Keywords: silk, silk modified, reactive dyes, dyeing, salt-free dyeing
Because of the unique silk silk Ming, excellent drape and good luster, with light wear comfortable, soft touch ease, while moisture absorption, moisture permeability, good ventilation, has always been known as the king of fibers. However, the traditional general use of silk dyeing and mordant dyes, acid dyes such as dyeing, bleaching easily dyed silk, silk market share has made little.
In order to improve the wash fastness of silk, in recent years, the reactive dyeing of silk to the increase in reports [1-4]. Dyed silk with reactive dyes, reactive dyes in particular, double-dyed silk, wash fastness up to 4 , 4 ~ 5 [5-7]. However, during reactive molecular design, in order to make the fabric easy to cook after transfection floating color, dye molecules are introduced in more ionic groups, easily makes the reactive dye soluble in water. in silk dyeing, the dyeing rate of the general, fixing the rate is not high, dye utilization is very low. which, in recent years, embarked on the ion silk dyeing of modified and other solvents . for cations and anions on the silk can be substantially modified to improve silk fixation rate [9-11], the modified solid-color silk part of the nearly 90%, and achieve low salt stain. Although the modification of existing research reports Silk fixation rate has been high, but there is still a need to increase the space, therefore, the paper reported the cationic modification of silkworm silk and high fixation rate of salt-free dyeing. 1 Experimental section
1.1 Experimental materials Habotai 11218 (Nanchong Silk Company), trimethylamine (chemical pure, Shanghai Reagent three plants), epichlorohydrin (analytically pure, Chengdu Kelong Chemical Reagent Factory), tetrabutylammonium bromide (analytically pure, Shanghai Chemical Reagent Company), reactive red X-3B100%, reactive brilliant blue X-BR140%, Reactive Brilliant Orange K-R100%, activated blue B-GLN (chemical dyes, Wenling City, Zhejiang Province).
1.2 Experimental apparatus
TU-1810 UV-visible spectrophotometer (Beijing General Instrument General analysis of limited liability company), SW-12-A washing fastness tester (Wuxi Textile Instrument Factory), CTA assessment of change in color gray card (China Textile Academy the textile industry Standardization Institute), digital temperature water bath HH-4 (Guohua Electric Appliance Co., Ltd.), DHG-9070A electric constant temperature drying oven (on Hai Qixin Scientific Instruments Co., Ltd.), Speclmm GX infrared spectrophotometer (FTIR, U.S. PE firm)
1.3 Experimental Methods
1.3.1 epoxy propyl trimethyl ammonium chloride in the flask by adding 200 mL of trimethylamine (33%), tetrabutylammonium bromide 0.2 g, placed in ice water mixture containing in the constant temperature water bath, thermostatic water bath using magnetic stirring device comes with stirring, while slowly dropping epichlorohydrin, dropping 5 mL / min, epichlorohydrin were added 80 mL (excess), after dropping to End holding 60 min, and then, heating temperature to 35 ℃, and then stirred 3h. reaction after the static 1h, after stratification to be an excessive amount of epichlorohydrin, epichlorohydrin with a separating funnel separation.
[email protected]### Page ###@=================1.3.2 cation of the synthetic silk grafted epoxy propyl trimethyl ammonium chloride, pH adjusted to pH7 with sulfuric acid to about 5 times and then diluted with distilled water. room temperature, the silk impregnated epoxy propyl trimethyl ammonium chloride solution, impregnated time 20 min, liquor ratio 1:10, fully mixed. impregnated dry after rolling out, with liquid rate of 100%. and then oven dried at 50 ℃, 90 ℃ baking 30 min. followed out the washing, drying .
220.127.116.11 General silk dyeing dye concentration was 0.2%, sodium sulfate concentration was 0,10 ~ 60 g / L. dyeing time 50 min, fixing time 30 min, liquor ratio 1:50, are fixing with sodium carbonate, sodium carbonate solid color bath a final concentration of 0.2%.
Reactive red X-3R100%, reactive brilliant blue X-BR140%, dyeing temperature 30 ℃, fixing temperature 400C; Reactive Brilliant Orange K-R100% dyeing temperature is 80 ℃, fixing temperature 90 ℃; activated blue B-GLN dyeing temperature, solid-color temperature were 60 ℃.
Cook floating color temperature 98 ℃, boiling floating color bath of sodium carbonate 0.2%, 0.1% soap, bath ratio 1:50, time 30 min.
Dyeing rate = 1-A1/A0, A1 for the fixing bath after the dye absorbance, A0 the absorbance of dye liquid.
Fixation rate = 1 - (A1 + A2) / A0, A2 is the absorbance of cooking floating color bath.
18.104.22.168 cationic silk dyeing cationic dyeing silk, silk dyeing and general conditions of the same, but not salt, as salt-free dyeing.
1.3.4 fastness fastness test: 98 ℃, bath ratio of 1:100, soaping 30 min, 0.2% sodium carbonate bath soap, soap 0.1%, and then assessing change in color with a gray card CTA determine the level of color fastness.
[email protected]### Page ###@=================1.3.5 cation Silk Silk IR cation with Speclmm GX infrared spectrophotometer, the infrared spectra of cationic graft case. 2 Results and discussion
IR 2.1 cationic synthetic silk propyl trimethyl ammonium chloride, pH value between 10.8 ~ 11.1, if that is not acid pH adjusted to 7 to about graft on silk change nature, the silk will be yellowed. Therefore, the need for pH adjustment.
Figure 1,2 is a cationic silk and silk in the infrared spectra of normal.
Figure 1 3 430.20 cm-1 for the cis, free state Chung amide N-H stretching vibration, 1 702.84 cm-1 for the cis-, Chung-free state in the C = O amide stretching vibration (amide Ⅰ spectrum band), 1 504.5 cm-1 for the N-H bending vibration (amide Ⅱ bands), 1 410.7 cm-1 and 1 238.53 cm-1 to C-N stretching vibration (amide bands Ⅲ ) and, 1 095.03 cm-1 for non-conjugated fatty amine C-N stretching vibration, 722.69 cm-1 for the Chung-amide Ⅳ, Ⅴ bands.
Figure 2 shows the spectral data: 3 293.16 cm-1 is a poly-association and the body-OH stretching vibration bands, 1 650.67 cm-1 for the tert-amide C = O stretching vibration (amide Ⅰ band) , Figure 1 Infrared spectra of silk fibroin is not tert-amide C = O stretching vibration, and only 1 702.84 cm-1 of the Chung-amide in the C = O stretching vibration, indicating that epoxy propyl trimethyl ammonium chloride ammonium in the grafting reaction with silk protein for some time connected to the amide N atom of the arbitration, the formation of a tertiary amide. 1 514.95 cm-1 has a strong trans-N-H and C-N bending vibration (amide Ⅱ bands), 1 231.99 cm-1C-N stretching vibration (amide Ⅲ bands) and 1 161.93 cm-1 and 1 070.41 cm-1 2 medium intensity bands are C-O (H), C-O-C and fatty tertiary amine C-N stretching vibration bands, 638.49 cm-1 has a strong C-O-H vibrational spectra of curling.
Comparative analysis shows that graft cationic fibroin contains a lot of-OH, an increase of-CON (R1R2) (tert-amide), C-O-C and a small amount of-COOR, and-NH2 little. That propylene trimethylammonium chloride and silk fibroin graft reaction, the epoxy group with-OH,-NH2,-COOH,-CONHR amine chemical reaction occurred. epoxypropyl generated with-OH-C-O- C-, and-CONHR Chung amide anti-generated-CON (R1R2) (tert-amide), and the-COOH produces-COOR, and-NH2 reaction no longer contains SF-NH2.
[email protected]### Page ###@=================2.2 Reactive Red X-3B100% of the staining Figure 3 is a reactive red X-3B100% sodium concentrations in different conditions, the dye uptake and fixation. can be seen from the figure, reactive red X-3B100% of the silk dye uptake and fixation rates are very low, even if the concentration of sodium sulfate 60 g / L, the dye uptake and fixation rate of ten per cent only. show that the reactive red X-3B100% have good water-soluble and if the use of their silk dyeing, its utilization will be very low.
Cation of silk with reactive red X-3B100% staining, in the absence of salt in the case, the infection rate 99.32%, 96.60% fixing rate, soaping fastness 5. Unmodified silk fastness after dyeing only four.
Cation silk dyeing, the dye residue is only very light color. Silk soaping generally use 40 ℃, the test cation wash fastness of silk dyed just how firm, this paper is 98 ℃ soaping , conditions are very harsh, but still achieve the 5 color fastness, and do not promote the use of sodium sulfate staining of true salt-free dyeing.
If the silk cationic modification, the synthesis of epoxy propyl trimethyl ammonium chloride is not diluted, but was modified with liquid, the modified silk dyeing rate and fixation rate can reach 100%, soaping prison Level 5. If the epoxy propyl trimethyl ammonium chloride modified after 15 times dilution, the dyeing rate can reach 98.50%, fixation rate was 94.3%, soaping still up 4 5.
This indicates that the modified high fastness of silk and silk, then a large number of cations and some anions related to the role of electric He Kulun not entirely reactive dyes and silk covalent contribution.
2.3 Reactive Brilliant Blue X-BR140% Figure 4 is a reactive dye brilliant blue X-BR140% sodium concentrations in different conditions, the dye uptake and fixation. Can be seen from the figure, reactive brilliant blue X-BR140 % of dye uptake and fixation rate than reactive red X-3B100% much higher, indicating that reactive brilliant blue X-BR140% on silk dyeing with good immediacy. it is not linear with the increase in sodium concentration It started fast, then slow down change, there is saturated. Reactive Blue X-BR140% of the modified silk dyeing, the dyeing rate of 99.88%, 99.86% rate of solid color, soap wash fastness 5. unmodified silk dyeing their fastness to 4. the dye bath and fixing bath clear, do not see any residual dye. silk grafted cation, the anions has a very good dye adsorption. cationic dye silk on the role of the charge may not only related to the role, but also directly correlated with the dye. Reactive Brilliant Red X-3B100% of good water solubility, poor directly, the dye uptake and fixation color ratio is relatively lower. and Reactive Blue X-BR140% itself, the dye uptake and fixation rates are better, the modified silk dyeing rate and fixation rate would better be able to exhaust dyeing.
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2.4 Reactive Brilliant Orange K-R100% 5 is a graph of reactive brilliant orange K-R100% dye uptake and fixation with the relationship between sodium concentration. From the figure we can see, Reactive Brilliant Orange K-R100 % of the silk dyeing in general, direct, dye uptake and fixation rate than reactive brilliant blue X-BR140% little worse, in the absence of sulfate, only reactive brilliant blue X-BR140% to 25%.
Reactive Brilliant Orange K-R100% of the cationic dye silk was 97.50%, fixation rate was 97.00%, soaping fastness 5. Unmodified silk dye Reactive Brilliant Orange K-R100% fastness of 4 ~ 5.
May be reactive brilliant orange K-R100% in the absence of salt when dyeing silk itself directly of not very good, while reactive brilliant orange K-R100% of the dyeing temperature is 80 ℃, fixing temperature was 90 ℃, when the dye temperature is too high, even in the modified silk dyeing, but also a small amount of dye can not be under high temperature dyeing, resulting in fixation rate decreases. but overall modified silk dyeing rate and fixation rate were relatively high.
B-2GLN 2.5 activated blue staining Figure 6 is activated blue B-2GLN in silk dyeing, dye uptake and fixation with the relationship between sodium concentration. From the figure we can see, although activity on the blue B-2GLN dye uptake and fixation rate increases with the sodium concentration of more moderate upward trend, but no salt, the dye uptake and fixation rate of reactive brilliant blue similar to a reactive red X-3B100% and reactive brilliant orange K -R100% 4 times.
Cation of activated blue B-2GLN silk dyeing, the dyeing rate of 99.93%, 99.92% fixation, washing fastness 5. Unmodified activated blue silk dyeing fastness B-2GLN 4 ~ 5.
Integrated reactive red X-3B100%, reactive brilliant blue X-BR140%, Reactive Brilliant Orange K-R100% of the silk and the dyeing of modified silk can be found, reactive brilliant blue X-BR140%, activity in the absence of blue B-2GLN salt, dye uptake and fixation rate of around 20%, relatively high dyeing of modified silk fixation rate can reach 99.86 and 99.92%%; and reactive red X-3B100%, activity Brilliant Orange K-R100% in the absence of salt, dye uptake and fixation rate is very low, only about 5%, with the modified silk dyeing, the dyeing rate and fixation rate can not be close to 100%, indicating that modification cation silk dyeing, the dyeing rate and fixation rate although the positive charge carried by the silk, but silk and dye itself directly correlated.
B-2GLN 2.6 activated blue dye cationic dye silk dyeing rate with the time variation of Figure 7 is activated blue B-2GLN dye cationic dye silk dyeing rate with the variation of the time. From the figure can be see modified silk dye quickly, in 4 min, the dye in the dyeing of modified silk on the already completed, there is no residue in the dye residues, the infection rate 99.90%. Of course, the dyeing process As the diffusion process also includes penetration, dyeing process was not completed.
[email protected]### Page ###@=================so fast on the dye should be a cationic dye silk with a large number of positive charge on the anionic dyes have a very strong force due to Coulomb force. Therefore, the dyeing process should be quick flip, so that the dye evenly.
2.7 Uniformity of cationic dyeing silk dyeing uniformity when the main cationic distribution and staining correlated with the degree flip, and when cationic modified cation distribution in the silk is even more important. Test found that if the modification time on the distribution of cations in the silk itself is uneven in the subsequent dyeing, no matter how flip, plus leveling agent, etc., cationic dye can not even silk. cationic dye distribution over the place dyeing, the few places on the dye less. Therefore, in the silk for cationic modification, the liquor ratio can not be too small; the same time, when the cation and neutral between the negatively charged carboxyl electrostatic adsorption quickly, so silk impregnated with a cationic modified solution, it can quickly turn and vibration, making silk uniform adsorption of cationic modifier. 3 Conclusion of the silkworm silk to modification, can greatly enhance the rate of silk dyeing, fixation and color fastness. part of the dye fixation rate can reach 100%, achieving exhaust dyeing; wash fastness can reach 5; the same time, salt-free dyeing, the dyeing does not produce salt water. Therefore, the change of silkworm silk Cationic dyeing is a very effective high dye uptake, fixation, washing fastness, salt-free dyeing methods, have great potential. References:
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