- Email: [email protected]
Synthesis and properties of the novel surface-active dyes containing fluorocarbon groups
Materials Chemistry and Physics 105 (2007) 199–203
Synthesis and properties of the novel surface-active dyes containing fluorocarbon groups Part 1. Synthesis and surface properties of the novel surface-active dyes on silk fabric Kongliang Xie a,∗ , Yanna Liu a , Xiaochun Li b a b
Modern Textile Institute, Donghua University, Shanghai 200051, China Huazhong University of Science and Technology, Wuhan 430074, China
Received 5 June 2006; received in revised form 7 March 2007; accepted 8 April 2007
Abstract A series of novel surface-active dyes containing fluorocarbon groups were designed. The dyeing behaviors of these dyes on silk were studied. The novel dye containing fluorocarbon groups imparted high surface activity due to use fluorocarbon groups. The results of dyeing on silk indicated that the novel surface-active dyes containing fluorocarbon groups showed good exhaustion on silk and the light fastnesses on silk were excellent. © 2007 Elsevier B.V. All rights reserved. Keywords: Synthesis; Surface-active dyes; Fluorocarbon groups; Dyeing; Silk fabric
1. Introduction The silk is highly appreciated for its outstanding characteristics such as comfortable hand, excellent softness, and good drape. Silk fabrics are widely used for clothing industry. It is commonly known that the acid and reactive dyes are used to dye silk fabric. The dyeing of silk with reactive and acid dyes has been extensively reviewed over the years [1–3]. However, there are important problems about leveling property and fastness to light for silk. Generally, the leveling property of small molecule reactive dyes is good. But the exhaustion of reactive dyes on silk is low. The reaction between silk and dyes can be carried out only under alkali condition. Silk can be damaged at this condition. Acid dyes have a higher exhaustion than reactive dyes on silk, but the leveling property is not good. Several studies on silk dyeing have already been carried in relation to dye leveling property and penetration into fiber. New dyes have been synthesized in order to improve fastness properties. For example, a polyfunctional reactive dyes containing disulphidebis (ethylsulphone-monochlorotriazine/sulphatoethylsulphone) reactive system has been applied to silk [4]. It has been reported
that acid dyes containing long carbon chain are preferred for fastness to light [5,6]. The acid dyes containing long carbon chain impart surface activity property. In this article, a series of novel surface-active dyes containing fluorocarbon groups were synthesized (Scheme 1). High surface activity was achieved using fluorocarbon groups. Novel surfaceactive dyes containing fluorocarbon groups maybe impart good light fastness on silk. The dyeing behaviors of these dyes on silk were investigated by measuring the exhaustion on silk fiber. Color fastnesses of the dyed fabric were also examined. 2. Experimental 2.1. Materials Silk fabric was obtained from Zibo Silk Textile Company. Silk fabric was treated for 0.5 h at 50 ◦ C in the presence of 1.0% Detergent 209, and then washed. The three reactive dyes containing a dichlorotriazine group (Reactive Red X3B, Reactive Yellow X-RG, Reactive Blue X-BR) were obtained from Shanghai Dyestuff Co. and were reagent grade in the study. Perfluorooctanesulphonyl fluoride (C8 F17 SO2 F) was obtained from Wuhan Chemical Co. All other chemicals were obtained from Shanghai Chemical Agent Co.
2.2. Measurements of FTIR and surface tension ∗
Corresponding author. Tel.: +86 21 6237 8237; fax: +86 21 6237 8392. E-mail address: [email protected] (K. Xie).
0254-0584/$ – see front matter © 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.matchemphys.2007.04.032
FTIR spectra of the dyes were measured by NICOLET 20 DXB FTIR. The surface tensions of novel surface-active dyes 1 and 3, Reactive Red X-3B and
200
K. Xie et al. / Materials Chemistry and Physics 105 (2007) 199–203 (C8 F17 SO2 F) was added in 1 h. The reaction mixture was agitated for 1 h at 0 ◦ C and for 3 h at 30 ◦ C. After cooling, the mixture was washed with 20 ml of 4.5% hydrochloric acid, and upon standing the aqueous and non-aqueous phases separated into layers, and the aqueous layer was removed. Then the isopropyl ether was removed by distilling. The crude product was recrystalled. The yield was 87.2%.
Scheme 1.
Reactive Blue X-BR were determined using DCA322 Surface Tension Meter (Therno Cahn Co.).
2.3. Synthesis of novel surface-active dyes (1–3) containing fluorocarbon groups (shown in Scheme 2)
2.3.2. The synthesis of dyes The synthesis of the novel dye 1 was carried out by initial preparation of the reactive dyes containing dichlorotriazine groups as described in the previous study (Scheme 4) [7]. A similar procedure was used for the synthesis of dyes 2 and 3. The purification was achieved by recrystallization with alcohol, dried. Dye 1: λmax = 525 nm. IR (cm−1 ): 3321.2, 1634.6, 1597.8, 1542.3, 1460, 1368, 1150, 1050, 886.8. Dye 2: λmax = 410 nm. IR (cm−1 ): 3324.1, 1595.2, 1542.1, 1523.7, 1462.4, 1372, 1204, 1152, 884.6, 561. Dye 3: λmax = 620 nm. IR (cm−1 ): 3324.1, 1542.1, 1462.4, 1371, 1204, 1102, 1152, 884.6, 559.
2.4. Dyeing 2.3.1. The synthesis of N-ethylamine sulphonamino derivative (C8 F17 SO2 NHCH2 CH2 NH2 ) (Scheme 3) A 250 ml glass flack equipped with thermometer, stirrer and distilling head, was charged with 100 ml isopropyl ether which was cooled to 0 ◦ C, and 0.02 mol of biethylamine was added. Then 0.02 mol of perfluorooctanesulphonyl fluoride
The silk fabrics were dyed in an IR dyeing machine (PYROTEC-2000), the liquor ratio being 20:1 and the dyeing solution pH value being maintained by an acetic acid/sodium acetate buffer solution. Fabric was immersed in the dye bath at 40 ◦ C and the temperature was increased to 95 ◦ C at a rate of 1 ◦ C min−1 .
Scheme 2.
K. Xie et al. / Materials Chemistry and Physics 105 (2007) 199–203
201
Scheme 3. Dyeing was carried out at this temperature for certain time. After dyeing, all the dyed samples rinsed with water and air-dried.
2.5. Measurement of dye exhaustion The exhaustion of the dyes on silk fabric was calculated by measuring the absorbance of the residual dye bath liquor. The percentages of dye bath exhaustion (E%) were calculated according to Eq. (1).
E (%) = 1 −
A1 A0
× 100
(1)
where A0 and A1 are the absorbance of the dye solution at λmax before and after dyeing, respectively.
2.6. Fastness testing Color fastness was determined according to the respective international standards: fastness to washing, ISO 105-C04 (1989), fastness to rubbing, ISO 105-X12 (1993), and fastness to light, ISO 105-B02 (1994).
Fig. 1. The surface tensions of novel surface-active dyes 1 and 3, Reactive Red X-3B and Reactive Blue X-BR.
tions decrease sharply. The minimum surface tensions 13.31 and 19.37 mN m−1 were achieved at certain concentration of dyes 1 and 3, respectively. High surface activity achieved using fluorocarbon groups could improve the leveling properties because of their excellent penetration.
3. Results and discussion 3.1. The surface activity of novel dyes containing fluorocarbon groups The novel surface-active dyes 1 and 3 containing fluorocarbon groups were synthesized from Reactive Red X-3B and Reactive Blue X-BR containing a dichlorotriazine group (Scheme 4). High surface activity was achieved with fluorocarbon groups. The surface tensions of novel surface-active dyes 1 and 3, Reactive Red X-3B and Reactive Blue X-BR were determined. The results in Fig. 1 show that Reactive Red X3B and Reactive Blue X-BR had no surface activity, and novel dyes 1 and 3 had high surface activity due to the use of fluorocarbon groups. When dyes 1 and 3 concentrations were more than 0.001 mol l−1 , the surface tension of the dyed solu-
3.2. Absorption process of dyes on silk The novel surface-active dyes containing fluorocarbon groups were used for silk as acid dyes. In order to investigate dyeing procedure, the exhaustion on silk of the novel and reactive dyes were compared. Figs. 2–4 show the exhaustion curves for dyes 1–3, 1% (o.w.f.) on silk at pH 4, respectively. Figs. 2–4 indicate that the exhaustions of the novel dyes on silk fabric at first stage were lower than corresponding to the reactive dyes. During the second stage of dyeing, the exhaustions of the novel
Scheme 4.
202
K. Xie et al. / Materials Chemistry and Physics 105 (2007) 199–203 Table 1 Effect of pH value on dye exhaustion on silk (%) Dyes
pH
1 2 3
Fig. 2. Exhaustion of dye 1 and Reactive Red X-3B on silk (1.0% o.w.f., pH 4).
4.0
5.0
6.0
7.0
72.78 70.01 75.65
65.71 65.08 39.13
62.08 63.75 35.65
49.61 26.25 21.74
hydrophobicity, the novel dyes can form micelles in the solution. The hydrophilic sulphonic acid groups outside of the micelles improved water solubility at the initial stage of dyeing process. The number of micelles decreased with temperature rising. At the last stage, therefore, maximum exhaustions of them on silk fabric were higher than those of the reactive dyes. 3.3. Effect of dyeing pH In order to determine the optimum dyeing conditions for novel surface-active dyes, a series of dyeing using 1% (o.w.f.) dyes were carried out from pH 4 to 7. The influence of dyeing pH on the dye exhaustions on silk was listed in Table 1. It clearly shows that the exhaustions of the novel dyes on silk decreased with pH rising. Under acidic conditions, the silk fiber had positive charges and had higher dye absorption ability. With increasing pH, the dye absorption ability was lessened. Therefore, the effect of pH value on dye exhaustion on silk was significant.
Fig. 3. Exhaustion of dye 2 and Reactive Yellow X-RG on silk (1.0% o.w.f., pH 4).
dyes on the silk fabric were almost the same as the reactive dyes. But at last stage, maximum exhaustions of them on silk fabric were higher than those of the reactive dyes. According to exhaustion curves of the dyes, the leveling properties of the novel dyes on silk were better than the reactive dyes. The results clearly show that compared with the reactive dyes, better exhaustions of dyes containing fluorocarbon groups were achieved after dyeing 60 min. It can be observed that the dyeing time of 60 min was necessary to achieve suitable exhaustion. High surface activity could improve the leveling properties because of their excellent penetration. In general, fluorocarbon groups are considered as
3.4. Effect of salt concentration The effect of salt concentration on the dye exhaustion on silk was discussed at pH 4, and the results were shown in Table 2. It can be seen that increasing the concentration of sodium sulphate from 0 to 15 g l−1 led to a slight increase in the exhaustion of the novel dyes on silk. A further increase in salt concentration gave little further improvement in the dye exhaustion, even a little decrease. 3.5. Effect of liquor ratio Dyeing of the novel dyes (1% o.w.f.) on silk was carried out at different liquor-to-goods ratio (10:1, 20:1, 30:1), sodium sulphate 15 g l−1 , pH 4, 95 ◦ C. The effect of liquor ratio on the exhaustion was shown in Table 3. It can be seen that when the liquor ratio was raised from 10:1 to 30:1, the exhaustions of dyes 1 and 2 on silk had significant decrease, and that of dye 3 on silk had slight decrease. Table 2 Effect of sodium sulphate concentration on dyes exhaustion on silk (%) Dyes
Fig. 4. Exhaustion of dye 3 and Reactive Blue X-BR on silk (1.0% o.w.f., pH 4).
1 2 3
Sodium sulphate concentration (g l−1 ) 0
2
5
10
15
20
73.06 70.13 75.65
72.99 72.50 78.26
73.51 75.12 79.13
75.30 78.75 83.48
79.98 80.11 87.83
79.02 77.5 87.83
K. Xie et al. / Materials Chemistry and Physics 105 (2007) 199–203 Table 3 Effect of liquor ratio on dye exhaustion on silk (%) Dyes
Liquor ratio
1 2 3
10:1
20:1
30:1
80.26 80.12 87.39
71.17 79.38 86.08
71.95 60.05 83.48
1 2 3
Dye 1 Dye 2 Dye 3
3.7. Fastness properties
Dyes concentration (%) o.w.f. 0.5
1.0
2.0
5.0
88.65 84.15 91.19
80.26 80.12 87.39
70.13 69.52 76.59
60.42 51.52 59.43
Table 5 Fastness properties of the novel dyes on silk Dyed sample
5.0% o.w.f.), liquor ratio being 20:1, sodium sulphate 15 g l−1 , pH 4, 95 ◦ C. The results were listed in Table 4. Table 4 shows that with the dyes concentration rising, the exhaustions of dyes 1–3 on silk gradually decreased.
The results of fastness tests for dyes 1–3 on silk fabric were summarized in Table 5. The results clearly indicate that the light fastness, rubbing fastness and washing fastness were all very good, especially light fastness.
Table 4 Effect of dyes concentration on exhaustion on silk (%) Dyes
203
Rubbing fastness
Washing fastness
Dry
Wet
SC
SW
5 5 5
4–5 4–5 4–5
4–5 5 5
5 4 4–5
Light fastness
4. Conclusions The novel surface-active dyes containing fluorocarbon groups were synthesized. Novel dyes containing fluorocarbon groups imparted high surface activity due to use fluorocarbon groups. The dyes on silk had good leveling properties. The suitable process of the novel dyes on silk was: sodium sulphate 15 g l−1 , pH 4, liquor ratio being 20:1, 95 ◦ C for 60 min. The fastness properties on silk were good. References
5 5 5
SC: staining on cotton; SW: staining on silk.
3.6. Effect of dyes concentration To examine the influence of dyes concentration, the dyeing was carried out at different dyes concentration (0.5, 1.0, 2.0,
[1] W. Zuwang, Rev. Prog. Color. 28 (1998) 32. [2] M.L. Gulrajani, Rev. Prog. Color. 23 (1993) 51. [3] C. Zaisheng, J. Guochuan, Q. Yiping, J. Appl. Polym. Sci. 91 (2004) 3579. [4] Y.A. Youssef, A.A. Mousa, Color. Technol. 118 (2002) 325. [5] C. Lubo, W. Zuwang, Dyestuffs Ind. 36 (1999) 1. [6] C. Xudong, Dyestuffs Color. 40 (2003) 10. [7] P. Guoguang, Dyestuffs Color. 41 (2004) 71.
Synthesis and properties of the novel surface-active dyes containing fluorocarbon groups Part 1. Synthesis and surface properties of the novel surface-active dyes on silk fabric Kongliang Xie a,∗ , Yanna Liu a , Xiaochun Li b a b
Modern Textile Institute, Donghua University, Shanghai 200051, China Huazhong University of Science and Technology, Wuhan 430074, China
Received 5 June 2006; received in revised form 7 March 2007; accepted 8 April 2007
Abstract A series of novel surface-active dyes containing fluorocarbon groups were designed. The dyeing behaviors of these dyes on silk were studied. The novel dye containing fluorocarbon groups imparted high surface activity due to use fluorocarbon groups. The results of dyeing on silk indicated that the novel surface-active dyes containing fluorocarbon groups showed good exhaustion on silk and the light fastnesses on silk were excellent. © 2007 Elsevier B.V. All rights reserved. Keywords: Synthesis; Surface-active dyes; Fluorocarbon groups; Dyeing; Silk fabric
1. Introduction The silk is highly appreciated for its outstanding characteristics such as comfortable hand, excellent softness, and good drape. Silk fabrics are widely used for clothing industry. It is commonly known that the acid and reactive dyes are used to dye silk fabric. The dyeing of silk with reactive and acid dyes has been extensively reviewed over the years [1–3]. However, there are important problems about leveling property and fastness to light for silk. Generally, the leveling property of small molecule reactive dyes is good. But the exhaustion of reactive dyes on silk is low. The reaction between silk and dyes can be carried out only under alkali condition. Silk can be damaged at this condition. Acid dyes have a higher exhaustion than reactive dyes on silk, but the leveling property is not good. Several studies on silk dyeing have already been carried in relation to dye leveling property and penetration into fiber. New dyes have been synthesized in order to improve fastness properties. For example, a polyfunctional reactive dyes containing disulphidebis (ethylsulphone-monochlorotriazine/sulphatoethylsulphone) reactive system has been applied to silk [4]. It has been reported
that acid dyes containing long carbon chain are preferred for fastness to light [5,6]. The acid dyes containing long carbon chain impart surface activity property. In this article, a series of novel surface-active dyes containing fluorocarbon groups were synthesized (Scheme 1). High surface activity was achieved using fluorocarbon groups. Novel surfaceactive dyes containing fluorocarbon groups maybe impart good light fastness on silk. The dyeing behaviors of these dyes on silk were investigated by measuring the exhaustion on silk fiber. Color fastnesses of the dyed fabric were also examined. 2. Experimental 2.1. Materials Silk fabric was obtained from Zibo Silk Textile Company. Silk fabric was treated for 0.5 h at 50 ◦ C in the presence of 1.0% Detergent 209, and then washed. The three reactive dyes containing a dichlorotriazine group (Reactive Red X3B, Reactive Yellow X-RG, Reactive Blue X-BR) were obtained from Shanghai Dyestuff Co. and were reagent grade in the study. Perfluorooctanesulphonyl fluoride (C8 F17 SO2 F) was obtained from Wuhan Chemical Co. All other chemicals were obtained from Shanghai Chemical Agent Co.
2.2. Measurements of FTIR and surface tension ∗
Corresponding author. Tel.: +86 21 6237 8237; fax: +86 21 6237 8392. E-mail address: [email protected] (K. Xie).
0254-0584/$ – see front matter © 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.matchemphys.2007.04.032
FTIR spectra of the dyes were measured by NICOLET 20 DXB FTIR. The surface tensions of novel surface-active dyes 1 and 3, Reactive Red X-3B and
200
K. Xie et al. / Materials Chemistry and Physics 105 (2007) 199–203 (C8 F17 SO2 F) was added in 1 h. The reaction mixture was agitated for 1 h at 0 ◦ C and for 3 h at 30 ◦ C. After cooling, the mixture was washed with 20 ml of 4.5% hydrochloric acid, and upon standing the aqueous and non-aqueous phases separated into layers, and the aqueous layer was removed. Then the isopropyl ether was removed by distilling. The crude product was recrystalled. The yield was 87.2%.
Scheme 1.
Reactive Blue X-BR were determined using DCA322 Surface Tension Meter (Therno Cahn Co.).
2.3. Synthesis of novel surface-active dyes (1–3) containing fluorocarbon groups (shown in Scheme 2)
2.3.2. The synthesis of dyes The synthesis of the novel dye 1 was carried out by initial preparation of the reactive dyes containing dichlorotriazine groups as described in the previous study (Scheme 4) [7]. A similar procedure was used for the synthesis of dyes 2 and 3. The purification was achieved by recrystallization with alcohol, dried. Dye 1: λmax = 525 nm. IR (cm−1 ): 3321.2, 1634.6, 1597.8, 1542.3, 1460, 1368, 1150, 1050, 886.8. Dye 2: λmax = 410 nm. IR (cm−1 ): 3324.1, 1595.2, 1542.1, 1523.7, 1462.4, 1372, 1204, 1152, 884.6, 561. Dye 3: λmax = 620 nm. IR (cm−1 ): 3324.1, 1542.1, 1462.4, 1371, 1204, 1102, 1152, 884.6, 559.
2.4. Dyeing 2.3.1. The synthesis of N-ethylamine sulphonamino derivative (C8 F17 SO2 NHCH2 CH2 NH2 ) (Scheme 3) A 250 ml glass flack equipped with thermometer, stirrer and distilling head, was charged with 100 ml isopropyl ether which was cooled to 0 ◦ C, and 0.02 mol of biethylamine was added. Then 0.02 mol of perfluorooctanesulphonyl fluoride
The silk fabrics were dyed in an IR dyeing machine (PYROTEC-2000), the liquor ratio being 20:1 and the dyeing solution pH value being maintained by an acetic acid/sodium acetate buffer solution. Fabric was immersed in the dye bath at 40 ◦ C and the temperature was increased to 95 ◦ C at a rate of 1 ◦ C min−1 .
Scheme 2.
K. Xie et al. / Materials Chemistry and Physics 105 (2007) 199–203
201
Scheme 3. Dyeing was carried out at this temperature for certain time. After dyeing, all the dyed samples rinsed with water and air-dried.
2.5. Measurement of dye exhaustion The exhaustion of the dyes on silk fabric was calculated by measuring the absorbance of the residual dye bath liquor. The percentages of dye bath exhaustion (E%) were calculated according to Eq. (1).
E (%) = 1 −
A1 A0
× 100
(1)
where A0 and A1 are the absorbance of the dye solution at λmax before and after dyeing, respectively.
2.6. Fastness testing Color fastness was determined according to the respective international standards: fastness to washing, ISO 105-C04 (1989), fastness to rubbing, ISO 105-X12 (1993), and fastness to light, ISO 105-B02 (1994).
Fig. 1. The surface tensions of novel surface-active dyes 1 and 3, Reactive Red X-3B and Reactive Blue X-BR.
tions decrease sharply. The minimum surface tensions 13.31 and 19.37 mN m−1 were achieved at certain concentration of dyes 1 and 3, respectively. High surface activity achieved using fluorocarbon groups could improve the leveling properties because of their excellent penetration.
3. Results and discussion 3.1. The surface activity of novel dyes containing fluorocarbon groups The novel surface-active dyes 1 and 3 containing fluorocarbon groups were synthesized from Reactive Red X-3B and Reactive Blue X-BR containing a dichlorotriazine group (Scheme 4). High surface activity was achieved with fluorocarbon groups. The surface tensions of novel surface-active dyes 1 and 3, Reactive Red X-3B and Reactive Blue X-BR were determined. The results in Fig. 1 show that Reactive Red X3B and Reactive Blue X-BR had no surface activity, and novel dyes 1 and 3 had high surface activity due to the use of fluorocarbon groups. When dyes 1 and 3 concentrations were more than 0.001 mol l−1 , the surface tension of the dyed solu-
3.2. Absorption process of dyes on silk The novel surface-active dyes containing fluorocarbon groups were used for silk as acid dyes. In order to investigate dyeing procedure, the exhaustion on silk of the novel and reactive dyes were compared. Figs. 2–4 show the exhaustion curves for dyes 1–3, 1% (o.w.f.) on silk at pH 4, respectively. Figs. 2–4 indicate that the exhaustions of the novel dyes on silk fabric at first stage were lower than corresponding to the reactive dyes. During the second stage of dyeing, the exhaustions of the novel
Scheme 4.
202
K. Xie et al. / Materials Chemistry and Physics 105 (2007) 199–203 Table 1 Effect of pH value on dye exhaustion on silk (%) Dyes
pH
1 2 3
Fig. 2. Exhaustion of dye 1 and Reactive Red X-3B on silk (1.0% o.w.f., pH 4).
4.0
5.0
6.0
7.0
72.78 70.01 75.65
65.71 65.08 39.13
62.08 63.75 35.65
49.61 26.25 21.74
hydrophobicity, the novel dyes can form micelles in the solution. The hydrophilic sulphonic acid groups outside of the micelles improved water solubility at the initial stage of dyeing process. The number of micelles decreased with temperature rising. At the last stage, therefore, maximum exhaustions of them on silk fabric were higher than those of the reactive dyes. 3.3. Effect of dyeing pH In order to determine the optimum dyeing conditions for novel surface-active dyes, a series of dyeing using 1% (o.w.f.) dyes were carried out from pH 4 to 7. The influence of dyeing pH on the dye exhaustions on silk was listed in Table 1. It clearly shows that the exhaustions of the novel dyes on silk decreased with pH rising. Under acidic conditions, the silk fiber had positive charges and had higher dye absorption ability. With increasing pH, the dye absorption ability was lessened. Therefore, the effect of pH value on dye exhaustion on silk was significant.
Fig. 3. Exhaustion of dye 2 and Reactive Yellow X-RG on silk (1.0% o.w.f., pH 4).
dyes on the silk fabric were almost the same as the reactive dyes. But at last stage, maximum exhaustions of them on silk fabric were higher than those of the reactive dyes. According to exhaustion curves of the dyes, the leveling properties of the novel dyes on silk were better than the reactive dyes. The results clearly show that compared with the reactive dyes, better exhaustions of dyes containing fluorocarbon groups were achieved after dyeing 60 min. It can be observed that the dyeing time of 60 min was necessary to achieve suitable exhaustion. High surface activity could improve the leveling properties because of their excellent penetration. In general, fluorocarbon groups are considered as
3.4. Effect of salt concentration The effect of salt concentration on the dye exhaustion on silk was discussed at pH 4, and the results were shown in Table 2. It can be seen that increasing the concentration of sodium sulphate from 0 to 15 g l−1 led to a slight increase in the exhaustion of the novel dyes on silk. A further increase in salt concentration gave little further improvement in the dye exhaustion, even a little decrease. 3.5. Effect of liquor ratio Dyeing of the novel dyes (1% o.w.f.) on silk was carried out at different liquor-to-goods ratio (10:1, 20:1, 30:1), sodium sulphate 15 g l−1 , pH 4, 95 ◦ C. The effect of liquor ratio on the exhaustion was shown in Table 3. It can be seen that when the liquor ratio was raised from 10:1 to 30:1, the exhaustions of dyes 1 and 2 on silk had significant decrease, and that of dye 3 on silk had slight decrease. Table 2 Effect of sodium sulphate concentration on dyes exhaustion on silk (%) Dyes
Fig. 4. Exhaustion of dye 3 and Reactive Blue X-BR on silk (1.0% o.w.f., pH 4).
1 2 3
Sodium sulphate concentration (g l−1 ) 0
2
5
10
15
20
73.06 70.13 75.65
72.99 72.50 78.26
73.51 75.12 79.13
75.30 78.75 83.48
79.98 80.11 87.83
79.02 77.5 87.83
K. Xie et al. / Materials Chemistry and Physics 105 (2007) 199–203 Table 3 Effect of liquor ratio on dye exhaustion on silk (%) Dyes
Liquor ratio
1 2 3
10:1
20:1
30:1
80.26 80.12 87.39
71.17 79.38 86.08
71.95 60.05 83.48
1 2 3
Dye 1 Dye 2 Dye 3
3.7. Fastness properties
Dyes concentration (%) o.w.f. 0.5
1.0
2.0
5.0
88.65 84.15 91.19
80.26 80.12 87.39
70.13 69.52 76.59
60.42 51.52 59.43
Table 5 Fastness properties of the novel dyes on silk Dyed sample
5.0% o.w.f.), liquor ratio being 20:1, sodium sulphate 15 g l−1 , pH 4, 95 ◦ C. The results were listed in Table 4. Table 4 shows that with the dyes concentration rising, the exhaustions of dyes 1–3 on silk gradually decreased.
The results of fastness tests for dyes 1–3 on silk fabric were summarized in Table 5. The results clearly indicate that the light fastness, rubbing fastness and washing fastness were all very good, especially light fastness.
Table 4 Effect of dyes concentration on exhaustion on silk (%) Dyes
203
Rubbing fastness
Washing fastness
Dry
Wet
SC
SW
5 5 5
4–5 4–5 4–5
4–5 5 5
5 4 4–5
Light fastness
4. Conclusions The novel surface-active dyes containing fluorocarbon groups were synthesized. Novel dyes containing fluorocarbon groups imparted high surface activity due to use fluorocarbon groups. The dyes on silk had good leveling properties. The suitable process of the novel dyes on silk was: sodium sulphate 15 g l−1 , pH 4, liquor ratio being 20:1, 95 ◦ C for 60 min. The fastness properties on silk were good. References
5 5 5
SC: staining on cotton; SW: staining on silk.
3.6. Effect of dyes concentration To examine the influence of dyes concentration, the dyeing was carried out at different dyes concentration (0.5, 1.0, 2.0,
[1] W. Zuwang, Rev. Prog. Color. 28 (1998) 32. [2] M.L. Gulrajani, Rev. Prog. Color. 23 (1993) 51. [3] C. Zaisheng, J. Guochuan, Q. Yiping, J. Appl. Polym. Sci. 91 (2004) 3579. [4] Y.A. Youssef, A.A. Mousa, Color. Technol. 118 (2002) 325. [5] C. Lubo, W. Zuwang, Dyestuffs Ind. 36 (1999) 1. [6] C. Xudong, Dyestuffs Color. 40 (2003) 10. [7] P. Guoguang, Dyestuffs Color. 41 (2004) 71.