Synthesis of novel polymeric colorants

Coloration
Max A Weaver,* Gerry Rhodes and Michael J Cyr Technology
Eastman Chemical Co., Kingsport, Tennessee, USA
Email: mweaver@[Link]
Received: 9 December 2002; Accepted: 20 December 2002

There are several structural types of polymeric dyes (polydyes) that have been synthesised as
colorants for thermoplastic materials, particularly polyesters. This paper reviews three synthetic
methods used to prepare polydyes. In method 1, anthraquinone polysulphonamide polydyes were
Society of Dyers and Colourists
prepared by reacting anthraquinonedisulphonyl chlorides with diamines in the presence of a base.
Polymethine polydyes were prepared in method 2 by reacting bis-aldehydes containing two linked
aromatic aldehyde moieties with a bis-(active methylene) component under Knoevenagel reaction
conditions. In the final method, a variety of polymer types were synthesised by reacting acidic dyes
containing two acidic groups with glycol sulphonates in the presence of a base. Most of the polydyes
were evaluated as colorants for polyesters, by melt blending and extruding, followed by the
preparation of films for further testing of properties such as fastness to light. The primary emphasis of
this paper is to discuss the synthetic methods involved and to present the various types of structure
that have been investigated.

Introduction were evaluated as colorants for polyesters by melt blending

and extruding [7–9]. Films were also prepared to test
The advantages and properties of polymeric colorants have
properties such as fastness to light.
been discussed in considerable detail [1–6]. Polymeric
colorants can be divided into four classes: (i) polymers
Dye analysis
where a non-coloured polymer backbone contains pendant
The polydyes were characterised using ultraviolet–visible
chromophores; (ii) polymers that contain chromophores as
(UV–vis) spectroscopy, 1H nuclear magnetic resonance
part of the polymer backbone; (iii) polymers in which at least
spectroscopy and field desorption mass spectroscopy. The
one non-coloured polymer chain is attached to a chromo-
UV–vis spectra were run in N,N-dimethylformamide (DMF)
phore as an end group; and (iv) polymers wherein each
as the solvent using a Lambda 9 UV/VIS/IR Perkin-Elmer
repeating unit contains a chromophoric moiety. The work
spectrophotometer. The number average molecular weights
described here relates to polymeric colorants that fall into
(Mn) and weight average molecular weights (M w) were
the last class. The term ‘polydye’ will be used in this paper
determined by gel-permeation chromatography (GPC).
to distinguish this class, at least partially, from the other
three classes. Considerable variation in properties is ob-
Gel-permeation chromatography
served from dye to dye and from class to class; however, in
Analysis in N-methyl-2-pyrrolidone: GPC analyses of
general it is true that polymeric colorants usually have
polydye samples in N-methyl-2-pyrrolidone (NMP) were
advantages over dyes in that they do not readily migrate,
performed at 40 °C and a flow rate of 0.8 ml/min, with a
sublime or bleed and are less easily extracted. They also
column set consisting of one Polymer Laboratories 10 µm
have reduced toxicity compared to their monomeric ana-
PLgel Guard column and one 30 cm Mixed B column. The
logues. They differ from pigments in that they have solubility
system was configured with a Perkin-Elmer (PE) LC250
in thermoplastics and are less abrasive in processing.
pump, a PE LC600 autosampler, a Waters column oven and
Polydyes obviously have the highest achievable colour
a Waters 410 refractive index detector. Sample solutions
strength obtainable with polymeric colorants since each
were prepared by dissolution of 25 mg of the polydye in
repeating unit is a coloured moiety. The polydyes described
10 ml NMP, with 10 µl toluene added as a flow rate marker.
in this paper are characterised by having relatively low
The injection volume was 20 µl. Detection was by
molecular weights and usually have oligomers present when
differential refractive index. The molecular weight
prepared by the available synthetic methods. In contrast to
distribution and averages were calculated as equivalent
some of the other types of polymeric colorant, they can be
polystyrene molecular weights, based on a calibration curve
synthesised by solution polymerisation in batch processes.
obtained with a set of monodisperse polystyrene samples
Three methods for the synthesis of polydyes are reviewed
over a molecular weight range from 580 to 4000 000.
in this paper.

Analysis in dichloromethane–hexafluoroisopropanol: GPC

analyses of polydye samples were performed in an elution
mixture of dichloromethane–hexafluoroisopropanol (HFIP)
Experimental (95:5 by volume) at ambient temperature (25 °C) and a flow
Dye preparation rate of 1 ml/min. The system was configured with a PE Series
The dye syntheses described in this paper have all been 200 pump, a PE ISS 200 autosampler and an Applied Bio-
published previously. Most of the polydyes thus prepared systems 785A UV-absorbance detector. Tetraethylammonium

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 bromide (0.5 wt%) was added to the solvent for suppression dicarboxylic acid chlorides, bis-haloformates and bis-
of non-size exclusion effects. The column set consisted of sulphonyl halides [10]. However, a significant shift in
one Polymer Laboratories 5 µm PLgel Guard column, one 30 colour from that of the diaminoanthraquinone monomer to
cm 1000 Å column and one 30 cm 100 Å column. Sample the polysulphonamide polydyes occurs which makes shade
solutions were prepared by dissolution of 10 mg of the control difficult. In contrast, little shift in colour from that
polydye in 10 ml of a 70:30 methylene chloride–HFIP of the anthraquinonedisulphonyl chlorides to that of the
mixture with 1.5 ml/l of toluene added as a flow rate marker. anthraquinone polysulphonamide polydyes [11], described
The injection volume was 10 µl. Detection was by UV herein, is observed. The general synthesis of anthraquinone
absorbance at a wavelength (λmax) of 255 nm. The calibration polysulphonamides is shown in Scheme 1.
curve for calculation of the molecular weight distribution The coloured intermediate anthraquinonedisulphonyl
and averages was obtained by identification of the indi- chlorides 1 were reacted at ca. 95–100 °C with a diamine
vidually resolved polydye oligomer peaks by mass spec- in a solvent in the presence of a base to give the general
trometry, and extrapolation to higher molecular weights by products 2 [11,12]. Typical red 4, blue 6 and yellow 8
comparison with the curve obtained with monodisperse polysulphonamide polydyes were prepared by the methods
polystyrene standards. shown in Scheme 2–4, respectively. Typical diamines used
All of the GPC results shown were obtained using the were 2,2-dimethyl-1,3-propanediamine 9, 1,6-hexamethyl-
NMP method except for those in Table 2, which were enediamine 10, 1,4-bis(aminomethyl)cyclohexane 11, 1,4-
obtained by the dichloromethane–HFIP method. phenylenediamine 12, piperazine 13 and N,N′ -dimethyl-
hexamethylenediamine 14. The reaction can be run in a
variety of polar aprotic solvents such as DMF. Trialkyl
Results and Discussion amines such as tri-n-butylamine serve to facilitate the
Polydyes prepared by method 1 reactions and to neutralise the hydrochloric acid formed.
Polydyes can be prepared by reacting diaminoanthra- Table 1 summarises some of the properties of the polydyes
quinones with non-coloured diacid halides such as such as molecular weight and visible absorption maxima.

Base
ClO2S AQ SO2Cl + HN(R2) R1 (R2)NH O2S AQ SO2N(R2)R1(R2)N
Solvent
n
1 2

AQ = Coloured anthraquinone divalent moiety

R1 = Alkylene, arylene, etc.
R2 = H, alkyl, etc.
Scheme 1

OCH3 OCH3

O HN O HN

SO2Cl SO2N(R2)R1(R2)N
ClO2S SO2
HN(R2)R1(R2)NH
NH O NH O

OCH3 OCH3
n

3 4
Scheme 2

C2H5

HN SO2Cl
O
C2H5 C2H5
C2H5 2 1 2
HN(R )R (R )NH
O2S HN NH SO2N(R2)R1(R2)N
C2H5

O C2H5 O O C2H5
HN SO2Cl

C2H5
n
5 6

Scheme 3

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 O S CH3 O S CH3

SO2Cl SO2N(R2)R1(R2)N

HN(R2)R1(R2)NH
H3C S O H3C S O

SO2Cl SO2
n

7 8
Scheme 4

NH2CH2CH(CH3)2CH2NH2 R NHCH2CH2CH2CH2CH2CH2NH R
9 10 R=H
14 R = CH3

H2NH2C CH2NH2 H2N NH2 HN NH

11 12 13

Table 1 Key properties of the anthraquinone polysulphonamide polydyes

synthesised from the anthraquinones 4, 6 and 8 and diamines 9–14 using method
1 [11]

Anthraquinone Diamine M w (g/mol) Mn (g/mol) Mw/Mna λ maxb (nm)

4 9 9163 6946 1.32 530

10 8111 5236 1.55
11 10 289 3936 2.62
12 2200 1848 1.19
13 10 716 4678 2.29
6 9 6930 5145 1.35 579, 624
10 4976 1081 4.6
13 19 858 10 946 1.81
14 2828 1329 2.12
8 9 3771 2471 1.53 445

a Mw/Mn = polydispersity index

b Solvent = DMF

Polydyes prepared by method 2 solvents such as DMF in the presence of bases normally
Terephthaldehyde can be condensed with bis-(active used to facilitate Knoevenagel-type reactions. The reaction
methylenes) such as 1,4-benzenediacetonitrile [13] and 4,4′ - mixtures were usually heated and stirred for about 2 h at
dicyanomethyl diphenyl ether [14] to produce methine 95–100 °C and the solid products were isolated by drown-
polydyes. These dyes have low tinctorial strength and ing into alcohols and collecting by filtration. It has been
relatively poor solubility in thermoplastics. In this synthetic reported that certain bis-aldehydes and bis-(active methyl-
method, bis-aldehydes containing two aromatic aldehyde enes) can react to give cyclic macromolecules [26].
moieties joined by a linking group were reacted with bis-
(active methylenes) to yield the polydyes (Scheme 5) [15], Polydyes prepared by method 3
which exhibited good solubility in thermoplastics [8]. In this very versatile synthetic method, diacidic dyes (H–A–
This type of polydye has also been reported to have H) were reacted with glycol disulphonates (X–B–X) to give
useful second-order nonlinear optical properties and to be polydyes [9], with the general reaction shown in Scheme 8.
useful for the modulation and switching of optical The diacidic dye contains two acidic functional groups
communication signals [16]. Suitable bis-aldehydes have having pKa values of ca. 1.5–12.0. The disulphonate of a
been described previously [17–24]. A typical bis-(active glycol (such as 1,2-ethanediol dimethanesulphonate) is
methylene) is ethylene bis-cyanoacetate prepared by re- represented by X–B–X, where B is ethylene and X is a
action of cyanoacetic acid with ethylene glycol [25]. The methyl sulphone group.
preparation of two typical yellow methine polydyes 15 and A wide variety of difunctional chromophore groups may
16 is shown in Schemes 6 and 7, respectively. be represented by A, with azo and anthraquinone groups
The polymerisation reactions were carried out in aprotic being preferred. Some of the useful acidic functional groups

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 L1 L2 L1 L2
H2A AH2 + OHC B B CHO A A B B
Base n
Bis-(active methylene) Bis-aldehyde Methine polydye

A = Organic active methylene group residue

B = Divalent electron-rich organic moiety
L1, L2 = Organic linking groups
Scheme 5

CH3 CH3 CN O
NCCH2CO2CH2CH2O2CCH2CN
OHC N CHO HC N O
O
O CN
n
15
[Mw/Mn = 1.16; λmax (DMF) = 446 nm]

Scheme 6

CHO

O O
N CH3
OHC C2H5

O
H3C N
C2H5 O

O CN
NCCH2CO2CH2CH2O2CCH2CN O
O
O O CN O
N CH3
C2H5

O
H3C N
C2H5 O
16 n
[Mw/Mn = 1.33; λmax (DMF) = 434 nm]
Scheme 7

A B Base over method 1, which uses dyes containing sulphonyl

H H + X X A B
–2HX n
chloride groups, and the known preparation of polydyes by
Diacidic dye Glycol disulphonate Polydye
reacting dyes containing two hydroxy or amino groups with
diacid chlorides [10,27–30], since the preparation, hand-
Scheme 8 ling and storage of diacid chlorides present problems with
corrosion and hydrolysis. Several intermediate anthra-
which may be attached to, or be a part of A, are carboxylic quinone dyes that contain two carboxy groups [9,31] or two
acid groups, aromatic hydroxy groups, CONHCO, SO2NHCO, acidic 1(H)-1,2,4-triazol-3-ylthio groups [9,32,33] are
SO2NHSO2, 1(H)-1,2,4-triazol-3-yl, imidazolyl, benzimida- known, as well as azo dyes containing two carboxy [9] or
zolyl, pyrazolyl, NHSO2-alkyl and sulphamoyl (SO2NH2). two 1(H)-1,2,4-triazol-3-ylthio groups [9,34]. Preparations
When the diacidic sulphamoyl group is present, only one of typical yellow 17, red 18 and blue 19 anthraquinone poly-
group is required to give the polydye. Suitable bases are ester polydyes are shown in Schemes 9–11, respectively.
alkali metal carbonates, tertiary amines and bicyclic The early work involved the use of 1,2-ethanediol
nitrogen containing bases such as 1,8-diazabicyclo- dimethanesulphonate (dimesylate of ethylene glycol) as the
[5,4,0]undec-7-ene (DBU). Particularly useful solvents are electrophilic reactant. However, dimesylates of other diols
polar aprotic solvents such as DMF, N,N-dimethylacetamide such as 1,3-propanediol, 1,4-butanediol, diethyleneglycol,
and NMP. Reaction times were usually ca. 2 h at 100–125 1,6-hexanediol, 1,4-cyclohexanedimethanol and 1,12-
°C. The polydyes were normally isolated by drowning the dodecanediol were used with very interesting results. The
reaction mixtures into an alcohol or mixture of water and structure of the electrophilic reactant (X–B–X) greatly
alcohol, followed by collection by filtration and washing influences the structure of the polydyes produced. It was
with water. Obviously, this method has some advantages found that the reaction of some diacid dyes with some

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 electrophilic reactants, particularly the dimesylate of 1,6- polydyes prepared by reacting 1,5-bis-(2-carboxyphenyl-
hexanediol, gave significant quantities of macrocyclic thio)anthraquinone with the dimesylates of several
compounds such as monomers, dimers, trimers, tetramers, different glycols were also studied and some key structures
etc., as well as the desired linear polydye. The yellow are shown in Table 2.

OH O CH2CH2
O O

O S O S

CH3SO2OCH2CH2OSO2CH3
S O S O
Base
O O
HO O
n
17
Scheme 9 [Mw/Mn = 2.03; λmax (DMF) = 450 nm]

O OH O O CH2CH2
OH O O O

S O S S O S
CH3SO2OCH2CH2OSO2CH3
Base

H3C S O S CH3 H3C S O S CH3

n
18
Scheme 10 [Mw/Mn = 1.94; λmax (DMF) = 529 nm]

HO OH O O CH2CH2
NH2 O NH2 NH2 O NH2
O O O O
CH3SO2OCH2CH2OSO2CH3
S S S S
Base

OH O OH OH O OH
n
19
[Mw/Mn = 2.52; λmax (DMF) = 629 nm]
Scheme 11

Table 2 Stuctures of some yellow anthraquinone polyester polydyes

B [A–B]1 a (wt%) [A–B]2 b (wt%) [A–B]3 c (wt%) [A–B]4 d (wt%) Linear (wt%)

(CH2)2 0.1 3.4 1.5 0.7 94.3

(CH2)3 0.8 3.3 1.3 < 0.7 94.5
(CH2)4 6.9 4.1 1.3 0.2 87.5
CH2CH2OCH2CH2 9.5 3.1 0.8 < 0.1 86.5
(CH2)6 26.7 4.0 1.1 0.2 68.0

H 2C CH2 20.4 4.0 0.7 < 0.1 74.8

(CH2)12 20.1 2.2 0.5 < 0.1 77.1

a Cyclic monomer
b Cyclic dimer
c Cyclic trimer
d Cyclic tetramer

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 O
HO
H
N CH3 O OCH2CH2
N CN
CH3SO2OCH2CH2OSO2CH3 O O
HO
O Base
O O
N N
N
CH2CH2OH
H 3C OH

NCH2CH2OH
CN
O
n
20
[Mw/Mn = 2.50; λmax (DMF) = 422 nm]
Scheme 12

N CH2 CO2H
2 R N
Diazotisation H3COCHN
R NH2 R N2 X N N CH2 CO2H
2
H3COCHN
R = aryl or heteroaryl

X B X

O2C CH2 N CH2 CO2 B

H3COCHN
N
N
R
n
21
C 6H 5
Cl NO2 NC NC NO2 NC CH3
N N
21a R = 21b R = 21c R = 21d R = 21e R =
SC2H5 N
S C 6H 5 S
CN

Scheme 13

Table 3 Key properties of the red–magenta polyester azo remaining amount of the polydye is linear. The trend
polydyes 21a–e
shown here may or may not be true when diacidic dyes,
which have different spatial configurations for the two acid
Mw Mn λmaxa groups, are used, but this has not been investigated further.
B Dye (g/mol) (g/mol) Mw/M n (nm)
Azo dyes have historically been the most studied class
of dyes because of their wide shade gamut, high tinctorial
CH2CH2 21a 5413 2197 2.46 517
(CH2)6 21b 4761 2139 2.23 521
strengths and good economics. In this work, several azo
CH2CH2 21c >7176 3553 2.02 525 dyes containing two carboxy groups were prepared and
(CH2)6 21d 4229 1827 2.31 543 converted to polydyes by reaction with the dimesylates of
(CH2)6 21e 2090 1235 1.64 545 glycols. The carboxy groups may be on the diazo component
or the coupler portion of the azo dye. The synthesis of a
a Solvent = DMF typical yellow polyester azo polydye 20 is shown in Scheme
12, with the two precursor carboxy groups on the diazo
The least amount of macrocyclic compound is obtained component [9].
using the dimesylates of 1,2-ethanediol (B = CH2CH2) and Scheme 13 shows the preparation of selected red–
1,3-propanediol (B = CH2CH2CH2). The largest amount of magenta azo polydyes 21 from a coupler containing two
cyclic material was formed when the dimesylate of 1,6- carboxy groups [9]. Table 3 shows the properties of some
hexanediol [B = (CH2)6] was used. It is assumed that the of the red–magenta polydyes prepared according to Scheme

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 13. The dyes have different λ max values, from 517–545 nm, Intermediate 2,6-dibromophenylazo dyes were prepared
and are arranged in order of increasing bathochromism. by diazotising the corresponding 2,6-dibromoanilines and
Dyes containing two acidic 1(H)-1,2,4-triazol-3-ylthio coupling the resulting diazonium salts with the desired
groups serve as valuable intermediates for polydyes prepared couplers. Nucleophilic displacement of the bromine atoms
by method 3 [9]. Schemes 14–16 illustrate the preparation was accomplished by treating the 2,6-dibromophenylazo
of yellow 22, red 23 and cyan 24 anthraquinone polydyes dyes with 3-mercapto-1(H)-1,2,4-triazole in the presence
from 1,5-bis[1(H)-1,2,4-triazol-3-ylthio]anthraquinone [32], of a base such as an alkali metal carbonate in polar aprotic
1-amino-2,4-bis[1(H)-1,2,4-triazol-3-ylthio]anthraquinone solvents such as DMF [34]. The polydyes were prepared
[32] and 1,4-bis[2,6-diethylanilino]-6,7-bis[1(H)-1,2,4- by the reaction of the intermediate bis-[1(H)-1,2,4-triazol-
triazol-3-ylthio]anthraquinone [33], respectively. 3-ylthio] dyes with glycol dimethanesulphonates in the
The versatility of the 1(H)-1,2,4-triazol-3-ylthio group in presence of base in a polar aprotic solvent [9]. Some key
polydye synthesis is further illustrated by the preparation properties of the polydyes prepared via Scheme 17 are
of azo polydyes 25, as shown in Scheme 17. shown in Table 4, with colours ranging from red to blue.

N NH N N CH2CH2
O S O S
N N
CH3SO2OCH2CH2OSO2CH3
Base
N N
S O S O
HN N N N
n
22
[Mw/Mn = 2.12; λmax (DMF) = 420 nm]

Scheme 14

N
O NH2 N S
N NH
N N N (CH2)6
S
N H2N S
CH3SO2O(CH2)6OSO2CH3 N
N NH Base O O
O S
N

n
23
[Mw/Mn = 3.65; λmax (DMF) = 527 nm]
Scheme 15

C2H5
N N N N CH2CH2
HN N HN S S
O N N
N S
C2H5 CH3SO2OCH2CH2OSO2CH3
C2H5 Base
N S C2H5 O O C2H5
O
HN N HN
NH NH

C2H5
C2H5 C2H5
n
24
[Mw/Mn = 3.04; λmax (DMF) = 600, 645 nm]

Scheme 16

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 R2 R3 N NH R2 R3
N N NH N
Br R4 S N R4
HS
N N N
N N
Base
NHCOCH3 NHCOCH3
R1 Br R1 S

N N
HN

CH3SO2OCH2CH2OSO2CH3 Base

CH2CH2
N N R2 R3
N
S N R4
N
N
NHCOCH3
R1 S

N N
N
n
25
Scheme 17

Table 4 Key properties of polydyes synthesised from bis[1-(H)-1,2,4-triazol-3-ylthio] azo dyes 25

R1 R2 R3 R4 Mw (g/mol) Mn (g/mol) Mw/M n λ maxa (nm)

SO2CH3 CH3 H CH(CH3)C2H5 4175 2562 1.63 522

SO2CH3 H C2H5 C2H5 2301 1346 1.71 524
NO2 H C2H5 (CH2CH2O)2C2H5 6400 3700 1.73 556
NO2 OCH3 H C6H11 11 645 3123 3.73 577
NO2 OCH3 C4H9 C4H9 8976 3567 2.52 586

a Solvent = DMF

Conclusions 3. J T Guthrie, in Encyclopedia of Polymer Science and

Engineering, Vol. 5 (New York: John Wiley & Sons, 1986)
Polymeric colorants wherein each repeating unit is a 277.
chromophoric moiety have been prepared by three differ- 4. J S Gow and J Griffiths, J.S.D.C., 104 (1988) 405, 416.
5. J Miley, Pure Appl. Chem., 68 (1996) 1423.
ent convenient methods. Coloured anthraquinonedisul-
6. J T Guthrie, Rev. Prog. Color., 20 (1990) 40.
phonyl chlorides have been reacted with diamines to give 7. M A Weaver, W P Pruett, S D Hilbert and K H Shackerford,
polysulphonamide polydyes. Bis-aldehydes containing two US6121351 (Eastman Chemical Co.; 1998).
electron-rich aromatic aldehyde moieties linked together 8. M A Weaver, J J Krutak, C A Coates, W P Pruett and S D
Hilbert, US5376650 (Eastman Chemical Co.; 1994).
have been reacted with bis(active methylene) compounds
9. M A Weaver, J J Krutak, Sr, B E Maxwell, G F Rhodes, S D
to produce polymethine polydyes. It has been shown that Hilbert, J C Fleischer and W W Parham, US6197223 (Eastman
reaction of dyes containing two acidic groups with glycol Chemical Co.; 1998).
dimethanesulphonates is a very versatile method for 10. N Blake and H W Hill, Jr, US2994693 (DuPont; 1961).
11. M A Weaver, J J Krutak, Sr, C A Coates, Jr, G F Rhodes and
preparing polydyes. Unlike pigments, the polydyes are
B E Maxwell, US6140517 (Eastman Chemical Co.; 1998).
soluble in thermoplastics yet provide advantages over 12. M A Weaver, W W Parham, J J Krutak and K S Chamberlin,
solvent dyes in that they do not readily migrate, sublime US5453482 (Eastman Chemical Co.; 1995).
or bleed and are less easily extracted. The polydyes may 13. W Funke and K Hamann, DE1088637 (1960).
14. W K Carrington and H A Smith, GB1130265 (Dow Chemical
be prepared in excellent yields in batch processing
Co.; 1968).
equipment and have high colour strength. 15. M A Weaver, J J Krutak, C A Coates, W P Pruett and S D
Hilbert, US5532332 (1996).
16. J D Stenger-Smith, R Henry, J Hoover, G Lindsay, J Fischer
and K J Wynne, US5247055 (1993).
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 19. M A Weaver, J I Dale and J M Straley, US3553245 (Eastman 28. M A Elmasry, US4619990 (Minnesota Mining & Mfg; 1986).
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