Supercritical carbon dioxide dyeing method for achieving high disperse dye exhaustion

Abstract

The objective of the present invention is to provide a supercritical carbon dioxide medium dyeing method for achieving a high disperse dye exhaustion rate. In the supercritical carbon dioxide medium dyeing method for achieving a high disperse dye exhaustion rate, a co-solvent that increases the dissolution rate and solubility of the disperse dye in the supercritical carbon dioxide medium is added to the dyeing system of the disperse dye of polyester fiber or its product, and the interactions between each substance, such as intermolecular interaction between the co-solvent and the supercritical carbon dioxide medium>intermolecular interaction between the co-solvent and the disperse dye>intermolecular interaction between the supercritical carbon dioxide medium and the disperse dye, are established, the solubility of the co-solvent in the supercritical carbon dioxide medium is higher than that of the disperse dye, and the co-solvent is solidified at a separation temperature of 30 to 50°C and a separation pressure of 5 to 6 MPa. The co-solvent used in the present invention significantly increases the solubility of the disperse dye in polyester fiber, while being easily separated from supercritical carbon dioxide, realizing the reuse of carbon dioxide.

Description

[Technical field]

[0001] The present invention relates generally to dyeing technology, and more particularly to a supercritical carbon dioxide medium dyeing method that can achieve a high disperse dye exhaustion rate. [Background technology]

[0002] As a non-aqueous dyeing method for polyester fiber, supercritical carbon dioxide medium dyeing uses supercritical carbon dioxide instead of the aqueous medium used in traditional dyeing. This method can reuse carbon dioxide, does not require auxiliary agents or wastewater, provides excellent levelness and dyeing reproducibility, and does not require drying, so it reduces time costs and energy consumption compared to conventional techniques.

[0003] Carbon dioxide is a linear molecule with no polarity, and has good solubility for weakly polar disperse dyes, while the high temperature and pressure associated with the supercritical state can also improve the plasticity of polyester fibers, making supercritical carbon dioxide a very suitable medium for dyeing polyester fibers using disperse dyes. However, there is still the problem of low dyeing rate in partial disperse dyes dyed with supercritical carbon dioxide. There are currently two main methods for increasing the dyeing rate for supercritical carbon dioxide dyeing. One is to add a small amount of co-solvents such as acetone or ethanol to the supercritical carbon dioxide medium during dyeing, but these co-solvents are easily volatile and difficult to effectively separate from the supercritical carbon dioxide medium, so the recovered supercritical carbon dioxide medium has low purity and cannot be reused. The other is to use new dyes suitable for supercritical carbon dioxide dyeing, but the development of new dyes is difficult because it takes time and costs money.

[0004] In other words, a simple method for avoiding the above defects and increasing the dyeing rate in supercritical carbon dioxide dyeing is a significant problem. Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion rate, and overcomes the difficulties in the prior art. [Means for solving the problem]

[0006] In response to the above problems, the present invention selects the following means for solving the problems.

[0007] The supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion is to add a co-solvent to the dyeing system of polyester fiber or its product, which improves the dissolution rate and solubility of the disperse dye.

[0008] The solubility of the co-solvent in the supercritical carbon dioxide medium is higher than that of the disperse dye. In the dyeing system, the interactions between each substance are as follows: intermolecular interaction between the co-solvent and the supercritical carbon dioxide medium > intermolecular interaction between the co-solvent and the disperse dye > intermolecular interaction between the supercritical carbon dioxide medium and the disperse dye.

[0009] The dyeing system of the disperse dye in the supercritical carbon dioxide medium of the present invention contains cosolvents. These cosolvents have a higher solubility in the supercritical carbon dioxide medium than the disperse dye, and can dissolve quickly in the supercritical carbon dioxide medium. In addition, there is a stronger intermolecular interaction (mainly π-π stacking) between the cosolvent and the disperse dye in the present invention, that is, there is an interaction between each substance, that is, the intermolecular interaction between the cosolvent and the supercritical carbon dioxide medium>the intermolecular interaction between the cosolvent and the disperse dye>the intermolecular interaction between the supercritical carbon dioxide medium and the disperse dye, so that the disperse dye dissolved in the supercritical carbon dioxide medium quickly combines with the cosolvent, and its solubility is significantly improved. Furthermore, when the content of the cosolvent is sufficiently large, the combining process between the disperse dye and the cosolvent becomes more obvious, and the improvement of the dissolution rate and solubility of the disperse dye becomes clear.

[0010] The co-solvent of the present invention is solidified at a separation temperature of 30-50°C and a separation pressure of 5-6MPa. The separation temperature and pressure mentioned above are the temperature and pressure at which the supercritical carbon dioxide medium gasifies and precipitates the dissolved dye and co-solvent. The co-solvent in the prior art is acetone, ethanol, etc., which is difficult to separate from supercritical carbon dioxide, making it difficult to reuse carbon dioxide. However, the co-solvent of the present invention is solidified at the separation temperature and separation pressure, and can be separated from supercritical carbon dioxide in a general-purpose separation tank after dyeing is completed. The pressure in the separation tank is lower than the supercritical pressure, where the supercritical carbon dioxide gasifies and precipitates the co-solvent. However, co-solvents such as acetone and ethanol are still highly volatile under such separation conditions, so they can hardly be separated from carbon dioxide.

[0011] High disperse dye exhaustion rate means that the exhaustion rate is 90.18-99.97%.

[0012] The supercritical carbon dioxide dyeing method of the present invention, which aims to achieve high exhaustion of disperse dyes, increases the exhaustion rate by 123% to 194.7% compared to the comparative method. The only difference between the two methods is that the comparative method does not use the co-solvent.

[0013] Preferred embodiments of the present invention are set forth below.

[0014] In the supercritical carbon dioxide medium dyeing method of the present invention aimed at achieving a high dyeing exhaustion rate of disperse dye, the binding strength between the disperse dye and polyester fiber or its product in the dyeing system is greater than the binding strength between the disperse dye and other substances, and the binding strength between the co-solvent and supercritical carbon dioxide fluid is greater than the binding strength between the co-solvent and other substances.

[0015] In a dyeing system in which co-solvent, disperse dye, supercritical carbon dioxide and polyester fiber or its product are mixed, polyester fiber or its product and disperse dye, which have similarly weak polarity, are easily combined with each other, while co-solvent is more easily combined with supercritical carbon dioxide than polyester fiber or its product. That is, the bonding strength between disperse dye and polyester fiber or its product is greater than the bonding strength between disperse dye and other substances (co-solvent, supercritical carbon dioxide), and the bonding strength between co-solvent and supercritical carbon dioxide fluid is greater than the bonding strength between co-solvent and other substances (disperse dye, polyester fiber or its product). Therefore, when a large amount of disperse dye and supercritical carbon dioxide fluid dissolved in the co-solvent comes into contact with polyester fiber or its product, the disperse dye is constantly adsorbed by polyester fiber or its product and diffuses into the fiber, but the co-solvent remains in the supercritical carbon dioxide without bonding with polyester fiber or its product, that is, in the dyeing tank, the disperse dye in the dyeing medium is constantly consumed, and the co-solvent is not consumed.

[0016] Since the co-solvent dissolved in the supercritical carbon dioxide is not consumed in the dyeing tank, the supercritical carbon dioxide returning from the dyeing tank can still increase the dissolution rate and solubility of the disperse dye in the co-solvent when passing through the dyeing tank with the disperse dye. Therefore, the concentration of disperse dye carried by the supercritical carbon dioxide in each dyeing cycle is higher than that of the prior art, and more dye is bonded to polyester fiber or its product in the same dyeing time. This is the reason for the improvement of the dyeing rate in the present invention.

[0017] In the supercritical carbon dioxide medium dyeing method of the present invention for achieving high dyeing rate of disperse dyes, the cosolvents mentioned are benzoic acid (solubility 5.7 g / L, dissolution rate 1.14 g / (L·min)), nicotinamide (solubility 3.2 g / L, dissolution rate 0.64 g / (L·min)), methyl p-aminobenzoate (solubility 2.5 g / L, dissolution rate 0.24 g / (L·min)), methyl p-hydroxybenzoate (solubility 2.3 g / L, dissolution rate 0.21 g / (L·min)), [ka] (solubility 1.5 g / L, dissolution rate 0.14 g / (L min)) and L-tryptophan methyl (solubility 1.2 g / L, dissolution rate 0.28 g / (L min)).

[0018] The disperse dye mentioned is Disperse Yellow 163 (solubility 2.12*10 ー3 g / L, dissolution rate 1.4*10 ー4 g / (L·min)), Disperse Blue 60 (solubility 4.56*10 ー3 g / L, dissolution rate 2.17*10 ー4 g / (L·min)), Disperse Orange 44 (solubility 2.56*10 ー3 g / L, dissolution rate 2.13*10 ー4 g / (L·min)), Disperse Orange 30:2 (solubility 7.59*10 ー4 g / L, dissolution rate 5.06*10 ー5 g / (L min) [ka] (Solubility 3.56*10 ー3 g / L, dissolution rate 7.12*10 ー4 g / (L·min)), Disperse Blue 104 (solubility 4.12*10 ー3 g / L, dissolution rate 1.87*10 ー4 g / (L min)) or [ka] (Solubility 2.38*10 ー3 g / L, dissolution rate 1.32*10 ー4 g / (L min)).

[0019] In the above two paragraphs, the solubility and dissolution rate were measured using supercritical carbon dioxide at 130°C and 27 MPa as the solvent.

[0020] In the supercritical carbon dioxide medium dyeing method of the present invention for achieving a high disperse dye exhaustion rate, the specific steps are as follows: (1) Powder the disperse dye and co-solvent separately. (2) A powdered disperse dye and a co-solvent are blended in a certain molar ratio to form a mixture. (3) The ground mixture is put into a dye tank, and at the same time, polyester fiber or its product is put into a dye tank, liquid carbon dioxide is introduced, and the temperature and pressure in the dye tank are adjusted to carry out high-temperature and high-pressure dyeing, and the polyester fiber or its product is taken out after dyeing is completed.

[0021] In the step (1) of the supercritical carbon dioxide dyeing method for achieving a high disperse dye exhaustion rate, the molar ratio of disperse dye to co-solvent is 1:1-10.

[0022] In the step (2) of the supercritical carbon dioxide medium dyeing method for achieving a high disperse dye exhaustion rate, the blending is carried out by evaporation crystallization, dry grinding, wet grinding, melt extrusion or melt crystallization.

[0023] In the step (3) of the supercritical carbon dioxide dyeing method for achieving a high disperse dye exhaustion rate, the temperature for high-temperature, high-pressure dyeing is 100 to 150° C., and the pressure is 16 to 30 MPa. Effect of the Invention

[0024] Advantages of the present invention include: (1) The co-solvent adopted in the present invention is environmentally friendly and has no hidden hazards for the safety of the operators. (2) In the present invention, the co-solvent significantly improves the dyeing rate of the disperse dye on the polyester fiber or its product, while the supercritical carbon dioxide is easily separated from the co-solvent and the dye and can be reused, so that the dyeing cost is significantly reduced.

[0025] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as it does not exceed the gist of the present invention. Even if various modifications of the present invention are permitted by a person skilled in the art who has read the contents of the present invention, they are also limited within the scope of the claims of the present invention as equivalent forms of the present invention.

[0026] Example 1 The supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion is carried out in anhydrous supercritical carbon dioxide dyeing equipment, and specifically includes the following steps: (1) Filter cake of Disperse Yellow 163 (purchased from Zhejiang Runtu Co., Ltd., China) and benzoic acid were separately ground into uniformly dispersed powders with no obviously visible debris. (2) Powdered Disperse Yellow 163 and benzoic acid were weighed out in a molar ratio of 1:3, and dry-polished with zirconia beads in an amount 10 times their total weight at a speed of 200 r / min to produce a 100 mesh mixed powder. (3) Put a certain amount of the mixed powder obtained from step (2) into the dye kettle, put 75D / 48F polyester wound yarn with a weight ratio of 100:1 to dye into the dye kettle, and then close the dye kettle and the dye kettle. (4) Open the booster pump and the valve of the carbon dioxide tank, pass liquid carbon dioxide through the dye kettle, open the circulation pump and set the carbon dioxide circulation rate to 30 seconds / cycle. At the same time, heat the entire anhydrous supercritical carbon dioxide dyeing equipment including the dye kettle and dyeing kettle at a rate of 1°C / min. Close the valve of the carbon dioxide tank and the booster pump until the ratio of the volume of liquid carbon dioxide (determined by the flow meter) to the mass of the wound yarn becomes 1L:60g. Continue to heat the dye kettle and dyeing kettle to 130°C at a rate of 1°C / min. Control the pressure of the dye kettle and dyeing kettle at 27MPa (carbon dioxide will reach a supercritical state under conditions of 130°C and 27MPa). Maintain the circulation rate of the supercritical carbon dioxide fluid at 30 seconds / cycle to carry out dyeing for 2 hours. After dyeing is completed, the supercritical carbon dioxide is passed into a separation tank (low-pressure zone) at a temperature of 30-50°C and a pressure of 5-6 MPa, where it is vaporized to precipitate Disperse Yellow 163 and benzoic acid. The pure carbon dioxide gas is then cooled to liquefy and sent to a tank (recovery rate 100%). Open the dyeing tank and dyeing tank, take out the wound yarn, and measure the exhaustion rate of the inner, middle and outer layers of the wound yarn according to the "Method for determining exhaustion rate in high temperature dyeing with disperse dyes" described in the Chinese national standard GB / T 9337-2009, and take the average value as the exhaustion rate of the dye. In the end, the exhaustion rate of Disperse Yellow 163 is 92.17%. The comparison method is basically the same as the above method, except that benzoic acid is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Yellow 163 is measured, which is 33.67% after all.

[0027] Example 2 The specific procedure of the supercritical carbon dioxide medium dyeing method for achieving a high disperse dye exhaustion rate is roughly the same as that in Example 1, with the only difference being that: after closing the valve of the carbon dioxide tank and the booster pump, the dye kettle and dyeing kettle are heated to 120°C at a rate of 1°C / min, and the pressure of the dye kettle and dyeing kettle is controlled at 26MPa, and dyeing is carried out under the conditions of 120°C and 26MPa. The measured dyeing rate of Disperse Yellow 163 was 90.18%. The comparison method is basically the same as the above method, except that benzoic acid is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Yellow 163 is measured, which is 31.52%.

[0028] Example 3 The specific procedure of the supercritical carbon dioxide medium dyeing method for achieving a high disperse dye exhaustion rate is roughly the same as that in Example 1, with the only difference being that: after closing the valve of the carbon dioxide tank and the booster pump, the dye kettle and dyeing kettle are heated to 140°C at a rate of 1°C / min, and the pressure of the dye kettle and dyeing kettle is controlled at 28MPa, and dyeing is carried out under the conditions of 140°C and 28MPa. The measured dyeing rate of Disperse Yellow 163 was 93.15%. The comparison method is basically the same as the above method, except that benzoic acid is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Yellow 163 is measured, which is 34.53%.

[0029] Example 4 The specific procedure of the supercritical carbon dioxide medium dyeing method for achieving a high disperse dye exhaustion rate is roughly the same as that in Example 1, with the only difference being that: after closing the valve of the carbon dioxide tank and the booster pump, the dye kettle and dyeing kettle are heated to 150°C at a rate of 1°C / min, and the pressure of the dye kettle and dyeing kettle is controlled to 29MPa, and dyeing is carried out under the conditions of 150°C and 29MPa. The measured dyeing rate of Disperse Yellow 163 was 93.96%. The comparison method is basically the same as the above method, except that benzoic acid is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Yellow 163 is measured, which is 34.69%.

[0030] Example 5 The specific steps of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion rate are almost the same as those in Example 1, with the only differences being that Disperse Yellow 163 is replaced with Disperse Blue 60 (filter cake, purchased from Zhejiang Runtu Co., Ltd., China), benzoic acid is replaced with nicotinamide, and the molar ratio of 1:3 in step (2) is replaced with a molar ratio of 1:2. The measured dyeing rate of Disperse Blue 60 was 92.55%. The comparison method is basically the same as the above method, except that nicotinamide is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Blue 60 is measured, which is 40.78%.

[0031] Example 6 The specific steps of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion rate are almost the same as those in Example 5, with the only difference being that the molar ratio of 1:2 in step (2) is replaced with a molar ratio of 1:4. The measured dyeing rate of Disperse Blue 60 was 92.55%. The comparison method is basically the same as the above method, except that nicotinamide is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Blue 60 is measured, which is 40.78%.

[0032] Example 7 The specific steps of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion rate are almost the same as those in Example 5, with the only difference being that the molar ratio of 1:2 in step (2) is replaced with a molar ratio of 1:6. The measured dyeing rate of Disperse Blue 60 was 98.69%. The comparison method is basically the same as the above method, except that nicotinamide is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Blue 60 is measured, which is 40.78%.

[0033] Example 8 The specific steps of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion rate are almost the same as those in Example 5, with the only difference being that the molar ratio of 1:2 in step (2) is replaced with a molar ratio of 1:8. The measured dyeing rate of Disperse Blue 60 was 99.52%. The comparison method is basically the same as the above method, except that nicotinamide is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Blue 60 is measured, which is 40.78%.

[0034] Example 9 The specific steps of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion rate are almost the same as those in Example 5, with the only difference being that the molar ratio of 1:2 in step (2) is replaced with a molar ratio of 1:10. The measured dyeing rate of Disperse Blue 60 was 99.97%. The comparison method is basically the same as the above method, except that nicotinamide is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Blue 60 is measured, which is 40.78%.

[0035] Example 10 The specific steps of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion rate are almost the same as those in Example 1, with the only difference being that the original step (2) is replaced by dissolving powdered Disperse Yellow 163 and benzoic acid in a molar ratio of 1:3 in acetone with a total powder:solvent ratio of 1g:50mL, evaporating and crystallizing at room temperature and pressure, and grinding the resulting mixture into a 100 mesh mixed powder. The measured dye exhaustion rate of Disperse Yellow 163 was 92.56%. The comparison method is basically the same as the above method, except that benzoic acid is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Yellow 163 is measured, which is 33.67%.

[0036] Example 11 The specific procedure of the supercritical carbon dioxide medium dyeing method for achieving a high disperse dye exhaustion rate is roughly the same as that in Example 1, with the only difference being that the original step (2) is replaced by adding ethanol to the powdered Disperse Yellow 163 and benzoic acid in a molar ratio of 1:3 in a total powder:ethanol ratio of 1 g:100 μL, and then wet grinding the mixed powder to 100 mesh. The measured dyeing rate of Disperse Yellow 163 was 92.89%. The comparison method is basically the same as the above method, except that benzoic acid is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Yellow 163 is measured, which is 31.52%.

[0037] Example 12 The supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion is carried out in anhydrous supercritical carbon dioxide dyeing equipment, and specifically includes the following steps: (1) Filter cake of Disperse Yellow 163 (purchased from Zhejiang Runtu Co., Ltd., China) and nicotinamide were separately ground into uniformly dispersed powders with no obviously visible debris. (2) Powdered Disperse Yellow 163 and nicotinamide are weighed out in a molar ratio of 1:3 and mixed for 1 minute at 200°C with a double screw at 60 r / min, and the resulting mixture is polished to 100 mesh. (3) Put a certain amount of the mixed powder obtained from step (2) into the dye kettle, put 75D / 48F polyester wound yarn with a weight ratio of 100:1 to dye into the dye kettle, and then close the dye kettle and the dye kettle. (4) Open the booster pump and the valve of the carbon dioxide tank, pass liquid carbon dioxide through the dye kettle, open the circulation pump and set the carbon dioxide circulation rate to 30 seconds / cycle. At the same time, heat the entire anhydrous supercritical carbon dioxide dyeing equipment including the dye kettle and dyeing kettle at a rate of 1°C / min. Close the valve of the carbon dioxide tank and the booster pump until the ratio of the volume of liquid carbon dioxide (determined by the flow meter) to the mass of the wound yarn becomes 1L:60g. Continue to heat the dye kettle and dyeing kettle to 130°C at a rate of 1°C / min. Control the pressure of the dye kettle and dyeing kettle at 27MPa (carbon dioxide will reach a supercritical state under conditions of 130°C and 27MPa). Maintain the circulation rate of the supercritical carbon dioxide fluid at 30 seconds / cycle to carry out dyeing for 2 hours. After dyeing is completed, the supercritical carbon dioxide is passed into a separation tank (the low-pressure zone) at a temperature of 30-50°C and a pressure of 5-6 MPa, where it is vaporized to precipitate Disperse Yellow 163 and nicotinamide. The pure carbon dioxide gas is then cooled to liquefy and sent to a tank (recovery rate 100%). The dye kettle and dyeing kettle are opened, the spools are removed, and the dye exhaustion rate of Disperse Yellow 163 is measured, which turns out to be 92.35%. The comparison method is basically the same as the above method, except that nicotinamide is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lids are opened, the wound yarn is taken out, and the dyeing rate of Disperse Yellow 163 is measured, which is 33.67% after all.

[0038] Example 13 The specific procedure of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion rate is roughly the same as that in Example 12, with the only difference being that the original step (2) is replaced by melt-mixing powdered Disperse Yellow 163 and nicotinamide in a molar ratio of 1:3 at 200°C for 5 minutes, followed by cooling and crystallizing, and polishing to 100 mesh. The measured dyeing rate of Disperse Yellow 163 was 92.21%. The comparison method is basically the same as the above method, except that nicotinamide is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Yellow 163 is measured, which is 34.69% after all.

[0039] Example 14 The specific procedure of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion rate is roughly the same as that in Example 1, with the only difference being that Disperse Yellow 163 is replaced with Disperse Orange 44 (filter cake, purchased from Zhejiang Runt Co., Ltd., China). The measured dyeing rate of Disperse Orange 44 was 93.85%, and the carbon dioxide recovery rate was 100%. The method for comparison is basically the same as the above, except that benzoic acid is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Orange 44 is measured, which is 35.32% after all.

[0040] Example 15 The specific procedure of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion rate is roughly the same as that in Example 1, with the only difference being that Disperse Yellow 163 is replaced with Disperse Orange 30:2 (filter cake, purchased from Zhejiang Runt Co., Ltd., China). The measured dyeing rate of Disperse Orange 30:2 was 92.55%, and the carbon dioxide recovery rate was 100%. The comparison method is basically the same as the above method, except that benzoic acid is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Orange 30:2 is measured, which is 39.87% after all.

[0041] Example 16 The specific procedure of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion is roughly the same as that in Example 1, with the only difference being that: Disperse Yellow 163 was used. Disperse Red 19 (Filter cake, purchased from Dalian Dye Factory, Liaoning Province, China). Measured Disperse Red 19 The dyeing rate is 93.89% and the carbon dioxide recovery rate is 100%. The comparison method is basically the same as the above method, except that benzoic acid is not added to the dye kettle. After dyeing is completed, the lids of the dye kettle and dyeing kettle are opened, the wound thread is removed, Disperse Red 19 The staining rate was measured and turned out to be 42.10%.

[0042] Example 17 The specific procedure of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion rate is roughly the same as that in Example 1, with the only difference being that Disperse Yellow 163 is replaced with Disperse Blue 104 (filter cake, purchased from Zhejiang Runt Co., Ltd., China). The measured dyeing rate of Disperse Blue 104 was 92.77%, and the carbon dioxide recovery rate was 100%. The method for comparison is basically the same as the above, except that benzoic acid is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Blue 104 is measured, which is 35.15% after all.

[0043] Example 18 The specific procedure of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion is roughly the same as that in Example 1, with the only difference being that: Disperse Yellow 163 was used. Disperse Violet 26 (Filter cake, purchased from Zhejiang Runtu Co., Ltd., China). Measured Disperse Violet 26 The dyeing rate is 92.18% and the carbon dioxide recovery rate is 100%. The comparison method is basically the same as the above method, except that benzoic acid is not added to the dye kettle. After dyeing is completed, the lids of the dye kettle and dyeing kettle are opened, the wound thread is removed, Disperse Violet 26 The staining rate was measured and turned out to be 39.78%.

[0044] Example 19 The specific procedure of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion rate is roughly the same as that in Example 1, with the only difference being that benzoic acid is replaced by methyl p-aminobenzoate. The measured dye exhaustion rate of Disperse Yellow 163 was 91.59%. The comparison method is basically the same as the above method, except that methyl p-aminobenzoate is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lids are opened, the wound yarn is taken out, and the dyeing rate of Disperse Yellow 163 is measured, which is 33.67% after all.

[0045] Example 20 The specific procedure of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion rate is roughly the same as that in Example 1, with the only difference being that benzoic acid is replaced by methyl p-hydroxybenzoate. The measured dyeing rate of Disperse Yellow 163 was 92.67%. The comparison method is basically the same as the above method, except that methyl p-hydroxybenzoate is not added to the dye kettle. After the dyeing is completed, the lids of the dye kettle and dye kettle are opened, the wound yarn is taken out, and the dyeing rate of Disperse Yellow 163 is measured, which is 33.67% after all.

[0046] Example 21 The specific procedure of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion is roughly the same as that in Example 1, with the only difference being that benzoic acid is L-Tyrosine Methyl Replace with. The measured dyeing rate of Disperse Yellow 163 was 92.23%. The comparison method is almost the same as the above, with the difference being the dye kettle. L-Tyrosine Methyl After the dyeing is completed, the dye kettle and the dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Yellow 163 is measured, which is 33.67% after all.

[0047] Example 22 The specific procedure of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion rate is roughly the same as that in Example 1, with the only difference being that benzoic acid is replaced with L-tryptophan methyl. The measured dye exhaustion rate of Disperse Yellow 163 was 93.30%. The comparison method is basically the same as the above method, except that L-tryptophan methyl is not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Yellow 163 is measured, which is finally 33.67%.

[0048] Example 23 The supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion is carried out in anhydrous supercritical carbon dioxide dyeing equipment, and specifically includes the following steps: (1) Filter cake of Disperse Yellow 163 (purchased from Zhejiang Runtu Co., Ltd., China) and nicotinamide were separately ground into uniformly dispersed powders with no obviously visible debris. (2) Powdered Disperse Yellow 163, benzoic acid, and nicotinamide are weighed out in a molar ratio of 1:1:2, and dry-polished at a speed of 200 r / min with zirconia beads in an amount 10 times their total weight to produce a 200 mesh mixed powder. (3) Put a certain amount of the mixed powder obtained from step (2) into the dye kettle, put 75D / 48F polyester wound yarn with a weight ratio of 100:1 to dye into the dye kettle, and then close the dye kettle and the dye kettle. (4) Open the booster pump and the valve of the carbon dioxide tank, pass liquid carbon dioxide through the dye kettle, open the circulation pump and set the carbon dioxide circulation rate to 30 seconds / cycle. At the same time, heat the entire anhydrous supercritical carbon dioxide dyeing equipment including the dye kettle and dyeing kettle at a rate of 1°C / min. Close the valve of the carbon dioxide tank and the booster pump until the ratio of the volume of liquid carbon dioxide (determined by the flow meter) to the mass of the wound yarn becomes 1L:60g. Continue to heat the dye kettle and dyeing kettle to 130°C at a rate of 1°C / min. Control the pressure of the dye kettle and dyeing kettle at 27MPa (carbon dioxide will reach a supercritical state under conditions of 130°C and 27MPa). Maintain the circulation rate of the supercritical carbon dioxide fluid at 30 seconds / cycle to carry out dyeing for 2 hours. After dyeing is completed, the supercritical carbon dioxide is passed into a separation tank (the low-pressure zone) at a temperature of 30-50°C and a pressure of 5-6 MPa, where it is vaporized to precipitate Disperse Yellow 163, benzoic acid, and nicotinamide. The pure carbon dioxide gas is then cooled to liquefy and sent to a tank (recovery rate 100%). Open the dyeing tank and dyeing tank, take out the wound yarn, and measure the exhaustion rate of the inner, middle and outer layers of the wound yarn according to the "Method for determining exhaustion rate in high temperature dyeing with disperse dyes" described in the Chinese national standard GB / T 9337-2009, and take the average value as the exhaustion rate of the dye. In the end, the exhaustion rate of Disperse Yellow 163 is 92.13%. The comparison method is basically the same as the above method, except that benzoic acid and nicotinamide are not added to the dye kettle. After the dyeing is completed, the dye kettle and dye kettle lids are opened, the wound yarn is taken out, and the dyeing rate of Disperse Yellow 163 is measured, which is 33.67% after all.

[0049] Example 24 The specific procedure of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion rate is roughly the same as that in Example 23, with the only difference being that benzoic acid is replaced by methyl p-aminobenzoate and nicotinamide is replaced by methyl p-hydroxybenzoate. The measured dyeing rate of Disperse Yellow 163 was 92.56%, and the carbon dioxide recovery rate was 100%. The comparison method is basically the same as the above method, except that methyl p-aminobenzoate and methyl p-hydroxybenzoate are not added to the dye kettle. After dyeing is completed, the lids of the dye kettle and dye kettle are opened, the wound yarn is taken out, and the dyeing rate of Disperse Yellow 163 is measured, which is finally 33.67%.

[0050] Example 25 The specific procedure of the supercritical carbon dioxide medium dyeing method for achieving high disperse dye exhaustion is roughly the same as that in Example 23, with the only difference being that benzoic acid is L-Tyrosine Methyl In addition, nicotinamide is replaced with L-tryptophan methyl. The measured dyeing rate of Disperse Yellow 163 was 93.87%, and the carbon dioxide recovery rate was 100%. The comparison method is almost the same as the above, with the difference being the dye kettle. L-Tyrosine Methyl After the dyeing is completed, the dye kettle and the dye kettle lid are opened, the wound yarn is taken out, and the dyeing rate of Disperse Yellow 163 is measured, which is 33.67% after all.

Claims

1. A supercritical carbon dioxide fluid dyeing method for achieving a high disperse dye exhaustion rate by adding a co-solvent that increases the dissolution rate and solubility of a disperse dye in a supercritical carbon dioxide fluid to a dyeing system of a disperse dye for polyester fibers or a product thereof, The disperse dye is Disperse Yellow 163, and the co-solvent is benzoic acid, nicotinamide, methyl p-aminobenzoate, methyl p-hydroxybenzoate, L-tyrosine methyl or L-tryptophan methyl, or benzoic acid and nicotinamide, or methyl p-aminobenzoate and methyl p-hydroxybenzoate, or L-tyrosine methyl and L-tryptophan methyl, or the disperse dye is Disperse Blue 60 and the co-solvent is nicotinamide; or the disperse dye is Disperse Orange 44 and the co-solvent is benzoic acid; or the disperse dye is Disperse Orange 30:2 and the co-solvent is benzoic acid; or the disperse dye is Disperse Red 19 and the co-solvent is benzoic acid; or the disperse dye is Disperse Blue 104 and the co-solvent is benzoic acid; or the disperse dye is Disperse Violet 26 and the co-solvent is benzoic acid; Compared to when the co-solvent is not added, the dye exhaustion rate is improved by 123% to 194.7%. A supercritical carbon dioxide fluid dyeing method for achieving a high disperse dye exhaustion rate.

2. (1) powdering a disperse dye and a co-solvent, (2) blending a powdered disperse dye and a co-solvent in a certain molar ratio to obtain a mixture; (3) the crushed mixture is put into a dye tank, and at the same time, the polyester fiber or its product is put into a dye tank, liquid carbon dioxide is introduced, and the temperature and pressure in the dye tank are adjusted to carry out high-temperature and high-pressure dyeing, and after the dyeing is completed, the polyester fiber or its product is taken out.

2. The method for dyeing with supercritical carbon dioxide fluid for achieving high dye exhaustion rate of disperse dye according to claim 1.

3. In step (1), the molar ratio of disperse dye to cosolvent is 1:1-10.

3. The method for dyeing with supercritical carbon dioxide fluid for achieving a high dyeing exhaustion rate of disperse dyes according to claim 2.

4. In step (2), the blending is carried out in the manner of evaporation crystallization, dry grinding, wet grinding, melt extrusion or melt crystallization.

3. The method for dyeing with supercritical carbon dioxide fluid for achieving a high dyeing exhaustion rate of disperse dyes according to claim 2.

5. In step (3), the temperature of high-temperature and high-pressure dyeing is 100-150°C, and the pressure is 16-30MPa.

3. The method for dyeing with supercritical carbon dioxide fluid for achieving a high dyeing exhaustion rate of disperse dyes according to claim 2.

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