Synthesis and dyeing performance of a novel polycarboxylic acid azo dye

Article abstract of DOI:10.1016/j.cclet.2010.11.010

A novel reactive polycarboxylic acid dye was synthesized by the reaction of polymaleic anhydride (PMA) with 3-methyl-1-(4-sulfonylphenyl)-4-(4- aminophenylazo)-2-pyrazoline-5-one. The structure of the novel dye was characterized by FTIR, UV-vis and ¹

Full text of DOI:10.1016/j.cclet.2010.11.010

Available online at www.sciencedirect.com
Chinese Chemical Letters 22 (2011) 424–426
www.elsevier.com/locate/cclet
Synthesis and dyeing performance of a novel
polycarboxylic acid azo dye
*
Hua Xu, Bing Tao Tang, Shu Fen Zhang
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, China
Received 23 August 2010
Available online 17 January 2011
Abstract
A novel reactive polycarboxylic acid dye was synthesized by the reaction of polymaleic anhydride (PMA) with 3-methyl-1-(4-
sulfonylphenyl)-4-(4-aminophenylazo)-2-pyrazoline-5-one. The structure of the novel dye was characterized by FTIR, UV–vis and
13C NMR spectra. The dyeing properties of dye on cotton were tested, and the novel dye possessed high fixation and good fastness.
# 2010 Shu Fen Zhang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
Keywords: Reactive polycarboxylic acid dye; Polymaleic anhydride; Dyeing
It is well-known that reactive dyes are widely applied in printing inks [1–3] and dyeing of natural fabrics [4–8]. The
research on this class of dyes has well been developed in the last fifty years. Aimed to further improve the fixation of
reactive dyes, research has focused both on the use of alternative reactive groups and combinations of different reactive
groups. Bi-functional reactive dyes have attracted considerable interest and have played an important role in the dye
and dyeing chemistry [4,6,9]. The fixation of bi-functional reactive dyes can reach 80–90% [9–11]. Carboxylic acid
groups were considered as substitute for conventional reactive groups, because carboxylic acid groups have the
potential to react with the hydroxyl groups of cotton and the amino groups of wool, and reactive dyes containing
carboxylic acid groups were developed by Oliveira and they were applied successfully to wool fibres [12,13]. Herein
we reported synthesis of a new type reactive polycarboxylic acid dye, which was obtained by the reaction of
polymaleic anhydride with azo chromophore. Because many reactive groups (carboxylic acid group) and
chromophores are in one polymeric dye molecule, even only one reactive group reacted with fibre, many
chromophores in the polymeric dye molecule can be linked to fibre by covalent bonding. The novel reactive
polycarboxylic acid dye was applied to cotton, and the results showed that this novel polycarboxylic acid dye had good
application prospects, because of their easy preparation method, high fixation and good fastness.
The synthetic route for polycarboxylic acid dye 5 was shown in Scheme 1. PMA was synthesized by radical
polymerization of maleic anhydride in toluene [14], and benzoyl peroxide (BPO) was used as initiator. The yield of
PMA was 90%, and its average number molecular weight was 1070. Intermediate 3 was synthesized by diazotization
and coupling reaction with 4-nitroaniline as diazo component and 1-(4-sulfonylphenyl)-3-methyl-2-pyrazoline- 5-one
as coupling component. 26 g (65 mmol) compound 3 and 150 mL water were added into a 500 mL three-necked flask
* Corresponding author.
E-mail address: zhangshf@dlut.edu.cn (S.F. Zhang).
1001-8417/$ – see front matter # 2010 Shu Fen Zhang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
doi:10.1016/j.cclet.2010.11.010

[()TD$FIG]
H. Xu et al. / Chinese Chemical Letters 22 (2011) 424–426
425
H C
3
NH
N
NCl
2
N
N
N
O N
2
N
H
a
b
O
NO
NO
2
2
3
SO H
3
2
1
COOH COOH
m
HOOC
n
H C
3
CO
N
N
N
NH
H N
N
H
2
c
d
e
O
4
SO H
3
H
N
N
O
N
CH
3
N
HO S
5
3
Scheme 1. Reaction conditions and reagents: (a) 35% HCl (aq.), NaNO2, 0–5 8C, 0.5 h. (b) 3-methyl-1-(4-sulfophenyl)-2-pyrazoline-5-one, 15%
Na2CO3 (aq.), 0–5 8C, 0.5 h, 96.9%. (c) Na2SÁ9H2O, NaHCO3, H2O, 75 8C, 4 h, 89.4%. (d) PMA, KOAc, HAc, 120 8C, 8 h. (e) H2O, 5% HCl (aq.),
5% Na2CO3 (aq.), 20 8C.
with a mechanical stirring bar, and heated to 75 8C. 22.6 g (130 mmol) sodium sulfide nonahydrate and 7.92 g
(130 mmol) sodium bicarbonate was dissolved in 200 mL water, and this mixture was dropped into the flask within
1 h, and kept at 75 8C for 4 h, and the reaction termination was determined by TLC (isobutyl alcohol: n-propanol: ethyl
acetate: water = 2:4:1:1). After the reaction was over, the pH of the mixture was adjusted to 5–6 with 5% hydrochloric
acid, and intermediate 4 was obtained by filtering. The product was dried to a constant weight under vacuum for 24 h,
the yield of the product was 89.4%. 2 g (6.83 mmol) compound 4 and 0.447 g (3.42 mmol) potassium acetate were
dissolved in 10 mL acetic acid, 1.17 g PMA was added into the mixture, and then the temperature was increased to
120 8C and kept at the temperature for 8 h. The reaction termination was determined by TLC (isobutyl alcohol: n-
propanol: ethyl acetate: water = 2:4:1:1). After that, the mixture was cooled to the room temperature and dissolved in
50 mL water, the pH of the solution was adjusted to 10–11 with 5% (wt/wt) sodium carbonate solution, and then
reduced the pH using 5% hydrochloric acid. At last, polycarboxylic acid dye 5 was precipitated from the solution and
obtained by filtration. FTIR 430 spectrophotometer, HP1100 mass spectrometer, HP-8453 UV–visible and Varian
Inova 400 NMR were used to determine the structures of the intermediates and the dye.
The API–ES mass spectra of 3 gave the correct quasi-molecular ion peak at 402 ([MÀH]À). lmax of 3 is 405 nm
(H2O). 1H NMR (400 MHz, DMSO-d6): d 13.25 (s, 1H, NH), 8.31 (d, 2H, J = 8.8 Hz, aryl), 7.87 (d, 2H, J = 7.2 Hz,
aryl), 7.85 (d, 2H, J = 8.0 Hz, aryl), 7.69 (d, 2H, J = 8.0 Hz, aryl), 2.33 (m, 3H, CH3). 13C NMR (400 MHz, DMSO-
d6): d 11.71 (CH3), 116.81 (aryl), 117.20 (aryl), 125.96 (aryl), 126.93 (aryl), 131.31 (aryl), 137.98 (aryl), 144.13 (aryl),
145.37 (aryl), 147.45 (C N–NH), 149.57 ([CH3]C N, ring), 156.39 (C O). FTIR (KBr): (–OH) 3434 cmÀ1, (C O on
the pyrazolone group) 1671 cmÀ1, (C C of aromatic ring) 1593, 1500 and 1448 cmÀ1, (–NO2) 1559 and 1340 cmÀ1
(–SO3H) 1340 and 1150 cmÀ1
,
.
The API–ES mass spectra of 4 gave the correct quasi-molecular ion peak at 372 ([MÀH]À). lmax of 4 is 450 nm
(H2O). 1H NMR (400 MHz, DMSO-d6): d 13.63 (s, 1H, NH), 7.89 (d, 2H, J = 8.4 Hz, aryl), 7.65 (d, 2H, J = 8.0 Hz,
aryl), 7.45 (d, 2H, J = 8.4 Hz, aryl), 6.65 (s, 2H, J = 8.0 Hz, aryl), 2.28 (m, 3H, CH3). 13C NMR (400 MHz, DMSO-
d6): d 12.01 (CH3), 114.87 (aryl), 117.03 (aryl), 118.41 (aryl), 125.16 (aryl), 126.87 (aryl), 130.86 (aryl), 138.81 (aryl),
144.31 (aryl), 148.43 (C N–NH), 148.63 ([CH3]C N, ring), 157.67 (C O). FTIR (KBr): (–OH) 3445 cmÀ1, (–NH2)
3352 cmÀ1, (C O on the pyrazolone group) 1658 cmÀ1, (C C of aromatic ring) 1593, 1500 and 1485 cmÀ1, (–SO3H)
1339 and 1155 cmÀ1
max of compound 5 is 395 nm (H2O). 13C NMR (400 MHz, DMSO-d6): d 173.11–175.72 (C O carboxylic group),
168 (C O amide), 157.01 (C O pyrazolone ring), 149.37 ([CH3]C N, pyrazolone ring), 147.1 (C N–NH), 144.13
.
l

426
H. Xu et al. / Chinese Chemical Letters 22 (2011) 424–426
Table 1
Dyeing characteristics of dye 5 and some conventional reactive dyes.
Dye
Fixation (%)
Wash-fastness
Change
Rub-fastness
Dry
Cotton
Wool
Wet
Dye 5
98.4
78.2
49.1
72.9
4
4–5
4
4–5
4
4–5
4
4–5
4–5
4
3–4
3
C.I. reactive yellow 17
C.I. reactive red 2
C.I. reactive blue 19
4
4
3–4
3–4
4–5
3–4
3–4
4
(C–N, pyrazolone ring), 141.38 (aryl), 139.12 (aryl), 138.54 (aryl), 128.08–129.92 (aryl), 127.47–127.66 (aryl),
126.82–126.95 (aryl), 124.75–124.89 (aryl), 116.97–117.23 (aryl), 33–45 (CH), 12.01 (CH3), FTIR (KBr): (–OH)
3445 cmÀ1, (C O carboxylic group) 1712 cmÀ1, (C O amide group) 1658 cmÀ1, (C C of aromatic ring) 1593, 1500
and 1485 cmÀ1, (–SO3H) 1339 and 1155 cmÀ1
.
The synthesized compound 5 was applied to dyeing of cotton through a ‘‘3-dip-3-nip’’ padding operation at room
temperature. The concentration of dye-bath was 0.5% (wt/wt), the dipping time of the dyed fibre in the padding bath
containing compound 5 was 3 min, and the pressure on the mangle was adjusted to give 70% wet pick up. After the
dyed fibre was dried at room temperature, it was dipped into the fixing-bath containing 1% (wt/wt) triethanolamine,
3% (wt/wt) dicyandiamine and 2% (wt/wt) zinc nitrate for 2 min and nipped once, the pressure on the mangle was
adjusted to give approximately 80% wet pick up. Then the fibre was heated to 180 8C for 5 min. At last, the dyed fibre
was rinsed completely with water. Dye fixation and fastness properties are shown in Table 1.
From Table 1, the overall fixation of dye 5 on cotton reached 98.4%. And when the cotton was dyed by the
conventional reactive dyeing method using C.I. reactive yellow 17, C.I. reactive red 2 and C.I. reactive blue 19, and the
fixation was only 78%, 49.1% and 72.9% [15–17], respectively. The wash fastness and rub fastness of dye 5 were as
good as that from dyed cotton using conventional reactive dyes with the conventional reactive dyeing method.
In conclusion, the prepared dye 5 possesses competitive advantages of high dye fixation and good fastness and can
be deemed promising in application.
Acknowledgments
This work was supported by the State Key Program of National Natural Science Foundation of China (No.
20836001), and the Program for Changjiang Scholars and Innovative Research Team in the University (No. IRT0711).
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