G Model
CCLET 3136 1–4
4
X.-J. Zhao et al. / Chinese Chemical Letters xxx (2014) xxx–xxx
16
14
12
by M3. It is also an indirect piece of evidence for covalent bond
formation between AMODB and silk fibers.
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M1, before stripping
M1, after stripping
M2, before stripping
M2, after stripping
M3, before stripping
M3, after stripping
4. Conclusion
245
Under the guidance of the finding that the tyrosine residues in
proteins could undergo three-component Mannich-type reactions
withformaldehydeand electron-richaniline-containingcompounds,
which forms covalent bonding connections between the protein of
interest and the anilines with high levels of selectivity under
relativelymild conditions, an orange electron-rich aniline-containing
dye AMODB was designed and readily synthesized for Mannich-type
dyeing on silk. It is proven that dye AMODB successfully reacts with
silk fiber under mild dyeing conditions according to a Mannich-type
dyeing mechanism by some indirect evidence such as higher color
depth, better anti-stripping ability to DMF and better washing
fastness in comparison to the control acid dye on silk fabric by the
acidic dyeing method. The Mannich dyeing method can bedeveloped
into a new energy-efficient, environmentally friendly and reactive
dyeing method suitable for silk, which might have much wider
application prospects over the traditional reactive dyes.
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10
8
6
4
2
0
400
450
500
550
600
650
700
Wavelength (nm)
Fig. 1. The K/S spectra of dye AMODB and C.I. Acid Yellow 11 on silk fabrics by
Mannich-type dyeing (M1), Mannich-type dyeing short of formaldehyde (M2) and
acidic dyeing (M3) before and after color stripping. Dyeing conditions: (M1)
AMODB, 3% owf, n (formaldehyde):n (AMODB) = 3:1, 75:1 liquor ratio, pH 5.5, 30 8C,
10 h; (M2) AMODB, 3% owf, no formaldehyde, 75:1 liquor ratio, pH 5.5, 30 8C, 10 h;
(M3) C.I. Acid Yellow 11, 3% owf, 40:1 liquor ratio, pH 5.5, 90 8C, 90 min.
Acknowledgments
262
The work was supported by the National Natural Science Q34 263
Foundation of China (nos. 21106135 and 51173168), Zhejiang
Provincial Key Innovation Team(no. 2010R50038), Zhejiang Provin-
cial Top Key Academic Discipline of Chemical Engineering and
Technology, and ‘‘521’’ Talent Project of Zhejiang Sci-Tech University.
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dye silk fabrics with the traditional acidic dyeing method (M3) to
compare the type of bonding with M1.
The soap-washed dyeing samples of M1, M2 and M3 were then
color stripped by DMF to verify the type of binding between dyes
and silk fibers. Fig. 1 shows the K/S spectra of M1, M2 and M3
before and after DMF stripping. It can be seen that the silk fabrics
are successfully dyed by M1, M2 and M3 with different color depth.
Both of the dyed silk fabric samples by M1 (before and after color
References
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stripping by DMF) showed the highest K/S value and the
DK/S is
lower relative to the K/S value before stripping, which is a strong
evidence for covalent bond formation via the Mannich reaction. By
comparison of the K/S spectra of M1 and M2 before and after color
stripping, it is easily concluded that formaldehyde plays an
important role in the Mannich dyeing. The absence of formalde-
hyde circumvents the Mannich reaction and the absorbed dyed on
silk fabric is easy to stripped by DMF. As is well known that the acid
dyes can combine with silk through ionic bonds, which is proved to
be the case for dyed silk fabric sample with C.I. Acid Yellow 11. The
great decline of K/S value of M3 after color stripping reveals the fact
that the ionic bonds between dyes and silk fibers can be readily
broken by polar solvent DMF. It can be predicted from the
aforementioned results that the Mannich dyeing really happens
among AMODB, formaldehyde and silk despite of the absence of
direct spectral data.
Table 1 shows the washing and rubbing fastness test results of
dyed silk fabrics by the M1 and M3 processes. Clearly, the dyed
sample by M1 exhibits same rubbing fastness and superior
washing fastness in comparison with those of the dyed sample
Table 1
Color fastness properties of AMODB by M1 and C.I. Acid Yellow 11 by M3 on silk
fabrics.
Dye
Dyeing
process
Washing
fastness
Rubbing
fastness
Color
Staining
Staining
of silk
Dry
Wet
change
of cotton
AMODB
M1
M3
4–5
3
4–5
4
4–5
3–4
3–4
3–4
3
3
C.I. Acid
Yellow 11
Please cite this article in press as: X.-J. Zhao, et al., Synthesis of an electron-rich aniline-containing dye and its dyeing behaviors on silk