l 1

Figure 9.1 Surface tension of water against surfactant concentration

Lamellar Spherical
Lamellar
Spherical

Figure 9.2 Micelle formation

In water the surfactant molecules orient themselves with their hydrophobes at the centre of the cluster. The CMC is typically quite low, perhaps 0.5–0.2 g/l. At concentrations lower than this the molecules orient themselves only at the interfaces of the solution, and it is this effect which brings about the lowering of surface tension. Once the CMC is reached the

496 THE CHEMISTRY AND PROPERTIES OF SURFACTANTS

interfaces become saturated and as the concentration increases micellar clusters of molecules begin to form in the bulk of the solution; there is little further reduction in surface tension beyond the CMC, nor are there changes in the other surfactant properties such as wetting and foaming. In general, the CMC decreases with increasing size of the hydrophobe, and the CMCs of nonionic agents tend to be lower than those of ionic types, since with the nonionics micelles can form more easily in the absence of polar charges. This ability to form micelles is vital to the efficacy of surfactants as emulsifying, dispersing and solubilising agents.

REFERENCES

1.

Colour terms and definitions (Bradford: SDC, 1988).

2.

Kirk-Othmer encyclopedia of chemical technology, 3rd Edn., Vol. 22 (New York: Wiley, 1983).

3.

M R Porter and M Porter, Handbook of surfactants, 2nd Edn. (Glasgow: Blackie Academic and Professional,

1994).

4.

D R Karsa, J M Goody and P J Donnelly, Surfactants applications directory (Glasgow: Blackie Academic and Professional, 1991).

5.

M R Porter and M Porter, Recent developments in the technology of surfactants (Glasgow: Blackie Academic and Professional, 1991).

6.

K Y Lai, Liquid detergents (New York: Marcel Dekker, 1996).

7.

M J Rosen, Surfactants and interfacial phenomena, 2nd Edn. (New York: Wiley, 1989).

8.

H W Stache, Anionic surfactants: organic chemistry (New York: Marcel Dekker, 1995).

9.

J M Richmond, Cationic surfactants: organic chemistry (New York: Marcel Dekker, 1990).

10.

V M Nace, Nonionic surfactants: polyoxyalkylene block copolymers (New York: Marcel Dekker, 1996).

11.

E G Lomax, Amphoteric surfactants, 2nd Edn. (New York: Marcel Dekker, 1996).

12.

I Piirma, Polymeric surfactants (New York: Marcel Dekker, 1992).

13.

E Kissa, Fluorinated surfactants: synthesis, properties, applications (New York: Marcel Dekker, 1993).

14.

A S Davidsohn and B Milwidsky, Synthetic detergents, 7th Edn. (Harlow: Longman, 1987).

15.

G Bevan, Rev. Prog. Coloration, 27 (1997) 1.

16.

D R Karsa, Rev. Prog. Coloration, 20 (1990) 70.

17.

Summary of Aachen conference, Alkylbenzenesulphonates in the environment, J. Amer. Oil Chem. Soc., 66 (1989) 748; full proceedings in Tenside Surf. Det., (Apr/May 1989).

18.

A J O’Lenick and J K Parkinson, Text. Chem. Colorist, 27 (Nov 1995) 17.

19.

R H Mehta and A R Mehta, Colourage, 43/45 (1996) 49.

20.

A Riva and J Cegarra, J.S.D.C., 103 (1987) 32.

21.

H Egli, Textilveredlung, 8 (1973) 495.

22.

W Mosimann, Text. Chem. Colorist, 1 (1969) 182.

23.

J Cegarra, Proc. IFATCC, Barcelona (1975).

24.

J Cegarra, A Riva and L Aizpurua, J.S.D.C., 94 (1978) 394.

25.

J Cegarra and A Riva, Melliand Textilber., 64 (1983) 221.

26.

D R Karsa and M R Porter, Biodegradability of surfactants (Glasgow: Blackie Academic and Professional, 1995).

27.

M J Schwuger, Detergents in the environment (New York: Marcel Dekker, 1996).

28.

S S Talmage, Environmental and human safety of major surfactants (London: Lewis Publications, 1994).

29.

C Gloxhuber and K Kunstler, Anionic surfactants: biochemistry, toxicology, dermatology, 2nd Edn. (New York:

Marcel Dekker, 1995).

30.

P Schöberl, K J Bock and L Huber, Tenside Surf. Det., 25 (1988) 86.

31.

C G Naylor, Text. Chem. Colorist, 27 (Apr l995) 29.

32.

K Tsujii, Surface activity: principles, phenomena and applications (San Diego: Academic Press, 1998).

33.

J C Berg, Wettability (New York: Marcel Dekker, 1993).

34.

A K Chattopadhyay and K L Mittal, Surfactants in solution (New York: Marcel Dekker, 1996).

35.

S D Christian and J F Scamehorn, Solubilisation in surfactant aggregates (New York: Marcel Dekker, 1995).

36.

A W Neumann and J K Spelt, Applied surface thermodynamics (New York: Marcel Dekker, 1996).

37.

The HLB system – a time-saving guide to emulsifier selection, Publication 103–3 10M (Wilmington: ICI Americas,

1984).

497

CHAPTER 10

Classification of dyeing and printing auxiliaries by function

Terence M Baldwinson

10.1 ELECTROLYTES AND pH CONTROL

The simplest auxiliaries of all are the neutral electrolytes such as sodium chloride and sodium sulphate. These are used in large quantities for dyeing cellulosic materials with direct or reactive dyes and wool with anionic dyes. The major effect of electrolytes on dyes of this type is to increase the degree of aggregation of the dye anions in solution by the common-ion effect, the degree of aggregation varying markedly with dye structure (section 3.1.2). The electrolyte suppresses ionisation of the dye in solution, thereby effectively reducing its solubility in the dyebath and modifying the equilibrium in favour of movement of dye anions from the solution into the fibre. The objective, of course, is to use the optimum amount of salt to give the required rate and degree of exhaustion of the dyebath; too little electrolyte is ineffective whilst too much may aggregate the dye to an extent that may inhibit its diffusion into the fibre, thus giving a tendency to surface coloration only, or even bringing about precipitation. The aggregating effect of electrolytes varies, sodium chloride having a stronger effect than sodium sulphate, but it is generally decreased by raising the temperature. This effect, which we may term the ‘salting-on’ effect, is the result of interactions between electrolyte and dye. However, there may also be interactions between electrolyte and fibre, giving rise to a positive levelling action as electrolyte anions compete with dye anions for the cationic sites in the fibre. Ionic surfactants (Table 8.1) can of course be regarded as electrolytes, although by hydrophobic interactions they tend to form micelles in concentrated solution and hence may be referred to as colloidal electrolytes. In some respects their levelling action is analogous to that of simple inorganic electrolytes – that is, ionic hydrophobes compete with dye ions of similar charge for sites of opposite charge in the fibre. Electrolytes are used to promote the exhaustion of direct or reactive dyes on cellulosic fibres; they may also be similarly used with vat or sulphur dyes in their leuco forms. In the case of anionic dyes on wool or nylon, however, their role is different as they are used to facilitate levelling rather than exhaustion. In these cases, addition of electrolyte decreases dye uptake due to the competitive absorption of inorganic anions by the fibre and a decrease in ionic attraction between dye and fibre. In most discussions of the effect of electrolyte on dye sorption, attention is given only to the ionic aspects of interaction. In most cases, this does not create a problem and so most adsorption isotherms of water-soluble dyes are interpreted on the basis of Langmuir or Donnan ionic interactions only. There are, however, some observed cases of apparently anomalous behaviour of dyes with respect to electrolytes that cannot be explained by ionic interactions alone.

497

498 CLASSIFICATION OF DYEING AND PRINTING AUXILIARIES BY FUNCTION

The fact is, ionic interaction between dyes, fibres and electrolytes is only part of the story. As Yang [1] has pointed out, hydrophobic interactions also need to be taken into consideration. Whilst this has been accepted for many years in relation to dye–fibre interactions, the extension of the concept to interactions involving neutral electrolytes is novel. Yang quotes as one of several examples the fact that sodium chloride has a stronger effect than sodium sulphate on decreasing the uptake of CI Acid Red 1 by nylon, which cannot be explained on the basis of ionic interaction alone. It can, however, be explained in terms of the effect of the electrolytes on hydrophobic interaction, the same explanation also being applied to other examples. A lyotropic series is used to explain the effectiveness of hydrophobic interactions, which always coexist with ionic interactions. A semi-quantitative representation of the lyotropic series is shown in Figure 10.1. In such a series, neutral ions have little influence on hydrophobic interactions. Kosmotropes increase hydrophobic interaction and therefore tend to increase dye adsorption, whilst chaotropes decrease both hydrophobic interaction and dye adsorption. Thus, in the example quoted above of CI Acid Red 1 on nylon, sodium chloride has a stronger effect on decreasing dye adsorption than the more kosmotropic sodium sulphate. On this basis, Yang has introduced a modified Donnan model that quantitatively predicts the various effects of electrolytes on either decreasing or increasing dye adsorption.

anions

cations

SO 4 2 > CH 3 COO > Cl > Br NO 3 SCN

H 2 PO

4

Li + > Na + > K + > Rb + Cs +

N

E

U

T

R

A

L

kosmotropes

(water

structure-makers)

chaotropes

(water

structure-breakers)

Figure 10.1 Lyotropic series: effectiveness of hydrophobic interactions [1]

R

CH 3 CH 3 + + N (CH 2 ) n _ N R CH
CH 3
CH 3
+
+
N
(CH 2 ) n
_
N
R
CH 3
X
CH
3 X

10.1

_

n = 3–12 R = n-propyl, n-butyl or benzyl

X = halide, e.g. bromide

Rather more complex compounds that are currently being researched are the bolaform electrolytes [2–4]. Bolaform electrolytes are organic compounds possessing two cationic or two anionic groups linked by a flexible hydrocarbon chain; the terminal groups may be aliphatic or aromatic (e.g. as in 10.1). Their interaction with sulphonated monoazo dyes in the presence of poly(vinylpyrrolidone) as substrate has been studied in detail. However, it remains to be seen what commercial developments take place with these interesting

ELECTROLYTES AND pH CONTROL

499

compounds. It seems likely that they would be used in complex formation rather than in the more traditional roles associated with electrolytes in textile processing. In whatever role electrolytes are used, their effects on the environment need to be considered, particularly when discharged to effluent. High salt loading is undesirable in waste water and sodium sulphate in particular causes corrosion of concrete pipes. It thus

makes sense to choose electrolytes carefully and to use the minimum amounts consistent with obtaining the desired effects. Automatic dosing is helpful in this respect. The use of shorter liquor ratios has been promoted on the grounds of economy (less water to heat and

less liquor to treat subsequently). However, it should not be overlooked that when dyeing in

a short liquor more rinsing baths are required to give the same residual concentration as at a

longer liquor ratio. Weible [5] has demonstrated this effect for the washing-off of reactive dyes from fabric having a retention capacity of 4 l/kg using 60 g/l of electrolyte. At a liquor ratio of 20:1, some 12 g/l and 2.4 g/l of electrolyte are found in the first and second rinses respectively. These rise to 30 g/l and 15 g/l when a liquor ratio of 8:1 is used. Equation 10.1 was used by Weible to calculate these concentrations.

C

cR

s FV

(g/l)

C

s = concentration in rinsing bath (g/l)

c

= concentration in treatment bath (g/l)

FV

= liquor ratio (l/kg)

R

= retention capacity of goods (l/kg)

(10.1)

More detailed information on attempts to reduce the impact of electrolytes on the environment is given under the individual dye classes discussed in Chapter 12. The great majority of coloration processes demand some control over the treatment pH, which varies from strongly alkaline in the case of vat, sulphur or reactive dyes, to strongly acidic for levelling acid dyes. The concept of pH is a familiar one; its theoretical derivation can be found in all standard physical chemistry textbooks and has been particularly well explained in relation to coloration processes [6,7] both in theory and in practice. We are concerned here essentially with the chemistry of the products used to control pH and their mode of action. It has been stated [7] that: ‘Unfortunately, pH control appears simple and easy to carry out. Add acid and the pH decreases; add base (alkali) and the pH increases. However, pH is the most difficult control feature in any industry’. The control of pH in textile coloration processes is ensured by three fundamentally different techniques:

(a)

the maintenance of a relatively high degree of acidity or alkalinity

(b)

the control of pH within fairly narrow tolerances mainly in the near-neutral region

(c)

the gradual shifting of the pH as a dyeing proceeds.

Approach (a) is normally the easiest to control, and is used in the application of levelling acid and 1:1 metal-complex dyes to wool or nylon, and of the reactive, sulphur or vat dyes to cellulosic fibres. The agents traditionally used are the stronger acids and alkalis such as sulphuric, hydrochloric and formic acids, sodium carbonate and sodium hydroxide. In

500 CLASSIFICATION OF DYEING AND PRINTING AUXILIARIES BY FUNCTION

certain operations, particularly fixation in steam (as in printing), steam-volatile acids are replaced with non-volatile products such as citric acid. Use of approach (a) can lead to the misconception already mentioned, that pH is easy to control, particularly as the dye– substrate systems involved are not normally sensitive to minor pH shifts. Nevertheless, strong acids and alkalis can react to produce quite drastic changes in pH; this can occur, for example, when alkali is carried over from wool scouring into initially acidic dyebaths. Wool and nylon absorb acid from dyebaths, thereby inducing a change in the dyebath pH, but wool will absorb significantly more acid than nylon [8] – a factor to be borne in mind when comparing results on these two fibres, especially in those systems using ‘half-milling’ acid dyes for which the controlling agent is generally the weaker acetic acid; such systems represent a compromise between approaches (a) and (b) and are moderately sensitive to change in pH. In this area, the organic formic and acetic acids are of interest. Formic, of course, is a stronger acid than acetic. Hence, acetic acid has been traditionally the preferred choice for the adjustment of slightly acidic media, down to about pH 4, whereas formic was the choice below this level. It has been demonstrated, however, that for general purposes formic acid is preferred to acetic acid, particularly on economical and environmental grounds [9]. Formic acid has an extremely low BOD, being biodegraded to carbon dioxide and water. In any case, being a much stronger acid, smaller amounts are needed, thus giving less load for disposal. For example, in order to obtain pH values of 4.5, 4.0 and 3.3, the amount of formic acid 85% needed is, respectively, about 62%, 50% and 12% of that of acetic acid 80%. Other advantages of formic acid are that it has a more powerful neutralising effect than acetic acid and it is less corrosive than mineral acids. Approach (b) needs greater awareness of the factors that not only determine pH but also help to stabilise it against interference. Most of the dye–fibre systems requiring approach (b) are operated in the near-neutral region (pH 4–9) and are much more sensitive to minor changes in pH. In addition, the pH of the water supply may vary, or drift during heating. Even the pH of pure water changes on heating, from 7.47 at 0 °C to 7.00 at 24 °C and 6.13 at 100 °C, but that of the process water used in dyehouses and printworks can change much more drastically, most commonly showing an increase. Changes in pH on heating may counteract the intended response of process liquors, especially in the central pH range associated with approach (b); even more critical can be the effect of any acids or alkalis carried over from previous processes. The dye–fibre systems of obvious interest for approach (b) are milling acid and 1:2 metal- complex dyes on wool or nylon, basic dyes on acrylic fibres and disperse dyes on various fibres. With wool and nylon there is often some overlap with approach (c) (section 12.2). Where control is not too critical, simple electrolytes of weak bases with strong acids (such as ammonium sulphate) or strong bases with weak acids (such as sodium acetate) are often used to produce slightly acidic or slightly alkaline media respectively. Ammonium acetate is also commonly used, producing a less acidic effect than ammonium sulphate. Occasionally acetic acid and sodium carbonate are used, necessitating careful control and monitoring. These simple expedients are not suitable for systems requiring more sensitive control, however, and use of single electrolytes such as ammonium sulphate or sodium acetate more properly belong to control systems based on approach (c). More precise control is achieved by the use of buffering systems. By the use of electrolyte pairs, these systems set the initial pH and exert a protective action that tends to resist changes arising from contaminants entering by way of the substrate or the water supply.

ELECTROLYTES AND pH CONTROL

501

Buffering systems are generally based on combinations of:

– a weak acid together with the salt of this acid formed from a strong base, or

– a weak base together with the salt of this base formed from a strong acid.

The most commonly used example of the first type is acetic acid/sodium acetate, which functions well over the pH range 3.8–5.8. Acetic acid with ammonium acetate is also used although it is less effective, especially in those boiling dyebaths from which ammonia can escape into the atmosphere, thus allowing the pH to fall. Such acetate buffers have the advantage of low cost. Somewhat more expensive are the phosphate buffers, of which the most commonly used is a mixture of sodium dihydrogen orthophosphate (NaH 2 PO 4 ) with disodium hydrogen orthophosphate (Na 2 HPO 4 ). Here, as with most polybasic acid systems, the distinction between the acid and its salt seems blurred at first sight. In fact, sodium

dihydrogen phosphate is the ‘acting acid’ and disodium hydrogen phosphate is its salt. The tribasic orthophosphoric acid and its three salts can be used to produce a series of buffers, each active within a particular pH range:

– orthophosphoric acid and the monosodium salt, main buffering region pH 2.5–3.5

– the mono- and di-sodium salts, main buffering region pH 6–8

– the di- and tri-sodium salts, main buffering region pH 10.5–11.

This can be seen from the titration curve for phosphoric acid [6] shown in Figure 10.2. In practice the mono- and di-sodium salt system is used most extensively, since this covers the pH range over which precise control is most often needed. These phosphate buffers are more resistant than the acetate systems to temperature-induced changes.

12

10

8

pH

6

4

2

Na 3 PO 4 Na 2 HPO 4 Main buffer region NaH 2 PO 4
Na 3 PO 4
Na 2 HPO 4
Main
buffer region
NaH 2 PO 4
pH 6.2–8.2
H
3 PO 4

Alkali added

Figure 10.2 Orthophosphate buffer system

The most common buffering system containing a weak base together with its salt formed with a strong acid is ammonia with ammonium sulphate. Some useful buffers are obtained from combinations of unrelated acids or bases with salts. The following combinations find occasional use in textile coloration processes, but the acetates and orthophosphates are most frequently used:

pH

502 CLASSIFICATION OF DYEING AND PRINTING AUXILIARIES BY FUNCTION

– pyrophosphoric acid (H 4 P 2 O 7 ) and its salts (pH 3–9)

– orthoboric acid (H 3 BO 3 ), sodium tetraborate (borax Na 2 B 4 O 7 ) and sodium hydroxide (pH 8.1–10.1)

– citric acid and sodium hydroxide (pH 2.1–6.4)

– sodium carbonate and sodium bicarbonate (pH 9.3–11.3).

The pyrophosphate buffer is of particular technical interest as it can be used over the relatively wide range of pH 3–9. Unlike the orthophosphate titration curve, that for the tetrabasic pyrophosphate system is almost straight [6]. This linearity (Figure 10.3) means that effective buffering action is available across the whole pH range simply by using various pairs of ionised components and varying their proportions; even so, however, it does not seem to be widely used.

9

7

5

3

Na 4 P 2 O 7 Strong acid added
Na 4 P 2 O 7
Strong acid added

Figure 10.3 Pyrophosphate buffer system

The mechanism of buffering can be described by reference to the acetic acid/sodium acetate system. In aqueous solution sodium acetate can be considered to be practically completely ionised (Scheme 10.1), the equilibrium being wholly to the right-hand side. Since acetic acid is a weak acid it is only slightly ionised, and the equilibrium represented by Scheme 10.2 lies mainly to the left-hand side. This low degree of ionisation is even further suppressed in the presence of sodium acetate as a result of the common ion (in this case acetate) effect operating through the law of mass action. The undissociated acetic acid is, in effect, a ‘bank’ of hydrogen and acetate ions that can be brought into play as a neutralising mechanism when either acidic or alkaline chemicals enter the system (either by deliberate addition or adventitiously). If a small amount of an acidic solute is added to the mixture, the added hydrogen ions combine with acetate ions to form undissociated acetic acid, which has only a minimal effect on the pH of the system. If an alkaline solute is added to the buffer, the added hydroxide ions react with the bank of hydrogen ions to form undissociated water and so again the ionic balance and hence the pH remain essentially the same. The mechanisms of other buffering systems are similar: buffering action is increased by adding more of the components, keeping their proportions constant.

 

CH 3 COONa

Scheme 10.1

 

CH 3 COOH

Scheme 10.2

ELECTROLYTES AND pH CONTROL

Na + CH 3 COO H + CH 3 COO
Na
+ CH 3 COO
H
+ CH 3 COO

503

Approach (c) for pH control involves a deliberate shift of pH during the processing cycle, in a consistent direction rather than randomly. Systems of this type are particularly useful for non-migrating anionic dyes on wool or nylon and have long been known in this connection. More recently, similar systems have been adopted for reactive dyes on cellulosic fibres. The simplest and most widely used of these systems consist of the salts of strong acids with weak bases or of strong bases with weak acids, examples being ammonium sulphate and sodium acetate respectively. Ammonium sulphate, for instance, dissociates in aqueous media to yield the dominant strong-acid species of sulphuric acid, so lowering the pH (Scheme 10.3) at a rate that increases with temperature, especially when the ammonia formed can be released from an open dyebath. Ammonium acetate functions in the same way but does not yield as great a pH shift. Similarly, a solution of sodium acetate tends to produce the dominant strong-alkali species of sodium hydroxide (Scheme 10.4), thus increasing the pH.

(NH 4 ) 2 SO 4 + 2H 2 O

Scheme 10.3

H 2 SO 4 + 2NH 4 OH 2H + SO 4 2–
H 2 SO 4 + 2NH 4 OH
2H
+ SO 4 2–

NH 4 OH

Scheme 10.4

CH 3 COONa + HOH

NaOH + CH 3 COOH Na + OH
NaOH + CH 3 COOH
Na
+
OH

NH 3

+

H 2 O

Acetic acid (b.p. 118 °C) is not boiled off from open dyebaths as readily as ammonia but is rapidly flashed off in steam or dry heat processes, thus developing the maximum degree of alkalinity under these conditions. The sodium salts of less volatile acids, such as sodium citrate, can be used to develop a lower degree of alkalinity. If the process demands a gradual shift from about pH 9 to a slightly acidic pH, ammonium sulphate together with ammonia can be used. This gives a safer, more uniform development of acidity than can be achieved by making additions of acid to an alkaline bath, although the degree of acidity developed will clearly depend on the ease with which ammonia can escape from the system. In enclosed or partially enclosed machines this system does not function so efficiently [10–12].

504 CLASSIFICATION OF DYEING AND PRINTING AUXILIARIES BY FUNCTION

Another method of obtaining a pH shift in the direction of acidity is to use an organic ester that hydrolyses to the alcohol and acid under the conditions of processing. Ethyl lactate (Scheme 10.5) and diethyl tartrate (10.2) have been recommended for applying milling and chrome dyes to wool [13]. 2-Hydroxyethyl chloroacetate (10.3) and γ-butyrolactone (10.4), which hydrolyses during processing to give 4-hydroxybutyric acid (Scheme 10.6), have also been recommended. Such hydrolysable esters may be used alone, beginning at a near-neutral pH, but more likely in conjunction with an alkali to give a higher starting pH. Thus γ-butyrolactone and sodium tetraborate (borax), giving a pH shift from about 8 to 5.6, have been recommended for the dyeing of wool [14], as has 2-hydroxyethyl chloroacetate with sodium hydroxide for the dyeing of nylon [15]. Such hydrolysable esters are sometimes sold under proprietary trade names. The disadvantages of hydrolysable esters have been their higher cost, a limited pH range and, where the dyebath is to be reused, the need for increasing quantities of ester to overcome the buffering effect caused by the accumulation of salts [7,16]. Interest in these systems has declined due to environmental pressures on the one hand and the increased availability and sophistication of automatic dosing and monitoring systems on the other.

H 3 C

CH
CH
O H H 3 C 2 O C CH
O
H
H 3 C
2 O
C
CH

O

C
C

HO

Scheme 10.5

 

HO

HO

Scheme 10.6

OCH 2 CH 3

 

HO

OH

+ HOCH 2 CH 3

O

C HC HC C
C
HC
HC
C
 

OCH 2 CH

3

OCH 2 CH

 

O

3

C
C

O

ClH 2 C

OCH 2 CH 2 OH

10.2

10.3

O

O CH 2 C CH 2 O CH 2
O
CH 2
C
CH 2
O
CH 2

10.4

H 2 O

C HO CH 2 HO CH 2 CH 2
C
HO
CH
2
HO
CH
2
CH 2

The advantages of automatic metering and monitoring devices were well described by Mosimann [17] and have recently been re-emphasised [9]. Such devices are clearly of great value in environmental terms since they are crucial in ensuring that the minimum quantity of agent is used, thus reducing the effluent load to a minimum. The use of strong acids and bases for control of pH-shift systems is obviously fraught with difficulties where the operation is carried out manually. If a sophisticated automatic monitoring and dosing system is used, however, the use of such compounds has certain very worthwhile advantages:

SEQUESTERING AGENTS

505

(a)

The adjusting chemicals are the cheapest available;

(b)

The entire range of pH values can be controlled by using just two chemicals;

(c)

Since a buffering system is not built up in the bath, the pH can be shifted in any direction to any degree, easily and with the minimum addition of chemicals;

(d)

As a result of (c), any variation in the intrinsic pH of the substrate or water supply can be easily neutralised;

(e)

Exhausted dyebaths can often be reused as there is no build-up of buffering agent; and

(f)

There are no environmental problems.

It should be noted that automatic dosing and monitoring of dyes and chemicals can be used generally and is not restricted to pH control.

10.2 SEQUESTERING AGENTS

The tendency of soaps and other carboxylates to form insoluble complexes with calcium and magnesium ions in hard water is mentioned in sections 9.4 and 9.8.2. Apart from decreasing the efficiency of the anionic surfactant, deposition of such insoluble complexes on the textile substrate can cause problems in subsequent processing and particularly in coloration. Even trace amounts of certain transition-metal or alkaline-earth elements may cause processing difficulties. The formation of ‘iron spots’, particularly in bleaching, is well known:

multivalent transition-metal cations catalyse the decomposition of hydrogen peroxide (although divalent calcium and magnesium ions have a stabilising effect) and localised staining or tendering of the fibre may occur. In coloration trace-metal ions can react with certain dyes, giving rise to precipitation, discoloration, unlevel dyeing and reduced fastness. The processing water is the most obvious source of such extraneous metal ions, but other potential sources should not be overlooked. For example, trace metals may be dissolved from the surfaces of machinery and fittings. The substrate may already contain such metals, as may also any chemicals or dyes used. Hence these problems cannot always be avoided simply by ensuring the supply of suitable water – indeed, the overzealous treatment of water can actually lead to the presence of troublesome aluminium ions that were not originally present! Such problems can be solved using chemicals that react preferentially with the metal ions, effectively preventing them from interfering with the mainstream reaction or process. Such chemicals are aptly known as sequestering agents. Other terms frequently used in the literature include the derivative ‘sequestrants’ and ‘complexing agents’, although complexing does cover a wider field than just metal–ion chelation with which we are concerned here. Sequestering agents work by a mechanism of complex formation, often in the form of chelation. A chelating agent contains substituents suitably located to form one or more chelate rings by electron donation to the metal ion (section 5.2), the resulting complex remaining soluble and innocuous under the conditions of processing. The most useful donating atoms are nitrogen, as found in amines or substituted amines, and oxygen in the form of carboxyl, phosphate or ionised hydroxy groups. As in the formation of dye–metal chelates (such as chrome mordant and metal-complex dyes), at least two electron-donating atoms in the sequestering agent structure must be arranged so that a stable ring can be formed with the metal ion, the highest stability resulting from five- and six-membered rings.

506 CLASSIFICATION OF DYEING AND PRINTING AUXILIARIES BY FUNCTION

A great many chemicals exhibit sequestering capability but not all are of commercial value in textile processing. Earlier literature [18,19] mentioned three main types:

– aminopolycarboxylates

– phosphates, mainly inorganic

– hydroxycarboxylates.

However, environmental awareness, in addition to commercial and technical exploitation, has resulted in considerable activity in this area, leading to a greatly expanded range of products in recent years, as well as some conflicting statements with regard to their environmental properties. The scheme of classification adopted here is as follows:

– aminopolycarboxylates and their analogues, e.g. hydroxyaminocarboxylates

– phosphates and phosphonates

– hydroxycarboxylates

– polyacrylic acids and derivatives.

10.2.1 Aminopolycarboxylates and their analogues

These are powerful chelating agents, having good environmental properties [20]. Important members include:

– ethylenediaminetetra-acetic acid

EDTA

(10.5)

– diethylenetriaminepenta-acetic acid

DTPA

(10.6)

– nitrilotriacetic acid

NTA

(10.7)

These products are sold as free acids or sodium salts. Analogues of these amino- polycarboxylic acids include the hydroxyaminocarboxylic acids. These structures are derived

Na

Na

Na

+

Na

+

O O _ C _ + O CH 2 H Na O 2 C N
O
O
_
C
_
+
O CH 2
H
Na
O
2 C
N
CH 2 CH 2
N
_
_ +
O
CH 2
C
H
Na
2 C
O
O
10.5 O

EDTA

+ O

_

+ O

_

O

O O _ C + Na O CH 2 C C CH 2 H C
O
O
_
C
+
Na
O
CH 2
C
C
CH 2
H
C
2
N
N
CH 2 CH 2
N
CH 2 CH 2
CH 2
H
C
2
C
C
10.6

O DTPA

O

_ +

O

Na

O

_ +

Na

O C + _ Na O CH 2 O N CH 2 C _ _
O
C
+ _
Na
O
CH 2
O
N
CH 2
C
_
_
+
Na
O
CH 2
O
Na
C
10.7
O

NTA

+

SEQUESTERING AGENTS

507

by replacing one or more carboxymethyl groups of the aminopolycarboxylate by a hydroxyethyl group. Examples include:

N-(hydroxyethyl)ethylenediaminetriacetic acid HEDTA (10.8) in which one of the carboxymethyl groups of EDTA has been replaced by a hydroxyethyl group N,N-bis(hydroxyethyl)glycine DEG (10.9) in which two of the carboxymethyl groups of NTA have been replaced by hydroxyethyl groups.

O O _ C C _ + Na O CH 2 H C O Na
O
O
_
C
C
_
+
Na
O
CH 2
H
C
O
Na
2
N
CH 2 CH
N
2
_
CH 2
H
HO
2 C
O Na
CH 2
C
10.8

HEDTA

O

+ HO

+

HO

CH 2 CH 2 N CH 2 CH 2
CH
2
CH 2
N
CH 2
CH
2
O CH 2 C _ + O Na 10.9
O
CH 2
C
_ +
O Na
10.9

DEG

These compounds are not persistent in the environment, NTA degrading slightly more quickly than EDTA, DTPA or HEDTA [20]. These aminopolycarboxylates act as sequestering agents by forming complexes in which each metal ion is chelated into one or more five-membered rings. It is often assumed that one molecule of sequestering agent interacts with one metal ion and for many practical purposes this is a valid assumption. The nature of the complexes actually formed, however, may depend on other factors such as the pH of the medium. It is difficult to represent such structures in detail, particularly as water of solvation is usually involved. It is convenient to adopt a simplified representation, omitting the water of solvation, as for the EDTA–calcium complex shown in structure 10.10, in which the arrows represent coordination bonds and the calcium ion is held by three five-membered rings. At pH values below 11 the structure tends to be more like that shown in 10.11, which also resembles the complex formed with NTA (10.12).

Na

_ _ O O O O C C Ca 2+ CH 2 O H 2
_
_
O
O
O O
C
C
Ca 2+
CH 2
O
H 2 C
O
N
N
C H 2 C
CH 2
C
_
CH
2 CH
2
_
+
+
O
O Na

10.10

508 CLASSIFICATION OF DYEING AND PRINTING AUXILIARIES BY FUNCTION

_

_

O

O

C C O O CH 2 H 2 C Ca 2+ N CH 2 CH
C
C
O
O
CH 2
H
2 C
Ca 2+
N
CH 2 CH 2
N
Ca 2+
CH 2
H
O
2 C
O
C
C
O
O

10.11

_

_

O

2 CH 2 N Ca 2+ CH 2 H O 2 C O C C O
 

C

O Ca 2+ O
O
Ca 2+
O

CH 2

N

CH 2

C

 

_

CH 2

O

C
C
 

_

_

 

O

 
CH 2 O C   _ _   O   O 10.12 + Na A more

O

10.12

+

Na

A more elaborate representation of an EDTA-metal complex (10.13), which gives some indication of the three-dimensional aspects of the structure, shows a complex of five five- membered rings [18]. A similar representation of a DTPA-metal complex shows a system of eight five-membered rings.

O

C O CH 2 O C CH 2 O N CH M 2 CH 2
C
O
CH
2
O
C
CH 2
O
N
CH
M
2
CH 2
O
N
CH 2
C
CH 2
O
O
C
10.13

O

10.2.2 Phosphates and phosphonates

Various polyphosphates are effective sequestering agents under appropriate conditions. The best known of these is sodium hexametaphosphate (10.14), the cyclic hexamer of sodium orthophosphate. Further examples are the cyclic trimer sodium trimetaphosphate (10.15), as well as the dimeric pyrophosphate (10.16), the trimeric tripolyphosphate (10.17) and other linear polyphosphates (10.18). All of these polyanions function by withdrawing the troublesome metal cation into an innocuous and water-soluble complex anion by a process of ion exchange as shown in Scheme 10.7 for sodium hexametaphosphate. Hence these compounds are sometimes referred to as ion-exchange agents. The disadvantage of the polyphosphates is that at the temperatures (100 °C or higher) used in many textile processes they can be hydrolysed into simpler phosphates that cannot retain the metal atom in the sequestered form. For example, dicalcium disodium hexametaphosphate hydrolyses on prolonged boiling to yield the insoluble calcium orthophosphate. This is one of the main reasons why polyphosphate sequestrants are used much less extensively than the more versatile and stable aminopolycarboxylates.

SEQUESTERING AGENTS

509

+

Na

_

Na

+ _

O

O

_ + O O Na O P O _ P O O P O Na
_ +
O O
Na
O
P
O
_
P
O
O
P
O Na
O
O
_
+
P
O
O
P
O
Na
O
P O
_
O O
Na
+ +
2

10.14

Sodium hexametaphosphate

_

O

_

O

_ + O O Na O P O P O O P O O P
_ +
O
O
Na
O
P
O
P
O
O
P
O
O
P
O
O
P
O
P
O
_
+
O
O
Na

O

_

O

_

O O P O O P O O P O P O _ + O O

Ca 2+

Ca 2+

Ca 2+

+

+

4 Na

_

Scheme 10.7

+

_

O

_ + O O Na P O O O P P O _ + O
_
+
O
O
Na
P
O
O
O
P
P
O
_
+
O
O Na

10.15

Sodium trimetaphosphate

_

Na

O O _ OPOPO _ + _ + O O Na
O O
_
OPOPO
_
+ _
+
O O
Na

Na

+

10.16

Sodium pyrophosphate

Na

+

Na +

Na

_

O

+

Na

O O O P O PO _ _ _ O O Na + O n
O
O
O
P
O
PO
_
_
_
O
O
Na
+ O
n

PO

Na

Na

+

Na

+

_

O

+

Na

O O O _ + P OPOPO Na _ _ _ + O O Na
O
O O
_ +
P
OPOPO
Na
_
_
_
+
O
O Na
+ O
Na

10.17

10.18

Sodium tripolyphosphate

Sodium polyphosphate

+

A structural compromise between these two types of compound can also give products

with sequestering properties, although they are phosphonates rather than phosphates, since they contain C–P rather than C–O–P linkages. Examples of these aminopolyphosphonates are:

– ethylenediaminetetramethylphosphonic acid EDTMP

(10.19)

– diethylenetriaminepentamethylphosphonic acid DETMP

(10.20)

– nitrilotrimethylphosphonic acid ATMP (10.21)

– hydroxyethylethylenediaminetrimethylphosphonic acid HEDTMP (10.22)

– hexamethylenediaminetetramethylphosphonic acid HMDTMP (10.23)

Two sequestrants of the phosphonate class unrelated to aminopolycarboxylic acids are:

1-hydroxyethane-l,1-diphosphonic acid

HEDP

(10.24)

2-phosphonobutane-1,2,4-tricarboxylic acid

PBTC

(10.25)

510 CLASSIFICATION OF DYEING AND PRINTING AUXILIARIES BY FUNCTION

HO

HO

HO

HO

O O P CH H 2 C P 2 HO OH N CH CH 2
O
O
P
CH
H 2 C
P
2
HO
OH
N
CH
CH 2
N
2
HO
OH
P
CH
P
H 2 C
2
O
10.19 O

EDTMP

O

CH 2 N 2 HO OH P CH P H 2 C 2 O 10.19 O

O HO

P CH 2 HO N HO P CH 2
P
CH
2
HO
N
HO
P
CH
2

O

HO

P CH 2 N
P
CH 2
N

O

P H 2 C OH N OH C P H 2
P
H 2 C
OH
N
OH
C
P
H 2

CH 2 CH 2

CH 2 CH 2

10.20 O

DETMP

OH

OH

O O HO P CH H 2 C P 2 HO OH N CH N
O
O
HO
P
CH
H 2 C
P
2
HO
OH
N
CH
N
2 CH 2
OH
HO
CH
P
H 2 C
2
CH 2
10.22 O

HEDTMP

OH

OH

OH

OH

HO

HO

O

P CH 2 O HO N CH 2 P HO OH P CH 2 O
P
CH
2
O
HO
N
CH 2
P
HO
OH
P
CH
2
O
10.21

ATMP

O O HO P CH H 2 C P OH 2 HO OH N CH
O
O
HO
P
CH
H 2 C
P
OH
2
HO
OH
N
CH 2 CH 2 CH 2 CH 2 CH 2 CH 2
N
HO
OH
HO
P
CH 2
P
OH
H 2 C
10.23
O
O
HMDTMP
OH
O
C
O
O
CH 3
O
O
C
CH 2 CH 2
C
P
HO
P
C
P
OH
HO
O
CH 2
OH
HO
OH
OH
C

10.24

HEDP

10.25 OH

PBTC

OH

OH

SEQUESTERING AGENTS

511

The consumption of these phosphonates in textile processing is small in relation to that of the aminopolycarboxylates; they are mainly used in detergent formulations [21,22] as sodium, potassium, ammonium or alkanolamine salts. Environmentally, phosphates generally have been a sensitive issue, not least because they can cause eutrophication of watercourses, and the situation is still not resolved completely. No aerobic or anaerobic bacterium has been found to date that will biodegrade aminopolyphosphonates under the treatment conditions used today, yet these products are not biologically persistent. They are partially eliminated photolytically, partially absorbed in sediment or eliminated by precipitation [23,24]. They show 50–80% elimination in the Zahn–Wellens test. They show low aquatic toxicity and are non-toxic to humans, animals and plants. Detailed ecological properties are listed by Schöberl and Huber [25]. Held [26] has investigated the ecological behaviour of sequestering agents based on phosphonic acids in detail, concluding that although they contain phosphorus they do show ecological advantages compared with other types and thus their use is justified.

10.2.3 Hydroxycarboxylates

The hydroxycarboxylic acids provide a range of sequestering agents of which the best known are citric (10.26), tartaric (10.27) and gluconic (10.28) acids. The toxic oxalic acid (10.29) is now rarely used. However, these acids are much less important as sequestering agents for textile processes than either the aminopolycarboxylates or the polyphosphates. Hydroxycarboxylates are easily biodegraded but do have a high COD. It has been pointed out [20] that glucoheptanoic acid (2,3,4,5,6,7-hexahydroxyheptanoic acid; 10.30) is also used in the USA, on the grounds that this compound is less prone to browning at high temperatures although it possesses no other advantages, having less binding power as well as being more expensive than other hydroxycarboxylic acids.

H OH H O O H OH O O C C C C C C
H
OH
H
O
O
H
OH
O
O
C
C
C
C
C
C
C
C
C
HO
OH
10.26
H
C
H
10.27
Citric acid
HO
OH
O
H
OH H
Tartaric acid
O
O
H
H
OH
H
OH
O
C
C
HO
C
C
C
C
C
C
HO
OH
10.28
OH
H
OH
H
OH
H
Gluconic acid
10.29
Oxalic acid
H
H
OH
H OH
H O
HO
C
C
C
C
C
C
C
OH
H
OH
H
OH
H
OH
10.30

512 CLASSIFICATION OF DYEING AND PRINTING AUXILIARIES BY FUNCTION

10.2.4 Polyacrylic acids and their derivatives

Recent research has led to some more complex sequestering agents, particularly the polymeric carboxylic acids referred to as polycarboxylates. These are, in effect, polyelectrolytes and as such have close similarities to the products described later as dispersing and solubilising agents (section 10.6), thickening agents or migration inhibitors (section 10.8). Common monomers used in the production of these compounds, either as homopolymers or as copolymers with each other, include acrylamide (10.31) and various unsaturated acids (10.32–10.34). The common and essential feature of these monomers is the carbon–carbon double bond.

H 2 C

H

C
C

CONH 2

10.31

Acrylamide

H 2 C

H

C
C

COOH

10.32

Acrylic acid

CH 3 H 2 C C COOH 10.33
CH 3
H 2 C
C
COOH
10.33

Methacrylic acid

H H C C HOOC COOH
H
H
C
C
HOOC
COOH

10.34

Maleic acid

Polymers which have been suggested for use as sequestering agents [23,27] include:

– poly(butadiene-1,2-dicarboxylic acid) which is an ethylene–maleic acid copolymer

EMA

(10.35)

– poly(α-hydroxyacrylic acid)

PHAS

(10.36)

– poly(3-hydroxymethylhexatriene-1,3,5-tricarboxylic acid) which is a copolymer of acrylic acid with hydroxymethacrylic acid

(10.37)

– poly(3-formylhexatriene-1,3,5-tricarboxylic acid) which is a copolymer of acrylic acid with 2-formylacrylic acid.

(10.38)

CH 2 CH 2 CH CH HOOC COOH 10.35
CH 2
CH 2
CH
CH
HOOC
COOH
10.35
OH CH 2 C COOH n n 10.36
OH
CH 2
C
COOH
n
n
10.36
EMA CH 2 OH CH 2 CH CH 2 C CH 2 CH COOH COOH
EMA
CH 2 OH
CH 2
CH
CH 2
C
CH 2
CH
COOH
COOH
COOH

n

PHAS

10.37

CHO CH 2 CH CH 2 C CH 2 CH COOH COOH COOH
CHO
CH 2
CH
CH 2
C
CH 2
CH
COOH
COOH
COOH

n

10.38