Journal of Textile Research ›› 2024, Vol. 45 ›› Issue (10): 128-136.doi: 10.13475/j.fzxb.20231102501

• Dyeing and Finishing Engineering • Previous Articles     Next Articles

Preparation of benzo[a]phenoxazine based functional dyes and their application on modified polyester fabrics

HAN Huayu1, YANG Wenlong2, WANG Fu1, HU Liu1,3(), HU Yi1   

  1. 1. College of Textile Science and Engineering, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
    2. Zhejiang Shengfa Textile Printing and Dyeing Co., Ltd., Huzhou, Zhejiang 313100, China
    3. College of Chemistry and Chemical Engineering, Donghua University, Shanghai 201620, China
  • Received:2023-11-14 Revised:2024-06-18 Online:2024-10-15 Published:2024-10-22
  • Contact: HU Liu E-mail:liuhuhl@zstu.edu.cn

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Abstract:

Objective Functionally modified polyester textiles with high added value have significant development value in the fields of both domestic and industrial textiles. Cationic dyeable modified polyester fabrics are often endowed with enhanced functionality by coating and cross-linking with polymers. However, these modifications can compromise their breathability and adversely affect their apparent color and luster. This study aims to synthesize a novel photo-functional benzo[a]phenoxazine cationic dye, aim to achieve an integrated construction of both color and functionality on cationic dyeable modified polyester fabrics via a streamlined dyeing process.

Method Two dyes, 5-ethylenediamino-9-(diethylamino)benzo[a]phenoxazine ammonium chloride (N1) and 5-propylamino-9-(diethylamino)benzo[a]phenoxazine ammonium chloride (N2), were synthesized via nucleophilic substitution reactions. The structural characterizations of these dyes were accomplished using proton nuclear magnetic resonance (1H NMR) spectroscopy and Fourier transform infrared (FT-IR) spectroscopy. Additionally, 5-amino-9-(diethylamino)benzo[a]phenoxazine ammonium sulfate (Nile Blue sulfate, N3) was selected as the comparative dye. The photophysical and chemical properties of these dyes, along with their dyeing performance on cationic dyeable modified polyester fabrics, were investigated using a color matching instrument, UV-visible spectrophotometer, and fluorescence spectrophotometer. The fluorescence emission and photodynamic properties of the dyed fabrics were also examined.

Results This study was focused on two photo-functional benzo[a]phenoxazine cationic dyes for dyeing cationic dyeable modified polyester fabrics.1H NMR and FT-IR confirmed the successful synthesis of 5-ethylenediamino-9-(diethylamino)benzo[a]phenoxazine ammonium chloride (N1) and 5-propylamino-9-(diethylamino)benzo[a]phenoxazine ammonium chloride (N2). The maximum absorption wavelengths (λmax) of the three dyes in water were 648 nm, 639 nm, and 635 nm, respectively, presenting a blue color. In DMF, both λmax and the maximum emission wavelengths (λem) of the three dyes exhibited a blue shift, with the solution color changing from blue to red and displaying orange-yellow fluorescence under a 365 nm ultraviolet lamp, which may be caused by the molecular deprotonation. Dye N2, with a propyl amino group at the 5-position, achieved a dye-uptake of 99.65% on cationic dyeable modified polyester fabric, demonstrating rapid dye uptake with good levelness. The a*(green-red axis) and b*(blue-yellow axis) values of the fabrics dyed with these dyes were all negative, while the lightness (L*) values were positive, indicating that the dyed fabric exhibited a bright blue with a greenish tint. Due to the enhanced π-π* transition caused by the propyl amino group in dye N2, fabric dyed with 1% (o.w.f) dosage exhibited strong red fluorescence, while the increasing dye dosage led to fluorescence self-quenching on the fabric. The photodynamic properties of the dyed fabrics were investigated. The bleaching rate of 1,3-diphenylisobenzofuran on fabric dyed with N3 (6%, o.w.f) reached over 80% after 40 min of red-light exposure. Under the same condition, the bleaching rate for fabric dyed with N1 was 63.5%, demonstrating that these dyed fabrics have the ability of photoinduced singlet oxygen generation. Additionally, color fastness tests indicated that the fabrics dyed with these three dyes (1%, o.w.f) achieved excellent rubbing and washing fastness which is over level 4, and the light fastness were in the range of levels 3 to 4.

Conclusion In this work, two benzo[a]phenoxazine-based functional dyes (N1 and N2) were developed and characterized. N1 and N2 exhibit solvatochromic behaviors, and they have excellent dyeing performance on cationic dyeable modified polyester fabrics with high dye-uptake rate and good color fastness. The dyed fabrics show red fluorescence emission and photodynamic1O2 generation ability. Dye N1 with an ethylenediamine group at the 5-position has better photodynamic1O2 generation performance than the dye N2. This offers a novel approach to the development of multicolor textiles for health and safety protection. In future research on benzo[a]phenoxazine cationic dyes, further modulation of molecular structure could enhance the photodynamic generation of reactive oxygen species by the dyes and the antibacterial activity of the dyed fabrics, thereby enriching the color palette and functional versatility of health protection textiles.

Key words: dyeing, benzo[a]phenoxazine, functional dye, cationic dyeable modified polyester, fluorescence, photodynamic

CLC Number: 

  • TQ614.2

Fig.1

Synthesis route of compound. (a) 5-diethylamino-2-nitrosophenol hydrochloride; (b)Dyes N1 and N2"

Fig.2

Schematic diagram of oxidative decomposition of DPBF"

Fig.3

Spectra of N1, N2 and N3. (a) UV-visible absorption spectra of N1, N2 and N3 in aqueous solution; (b) Fluorescence emission spectra of N1 in different solvents; (c) Fluorescence emission spectra of N2 in different solvents; (d) Fluorescence emission spectra of N3 in different solvents"

Tab.1

Spectral data of dyes in different solvents"

染料 溶剂 λmax/
nm		 λem/
nm		 斯托克
斯位移/
nm		 ε/
(L·mol-1·cm-1)
H2O 648 682 34 25 375.36
DMF 511 605 94 18 080.56
N1 EA 503 585 82 11 707.32
DCM 645 665 20 28 666.91
EtOH 640 671 31 19 292.52
H2O 639 679 40 17 090.54
DMF 507 602 100 10 492.96
N2 EA 494 584 90 12 935.74
DCM 633 661 25 26 726.78
EtOH 636 668 32 24 237.17
H2O 635 679 44 55 997.14
DMF 505 593 88 46 637.15
N3 EA 496 579 83 20 486.69
DCM 629 659 30 30 607.09
EtOH 627 667 40 99 586.79

Fig.4

Dyeing rate curves of dyes N1, N2, and N3"

Fig.5

Influence of dye dosage on K/S value of fabrics"

Tab.2

Color parameters of dyes for cationic dyeable modified polyester dyeing"

染料 K/S值 λmax/nm L*值 a*值 b*值 Sr值
N1 17.23 640 40.95 -15.09 -30.26 0.022
N2 15.34 640 45.85 -22.77 -22.72 0.011
N3 22.12 640 32.32 -11.34 -32.92 0.017

Fig.6

Fluorescence emission spectra and fluorescence photos of fabrics. (a) Fluorescence emission spectra of dyed fabrics at different dye concentrations (λex=365 nm); (b) Fluorescence photographs of dyed fabrics at different dye dosage under 365 nm UV light"

Fig.7

Photo-induced bleaching efficiency of dyed fabrics to DPBF"

Fig.8

Schematic diagram of photodynamic effect of dyed fabric"

Tab.3

Color fastness of dyed fabrics 级"

染料
编号		 耐摩擦
色牢度		 耐洗色牢度 耐光
色牢度
干 湿 变色 沾色
羊毛 腈纶 涤纶 锦纶 棉 醋酯
N1 4~5 4~5 4~5 4~5 4~5 4~5 4 4~5 4~5 3~4
N2 4~5 4~5 4~5 4~5 4~5 4~5 4~5 4~5 4~5 4~5
N3 4 4 4~5 4~5 4~5 4~5 4 4~5 4~5 3~4
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