Salt-free reactive dyeing of betaine-modified cationic cotton fabrics with enhanced dye fixation

    Salt-free Reactive Dyeing of Betaine-modified Cationic Cotton Fabrics with Enhanced Dye Fixation Wei Ma, Mei Meng, Shumin Yan, Shufen Zhang PII: DOI: Reference:

S1004-9541(15)00235-9 doi: 10.1016/j.cjche.2015.07.008 CJCHE 334

To appear in: Received date: Revised date: Accepted date:

14 October 2014 20 May 2015 20 May 2015

Please cite this article as: Wei Ma, Mei Meng, Shumin Yan, Shufen Zhang, Salt-free Reactive Dyeing of Betaine-modified Cationic Cotton Fabrics with Enhanced Dye Fixation, (2015), doi: 10.1016/j.cjche.2015.07.008

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ACCEPTED MANUSCRIPT Energy, Resources and Environmental Technology

Salt-free Reactive Dyeing of Betaine-modified Cationic Cotton

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Fabrics with Enhanced Dye Fixation*

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Wei MA (马威)**, Mei MENG (孟梅), Shumin YAN (闫淑敏), Shufen ZHANG (张淑芬)

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State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116023, P.R. China

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Abstract Novel cationic cotton fabrics were prepared by an efficient and simple one-step pad-dry-bake

pretreatment process with betaine as cationic reagent. Ester bonds formed between cotton fibers and betaine

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hydrochloride were proved by Fourier transformed infrared attenuated total reflection (FTIR-ATR) spectra.

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Moreover, the properties of the cationic fabrics, including X-ray Diffraction (XRD), tensile strength and whiteness

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and yellowness index, were investigated in comparison with that of the untreated ones. The cationic fabrics were

applied in salt-free dyeing of C. I. Reactive Red 195, C.I. Reactive Yellow 145 and C.I. Reactive Blue 19.

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Different dye fixation processes were applied and compared for untreated and cationic cotton. Dye fixation and

color fastness properties of the dyes were tested, and the results presented that dye fixation on the cationic fabrics

in the absence of salt was improved with satisfactory light fastness property and applicable wash and rub

fastnesses.

Keywords Salt-free dyeing, betaine, cationic cotton, reactive dyes

*

Supported by the National Natural Science Foundation of China (21376042, 21421005), the National Key Technology R&D Program (2013BAF08B06) and Innovative Research Team of Ministry of Education (IRT-13R06) and Dalian University of Technology (DUT2013TB07).

**

Corresponding author. E-mail address: [email protected]

Received 2014-10-14， revised 2015-5-20， accepted 2015-5-20.

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1 INTRODUCTION

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In recent years, environmental pollution in dyeing industry has aroused great public concern

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and substantial researches were focused on solving the problem [1-5]. Reactive dyes are a kind of popular dyes for cotton dyeing due to their excellent properties, such as wide range of hue, brilliancy and good wet fastness. However, owing to low affinity between the dyes and the fibers,

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a large amount of salt (30-100 g·L-1), such as sodium sulfate or sodium chloride, is added in the

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dyebath to promote dye adsorption in exhaust dyeing method [6]; As it is not consumed during dyeing process, the added salt is all released after dyeing. However, the salt-containing dye

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wastewater is quite difficult to deal with and does great harm to the environment. In order to solve

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the problem, cationization of cotton has been widely studied in recent years for effective

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adsorption of reactive dyes in the absence of salt [7-15]. Among the cationic agents used, most of them are synthetic compounds which may present safety problem in application. Although some

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biopolymers or their derivatives, such as chitosan and its derivative, have been studied, the polymers on cotton may prevent dye penetration into the fibers and influence dye fixation. In addition, the existence of cationic groups on cotton surface easily leads to color staining and results in inferior color fastnesses, especially low light fastness [16-19]. In this study, a novel cationic agents- betaine is designed to be used to modify cotton fibers. Betaine (N,N,N-trimethyl glycine) is a kind of natural product. It was named after its discovery in sugar beets (Beta vulgaris) in the 19th century. Betaine shows good biodegradability and biocompatibility. It is even edible for health care, and usually used as additive in food or animal feed. Under acidic condition, betaine partially or totally turns to be betaine hydrochloride which

ACCEPTED MANUSCRIPT contains both quaternary ammonium group and carboxyl group. Cationization of the fibers can be realized through reaction of the carboxyl group of betaine hydrochloride and the hydroxyl group

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of cotton to form ester bond (See Figure 1). In this study, as-prepared cationic fabrics were the

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first time designed to be applied in salt-free dyeing of reactive dyes. Another merit of the betaine-modified fabrics is that the formed ester bonds could hydrolyze under alkaline and high-temperature conditions, which just accords with the dye fixation conditions, thus the cationic

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groups could be removed off from cotton to decrease the influence of color staining. H OR1

H OH O

O CI H

HO H

HO

CH3 N+

CH3

CH3 O

n

H

O CI H

R1O

H H

OR1 O

O R1=H or

n

CH3 N+

CH3

CH3

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H

OH

+

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H

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Figure 1 Preparation of cationic cotton

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As known, ester bonds are usually formed in organic solvents and the reaction conditions are severe, which are not suitable for treatment of cotton fabrics. Our previous study showed that with dry method and dicyandiamide as condensing agent, a kind of novel cationic cellulose- cellulose

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betainate was successfully prepared [20]. Borrowing the synthesis idea above, a facile pad-dry-bake method was designed for pretreatment of cotton fabrics with betaine as cationic agent. In addition, to achieve high dye fixation and effective hydrolysis of ester bonds, steaming dye fixation process was designed for the cationic cotton [21]. The objectives of this study are to characterize the betaine-modified cationic fabrics, measure their properties and investigate their dyeing performance with three commercial dyes- C. I. Reactive Red 195, C. I. Reactive Yellow 145 and C.I. Reactive Blue 19 (as shown in Figure 2).

ACCEPTED MANUSCRIPT Cl N SO3Na

OH HN

N N

N N

N H

NaO3S

SO3Na

SO2C 2H4OSO3Na

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SO3Na

SO3Na

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C.I. Reactive Red 195

O

NaO3S N N N H

N N

N

N H

SO2C 2H4OSO3Na

O

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H3C Cl

SO3Na

HN

SO2C2H4OSO3Na

C.I. Reactive Blue 19

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C.I. Reactive Yellow 145

NH2

Figure 2 Structures of the dyes applied

2.1 Materials

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2 EXPERIMENTAL

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100% cotton, bleached, desized and mercerized, was purchased from Testfabrics, Inc., Shanghai (China). Anhydrous betaine was purchased from Hangzhou Wan Jing New Materials Co.,

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Ltd. (Zhejiang, China). Dicyandiamide was purchased from Tianjin Bodi Chemical Co., Ltd. (China) and was analytical pure. The reactive dyes in this study were obtained from Shanghai Dyestuff Co. (China) and used as received. The other reagents and solvents were analytical pure.

2.2 Pretreatment of cotton fabrics Anhydrous betaine was dissolved in water to obtain 8% (w/w) solution and certain amount of hydrochloric acid was added to yield molar ratio of it to betaine of 1:1. Then dicyandiamide was added to above solution to obtain 5% (w/w) concentration. Cotton fabrics were dipped into the above aqueous solution at a liquor ratio of 10:1 and padded on a mangle to give 90% pickup.

ACCEPTED MANUSCRIPT Two-dip-two-pad procedure was used. The padded fabrics were dried at 80℃ for 3min, and then

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vacuo. The nitrogen content of the pretreated cotton was 0.027 mol·g-1.

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baked at 150℃ for 40s. In the following, the pretreated fabrics were washed and then dried in

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2.3 Dyeing procedure

Dyeing was carried out using a liquor ratio of 20:1. C.I. Reactive Red 195 applied was 2%

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o.w.f, C.I Reactive Yellow 145 was 1% o.w.f and C.I. Reactive Blue 19 was 3% o.w.f. Exhaust dyeing was used for both untreated and cationic cotton fabrics, while two different dye fixation

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procedures – dye-bath fixation and steaming fixation were employed and compared.

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Procedure 1: untreated cotton fabrics were dyed at 30℃ over 40 min in dyebath with addition

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of 60 g·L-1 anhydrous sodium sulphate, and then the temperature rose to 60℃ with the heating-rate of 2℃·min-1, followed by addition of 10 g·L-1 of sodium carbonate for dye fixation

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and kept at fixation temperature for 40 min. Procedure 2: cationic cotton fabrics were dyed at 30℃ over 40 min in dyebath without

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addition of sodium sulphate, and then the temperature rose to 60℃ with the heating-rate of 2℃·min-1, followed by addition of 10 g·L-1 of sodium carbonate for dye fixation and kept at fixation temperature for 40 min. Procedure 3: untreated cotton fabrics were dyed at 30℃ over 40 min in dyebath with addition of 60 g·L-1 anhydrous sodium sulphate. After that, the fabrics were taken out of the dyebath and padded, then dipped in 10 g·L-1 of Na2CO3 aqueous solution and padded with 80% pick-up. The dyed cotton was dried and steamed for 10 min. Procedure 4: cationic cotton fabrics were dyed at 30℃ over 40 min in dyebath without addition of sodium sulphate. After that, the fabrics were taken out of the dyebath and padded, then

ACCEPTED MANUSCRIPT dipped in 10 g·L-1 of Na2CO3 aqueous solution and padded with 80% pick-up. The dyed cotton was dried and steamed for 10 min.

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All of the dyed cotton fabrics above were rinsed successively in cold, warm and cold water

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and soaped at 95℃ with anionic detergent LS (2 g·L-1, Shanghai Dyestuff Co.) using a liquor ratio of 20:1 for 15 min. Then, the bath was dropped and the fabrics were washed with water and dried.

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2.4 Measurements

The nitrogen content of the cotton was obtained by the Kjeldahl method (GB12091-89).

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Fourier-transform infrared spectroscopic (FT-IR) study was recorded on a NICOLET 6700 FT-IR

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spectrometer (Thermo Fisher, America) with universal ATR sampling accessory to measure FT-IR

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spectra of the pretreated and untreated cotton fabrics. X-ray diffraction of cotton fibers was measured stepwise in the 2θ between 4° and 60° by a diffractometer

D/max-2400

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Rigaku

(Rigaku,

Japan)

and

Monochromatic

(Graphite

monochromator) Cu-Ka1-radiation (40 kV, 100 mA) was used.

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Tensile strength of the cationic cotton was measured using a YG026 tensile strength machine (Changzhou Textile Apparatus Plant, China). K/S values and whiteness and yellowness index were measured using an UltraScan XE Color Measuring and Matching Meter (Roaches Co.). Light fastness was tested according to ISO 105-B06-1998 using a Xenotext 150s Weatherometer (Heraeus Co., Germany). Wash fastness of the dyes was tested according to ISO 105-B01:1994 using S-1002 two-bath dyeing and testing apparatus (Roaches Co.). Rub fastness was tested according to ISO 105-X12:1993 using a Y(B)571-II crockmeter (Wenzhou Darong, Co., China).

ACCEPTED MANUSCRIPT Cross-sections of the dyed cotton fibers were prepared using an LEICA EM UC6 microtome (Leica, Germany). Images of the cross-sections were obtained at 600× magnification using

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Olympus BX63 light microscope (Japan).

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3 RESULTS AND DISCUSSION 3.1 IR analysis of the cotton fabrics

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In order to characterize the structure of the cationic cotton fabrics, IR spectra of the untreated

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fabric, the cationic one and the cationic one after treatment under alkaline steaming condition were measured and compared (see Figure 3).

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In Figure 3, the principal spectral features of the untreated cotton fabric were shown as

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follows: 3277 cm-1 (absorption peak of stretching vibration of O–H), 2890 cm-1 (absorption peak

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of stretching vibration of C–H), 1637 cm-1 (absorption peak of bending vibration of O–H), 1425 cm-1 and 1363 cm-1 (absorption peaks of deformation vibration of C–H of CH2 and CH), 1157

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cm-1 (adsorption peak of bending vibration of CH2), and 1015 cm-1 (absorption peak of stretching vibration of C-O-C). Compared to the untreated cotton, the cationic one present a small new peak at 1753 cm-1, which was assigned to the stretching vibration of C=O of the ester carbonyl group, indicating formation of ester bonds between cotton fibers and betaine hydrochloride. Evidence was also observed in references that adsorption peaks of the ester bonds of cellulose betainate and starch betainate both appeared at ~1750 cm-1 [20, 22, 23].

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cotton cationic cotton after-treated cationic cotton

200

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cotton

1753

cationic cotton

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150

3500

3000

2500

2000

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0 4000

1051 1015 992 892

3277

2890

after-treated cationic cotton

50

1425 1363 1313 1157

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100 1637

Transmittance/ %

250

1500

1000

Wavenumbers/cm-1

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Figure 3 IR spectra of cotton fabric, cationic one and cationic one after treatment under alkaline steaming condition

In addition, it showed the peak at 1753 cm-1 disappeared on the IR spectrum of the cationic

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cotton after treatment under alkaline steaming condition and washing, which demonstrated the

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hydrolysis of the ester bonds under the condition.

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3.2 XRD of the cotton fibers

1200 Untreated Cationic

Untreated Cationic

1000

Intensity

Intensity

800 600 400 200 0

5

10

15

20

25

2(degree)

(a)

30

35

40

5

10

15

20 25 30 2(degree)

35

40

(b)

Figure 4 X-ray diffraction patterns of untreated cotton fibers and cationic one

X-ray diffraction spectra of the untreated fibers and the cationic ones were also measured and the results were shown and compared in Figure 4 (a) and (b). It shows that their X-ray spectra are

ACCEPTED MANUSCRIPT almost the same with typical diffraction peaks appearing at 22.6º, 16.2º and 14.8º. Figure 4 (b) presents that the peak intensity of both patterns are almost the same, indicating the facile

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pad-dry-bake pretreatment process showed little influence on the degree of crystallinity of the

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cotton fibers.

3.3 Tensile strength of the cotton fabrics

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Chemical modification under acidic and high temperature usually decreases the tensile strength of the cotton fabrics, which will affect their application properties [24]. The tensile strength of the

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cationic fabrics was measured and compared with that of the untreated ones. The results were

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listed in Table 1.

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It could be observed that through modification of cotton fabrics, tensile strength in warp decreased by 6.1% and that in woof decreased by 4.2%. Since modification was carried out under

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acidic and high-temperature conditions, the tensile strength of the fibers decreased, indicating the adverse effect of the pretreatment. While as the average decrease was only about 5%, application

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properties would not be affected much. Table 1 Tensile strength of the untreated cotton fabrics and the cationic ones

Tensile strength Cotton Warp /N

Untreated

578.7

Cationic

543.4

Dec. /%

Woof /N

Dec. /%

577.1

6.1

552.9

4.2

3.4 Whiteness and yellowness of the cotton fabrics Cotton fabrics may turn yellow under acidic and high temperature conditions [25]. If so, the

ACCEPTED MANUSCRIPT wearability of the fabrics will be affected. Moreover, when being dyed, the fabrics will exhibit darker color. Whiteness and yellowness index can be used to evaluate the color of the undyed

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fabrics. These values presented the consistency, which means the higher the whiteness is, the

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lower the yellowness is. In this study, the whiteness and the yellowness of the cotton fabrics before and after pretreatment were examined, and the results were shown in Table 2.

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Table 2 Whiteness and yellowness of the untreated and cationic cotton fabrics

Whiteness

Yellowness

(WIE 313-98)

(YIE 313-98)

63.97

7.93

66.6

7.41

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Untreated

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Cotton

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Cationic

From Table 2, the whiteness of the untreated cotton was 63.97, while that of the cationic one was 66.6, which indicated that after pretreatment, the cotton became even whiter. From the values

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of yellowness of the cotton in Table 2, it also gave the same result that the cationic fabrics were less yellow than the untreated ones. Although temperature as high as 150℃ was employed for baking, as the treatment time is quite short, the fabrics did not influence the color even under acidic condition. A little increase in whiteness may be illustrated by that some impurity was removed off from the surface of the fabrics during pretreatment.

3.5 Dye penetrability Dye penetrability commonly influences dye fixation and color fastness properties. If dyes can penetrate into fibers well, it is beneficial for reaction of the dyes with the fibers to achieve high

ACCEPTED MANUSCRIPT dye fixation. In the study, dye penetrability into the cationic cotton fibers was tested by light microscope and the results were shown in Figure 5 (a) and (b). From cross-section photographs of

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the cotton fibers dyed with C.I. Reactive Red 195, it was observed the inner parts of both the

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untreated (a) and cationic (b) fibers were colored, that meant the dyes penetrated well in the fibers. In addition, it is clearly seen that the color is deeper in Figure 4 (b) than that in (a), which should

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be mainly due to much higher color yield of the cationic cotton fibers.

Figure 5 Cross-sections of cotton fibers dyed with C.I. Reactive Red 195 (a) untreated and (b) cationic fibers

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3.6 Dyeing test

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The untreated and cationic cotton fabrics were all dyed with C.I. Reactive Red 195, C.I. Reactive Yellow 145 and C.I. Reactive Blue 19. Besides dye-bath fixation procedure, steaming fixation procedure was designed and comparison was made between them. The dye fixation of all three dyes was listed in Table 3. The results showed that with conventional dye-bath fixation procedure (Proc. 1 and Proc. 2), F% of C.I. Reactive Red 195, C.I. Reactive Yellow 145 and C.I. Reactive Blue 19 on the untreated cotton in the presence of 60 g·L-1 sodium sulphate reached 78.2%, 75.7% and 67.2%, respectively (Proc. 1). However, with this dyeing method, the cationic cotton could not achieve good dye fixation, only about 50% of the dyes applied was utilized (Proc. 2). While with the steaming fixation procedures (Proc. 3 and Proc. 4), dye fixation of all

ACCEPTED MANUSCRIPT three dyes on the untreated cotton (Proc. 3) was much lower than that obtained with Proc. 1, even in the presence of salt. While for the cationic cotton fabrics with Proc. 4 in the absence of sodium

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sulphate, dye fixation of C.I. Reactive Red 195, C.I. Reactive Yellow 145 and C.I. Reactive Blue

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19 reached 84.9%, 85.2% and 74.9%, respectively, which were 6.7%, 9.5% and 7.7% respectively higher than that obtained with Proc. 1. These results revealed that fixation procedure influence the dye fixation on different fabrics very much. And steaming fixation procedure is

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more suitable for the betaine-modified cationic cotton. The reason is now under investigation.

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Table 3 Comparison of dye fixation of three reactive dyes with different dye fixation procedures

Dye fixation, F/%

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Dyes

Proc.2

Proc.3

Proc.4

78.2

48.7

58.6

84.9

C.I. Reactive Yellow 145

75.7

52.0

70.6

85.2

C.I. Reactive Blue 19

67.2

47.6

30.2

74.9

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Proc.1

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C.I. Reactive Red 195

The color fastness of C.I. Reactive Red 195, C.I. Reactive Yellow 145 and C.I. Reactive Blue 19 on both the cationic and untreated cotton were also measured and compared. The results were listed in Table 4. It can be seen from Table 4, light fastness of C.I. Reactive Red 195, C.I. Reactive Yellow 145 and C.I. Reactive Blue 19 on cationic cotton fabrics was 4, 5 and 7 grade, respectively, which was the same with that on the untreated ones. These results were inspiring as some reports presented cationization of the fabrics decreased light fastness of the dyes on them [15-17]. It was presumably due to that good dye penetrability and high dye fixation was achieved, light fastness

ACCEPTED MANUSCRIPT could maintain good. As for wash fastness, most result data reached 3-4 grade except that wool staining of C.I. Reactive Blue 19 was 3 grade; For rub fastness, dry rub fastness of the dyes on

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cationic cotton was excellent, which was not lower than 4 grade; while wet rub fastness on the

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cationic fabrics was all half grade lower than that on the untreated ones. The color fastness results showed that even with the steaming fixation process, the influence of cationization of cotton on dyeing still existed. It was analyzed that although ester bonds could break under the steaming

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fixation condition and the cationic groups be easily removed off without addition of dyes, the

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washing off of the unfixed dyes together with the cationic groups could not be as easy as expected after dyeing. While as all of the fastnesses obtained could reach 3 grade or higher and dye fixation

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increased distinctly without addition of salt, this dyeing method still showed good application

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prospect.

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Dye

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Table 4 K/S and fastness properties of the dyes on cationic and untreated cotton

Wash fastness Fixation,

Light

Proc.

Color F/%

Rub fastness

Wool

Cotton

fastness change

staining

staining

Dry

Wet

C.I. Reactive Red

4

84.9

4

4

4-5

4

4-5

3

195

1

78.2

4

4

4-5

4-5

4-5

3-4

C.I. Reactive Yellow

4

85.2

5

3-4

4-5

4-5

4-5

3-4

145

1

75.8

5

4

4-5

4-5

4-5

4

4

74.9

7

3-4

3

3-4

4

3

1

67.2

7

4

4

4

4

3-4

C.I. Reactive Blue 19

4 CONCLUSIONS

ACCEPTED MANUSCRIPT Novel cationic cotton fabrics were prepared by pretreating the fabrics with betaine acidic solution with a pad-dry-bake method. FTIR-ART analysis of the cotton fabrics with different

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treatment procedures showed that ester bonds formed under pretreatment conditions and could

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break under steaming fixation conditions. Tensile strength of the cationic fabrics decreased by about 5% compared with that of the untreated ones, while the whiteness of the cationic ones increased a little bit. It showed with the salt-free dyeing method, higher dye fixation was obtained

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on the cationic fabrics and more dyes could penetrate into the fibers. Compared with that on the

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untreated ones, the increase in dye fixation of C.I. Reactive Red 195, C.I. Reactive Yellow 145 and C.I. Reactive Blue 19 was 6.7%, 9.5% and 7.7%, respectively, on cationic fabrics. Color

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fastness tests showed that all light and dry rub fastnesses of the dyes on the cationic cotton were

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excellent. However, some wash and wet rub fastnesses could not keep as good as that of the

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conventional dyeing, which was probably due to partial color staining. Further study should be carried out on improving color fastness. Anyway, in consideration of the high dye fixation,

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applicable color fastness, and the most important environmental concern of eliminating salt usage, this dyeing method is promising in application.

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Synthesis, characterization and structure-property relations”, Cellulose, 10, 283-296 (2003). [24] Kang, I. S., Yang, C. Q., Wei, W. S., Lickfield, G. C., “Mechanical Strength of Durable Press

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Finished Cotton Fabrics Part I: Effects of Acid Degradation and Crosslinking of Cellulose by Polycarboxylic Acids”, Text. Res. J., 68, 865-870 (1998). [25] Dehabadi, V. A., Buschmann, H. J., Gutmann, J. S., “Durable press finishing of cotton fabrics

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with polyamino carboxylic acids”, Carbohyd. Polym., 89, 558-563 (2012).

ACCEPTED MANUSCRIPT

Graphic Abstract O

O CI H

HO H

HO

H

CH3 N+

CH3

H

R1O

H

CH3 O

n

O

H

OR1 O

R1=H or

n

CI O

CH3 N+

CH3

CH3

SC R

H

OH

+

IP

H

T

H OR1

H OH

Cationic cotton fabrics were prepared by an efficient and simple one-step pad-dry-bake process with betaine as

NU

cationic reagent. The structure of the cationic fabrics was analyzed to show formation of ester bonds. XRD, tensile

strength and whiteness and yellowness index were all investigated to present good applicability of the cationic

MA

fabrics. Salt-free dyeing results showed F% of C.I. Reactive Red 195, C.I. Reactive Yellow 145 and C.I. Reactive

D

Blue 19 increased by 6.7%, 9.5% and 7.7%, respectively, in comparison with that of the conventional dyeing. And

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satisfactory light fastness and applicable wash and rub fastnesses properties were all obtained, indicating this

AC

CE P

dyeing method showed good application prospect.