阅读说明：本技术 用低成本Pickering型乳化剂制备W/C反相胶束的方法及染色方法 (Method for preparing W/C reversed micelle by using low-cost Pickering type emulsifier and dyeing method ) 是由 范荣 姚友西 于 2021-08-30 设计创作，主要内容包括：本发明公开了用低成本Pickering型乳化剂制备W/C反相胶束的方法及染色方法,包括亲油性Pickering粒子乳化剂,阴离子表面活性剂,二氧化碳,去离子水,在高压可视反应器中,由磁力搅拌高速旋转800～1500rpm制备上述W/C反相胶束,上述W/C反相胶束被应用于天然纤维染色,染料为常规水溶性染料。本发明所述的用低成本Pickering型乳化剂制备W/C反相胶束的方法及染色方法,避免了构建W/C反相胶束中含氟、含硅高成本表面活性剂的使用以及对Pickering乳化剂复杂及难控的表面改性过程,是一种真正的Pickering乳化剂和阴离子表面活性剂协同配伍的构建W/C反相胶束的低成本乳化剂体系,染色效果优良,同时避免了常规染色中大量水的使用,是一个符合绿色化学理念的化学过程。(The invention discloses a method for preparing a W/C reversed-phase micelle by using a low-cost Pickering type emulsifier and a dyeing method. The method for preparing the W/C reversed-phase micelle by using the low-cost Pickering emulsifier and the dyeing method avoid the use of fluorine-containing and silicon-containing high-cost surfactant in the W/C reversed-phase micelle and the complex and uncontrollable surface modification process of the Pickering emulsifier, are a real low-cost emulsifier system for constructing the W/C reversed-phase micelle by the synergistic compatibility of the Pickering emulsifier and the anionic surfactant, have excellent dyeing effect, avoid the use of a large amount of water in conventional dyeing, and are a chemical process conforming to the concept of green chemistry.)

1. The method for preparing the W/C reversed micelle by using the low-cost Pickering type emulsifier is characterized by comprising the following steps of: the method comprises the following operation steps:

s1: preparation of materials: preparing a certain amount of lipophilic particles, wherein the lipophilic particles comprise titanium dioxide, aluminum oxide, polytetrafluoroethylene, carbon black, coal powder ground by coal and the like, preparing a certain amount of anionic surfactant, and the anionic surfactant comprises sodium disulfosuccinate, namely 2-ethylhexyl, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and the like, and preparing a certain amount of carbon dioxide and deionized water;

s2: the material ratio is as follows: proportioning 5-20% of lipophilic particles, 0.2-3% of anionic surfactant, 70-90% of carbon dioxide and 0.1-1.5% of deionized water;

s3: mixing treatment: adding fibers and lipophilic particles into a 20ml high-pressure visual reaction kettle, pumping carbon dioxide and deionized water, and starting magnetic stirring at the rotating speed of 800-1500 rpm;

s4: magnetic stirring: pumping the anionic surfactant into the carbon dioxide and deionized water for magnetic stirring at the rotating speed of 800-1500 rpm;

s5: molding: the lipophilic particles and the anionic surfactant rotate at high speed in carbon dioxide and deionized water through magnetic stirring to obtain the W/C reversed micelle.

2. The method for preparing W/C reverse micelles with low-cost Pickering-type emulsifiers according to claim 1, characterized in that: the lipophilic particle accounts for 10%, the anionic surfactant accounts for 1%, the carbon dioxide accounts for 88.77%, and the deionized water accounts for 0.23%.

3. The method for preparing W/C reverse micelles with low-cost Pickering-type emulsifiers according to claim 1, characterized in that: the lipophilic particle accounts for 10 percent, the anionic surfactant accounts for 1 percent, the carbon dioxide accounts for 88.45 percent, and the deionized water accounts for 0.55 percent.

4. The dyeing method for preparing the W/C reversed micelle by using the low-cost Pickering type emulsifier is characterized by comprising the following steps of: the method comprises the following operation steps:

s1: magnetic stirring: filling fibers, oleophylic particles and an anionic surfactant into a 20mL visible high-pressure reactor, introducing quantitative carbon dioxide, and magnetically stirring at the rotating speed of 800-1500 rpm;

s2: water bath ratio: dissolving a dye in quantitative deionized water, and injecting the dye into a high-pressure reactor by using a high-pressure injection pump within 5-90 min to obtain a W/C reverse micelle system, wherein the bath ratio is 1: 30-1: 300, and the dye concentration is 0.5-5% o.w.f;

s3: dyeing: controlling the temperature of the high-pressure reactor to be 20-100 ℃, the pressure to be 3-40 MPa, the magnetic stirring rotating speed to be 800-1500 rpm, and dyeing for 30-300 min;

s4: removing floating color: introducing fresh carbon dioxide, and removing the floating color for 10-90 min;

s5: and (3) pressure reduction forming: the high-pressure reactor was depressurized to normal pressure, and the fibers were taken out.

5. The dyeing method for preparing W/C reversed micelles with low-cost Pickering type emulsifier according to claim 4, characterized in that: the W/C reversed micelle is applied to natural fibers, such as: the dyeing method is characterized in that silk, cotton, cashmere and the like are dyed, and the dye is water-soluble dye, such as direct dye, weak acid dye, reactive dye and the like.

6. The dyeing method for preparing W/C reversed micelles with low-cost Pickering type emulsifier according to claim 4, characterized in that: the rotation speed in the step S1 is 1300rpm, the high-pressure injection pump in the step S2 is injected into the high-pressure reactor within 30min, the temperature of the high-pressure reactor is controlled to be 40 ℃, the pressure is 10MPa, the magnetic stirring rotation speed is 1300rpm, dyeing is carried out for 150min, and flooding is removed for 30min in the step S4.

7. The dyeing method for preparing W/C reversed micelles with low-cost Pickering type emulsifier according to claim 4, characterized in that: the rotation speed in the step S1 is 1300rpm, the high-pressure injection pump in the step S2 is injected into the high-pressure reactor within 30min, the temperature of the high-pressure reactor is controlled to be 40 ℃, the pressure is 10MPa, the magnetic stirring rotation speed is 1300rpm, dyeing is carried out for 70min, and flooding is removed for 15min in the step S4.

8. The dyeing method for preparing W/C reversed micelles with low-cost Pickering type emulsifier according to claim 5, characterized in that: the natural fiber material is made of 21/22D real silk, and the degumming rate of the 21/22D real silk is 25%.

Technical Field

The invention relates to the field of preparation and dyeing of reversed micelles, in particular to a method for preparing a W/C reversed micelle by using a low-cost Pickering type emulsifier and a dyeing method.

Background

Paul t.anastas et al in 1998 proposed the concept of "Green Chemistry" (Green Chemistry) to emphasize Sustainable Development (Sustainable Development), i.e. in the chemical reaction process, minimizing the generation of waste and the consumption of energy required for the reaction, increasing the use of renewable, low-toxic substances, and effectively treating the existing toxic substances for the purpose of reducing environmental pollution, so-called Sustainable Development definition is a Development that not only meets the needs of contemporary people but also does not pose a hazard to the ability of later generations to meet their needs, Green Chemistry emphasizes a new strategy of preventing the generation of pollutants from the source, i.e. the transition from traditional environmental pollution first to pollution prevention, in recent years, the world has progressively strengthened the environmental strength due to increasingly worsened global climate and severe environmental problems, and chemical industry is a supporting industry for social Development, at present, there are more and more objections, and therefore, the global world is more and more urgent to replace the traditional chemical industry with the green chemical concept, in the traditional chemical industry, the use of a large amount of volatile organic solvents can cause serious pollution to the atmosphere, soil and water resources, and further the whole ecosystem is affected, as a substitute of the volatile organic solvents, the green solvents (such as water, carbon dioxide and the like) have good environmental friendliness, and thus can be used for replacing the toxic and harmful volatile organic solvents in the traditional chemical industry to achieve the purpose of green chemistry, carbon dioxide (CO2) is the second most abundant solvent next to water on the earth, and compared with the traditional organic solvents, CO2 has the following advantages: no toxicity, no combustion and low cost! Because CO2 has no permanent dipole moment and possesses weak van der Waals force and low polarity per unit volume, CO2 is often considered as a poor solvent, only a small part of molecules with lower polarity can be dissolved in liquid or supercritical carbon dioxide, and for polymers, only silicon-containing or fluorine-containing polymers and a small part of hydrocarbon polymers can be dissolved in carbon dioxide to a certain extent, which is a major bottleneck facing the technical popularization of CO2 as a single green solvent at present, however, normal phase (C/W) or reverse phase (W/C) micelles formed by CO2 and water can significantly improve the dissolving capacity of CO2 in supercritical or liquid state, so that the use of CO2 can be greatly expanded, CO2 and water can form micelles or emulsions, and under the stabilizing effect of surfactant molecules, the stable CO 2-water emulsion can be used for oil displacement, the key to the construction of CO 2-water emulsions is the selection of suitable emulsifiers, commonly used emulsifiers are surfactants, which often have poor solubility in CO2 leading to poor stability of the CO2 and water-constructed emulsions, and for polymer stabilizers, which are often less soluble, it is often necessary to use monomers with low cohesive energy density, such as: siloxane, trisiloxane, fluorocarbon, fluoroether, and fluoropropionate, fluorine-containing and silicon-containing polymer surfactants are generally expensive, and fluorine-containing surfactants are also difficult to degrade, so there is concern in environmental protection, using low molecular weight surfactants or "short and coarse" hydrocarbon surfactants with less tail end overlap, plus a low free volume at the CO 2-water interface, the tail end solubility of the surfactants can be enhanced, but hydrocarbon surfactants are less thermally stable, emulsions constructed are prone to break at high temperatures, in addition, because of the limitations of CO2 thermodynamic and transfer, W/C emulsions are more difficult to stabilize than C/W emulsions, so finding an environmentally friendly emulsifier for constructing high temperature resistant, high stability emulsions becomes a problem to be solved urgently, with the continuous development of technology, the requirements of people on the preparation of reversed micelles and the dyeing manufacturing process are higher and higher.

In the prior art, the patent with the publication number of CN105038756B discloses a carbon dioxide foam system added with hydrophilic nano particles for oil displacement and a preparation method thereof, 0.1-0.3 part of nonionic surfactant, 1-2 parts of hydrophilic nano particles, 0.01-0.2 part of inorganic salt, 0.2-0.8 part of carbon dioxide and 100 parts of water are mixed according to a proportion to prepare a foaming agent system, then the foaming agent system is dispersed uniformly by an ultrasonic disperser, carbon dioxide is introduced into a stirring cup and then stirred by a Waring Blender method to obtain the carbon dioxide foam system, the carbon dioxide foam added with the hydrophilic nano particles has better temperature resistance and salt resistance compared with the carbon dioxide foam generated by a common surfactant, has lower cost and better dispersion stability compared with the foaming agent added with hydrophobic nano particles, is easier to popularize and apply in oil fields, the preparation and dyeing of the existing reversed phase micelle have certain disadvantages in use, and the preparation and dyeing cost of the existing reversed phase micelle is high, the method for preparing the W/C reversed micelle by using the Pickering type emulsifier has low efficiency, consumes time, is not beneficial to the use of people, and brings certain adverse effect to the use process of people.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a method for preparing a W/C reversed-phase micelle by using a low-cost Pickering type emulsifier and a dyeing method, avoids the use of fluorine-containing and silicon-containing high-cost surfactants in the W/C reversed-phase micelle and the complex and difficult-to-control surface modification process of the Pickering emulsifier, is a real low-cost emulsifier system for constructing the W/C reversed-phase micelle by cooperatively matching the Pickering emulsifier and an anionic surfactant, has excellent dyeing effect, avoids the use of a large amount of water in conventional dyeing, is a chemical process conforming to the green chemical concept, and can effectively solve the problems in the background technology.

(II) technical scheme

In order to achieve the purpose, the invention adopts the technical scheme that: the method for preparing the W/C reversed micelle by using the low-cost Pickering type emulsifier comprises the following operation steps:

s1: preparation of materials: preparing a certain amount of lipophilic particles, wherein the lipophilic particles comprise titanium dioxide, aluminum oxide, polytetrafluoroethylene, carbon black, coal powder ground by coal and the like, preparing a certain amount of anionic surfactant, and the anionic surfactant comprises sodium disulfosuccinate, namely 2-ethylhexyl, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and the like, and preparing a certain amount of carbon dioxide and deionized water;

s2: the material ratio is as follows: proportioning 5-20% of lipophilic particles, 0.2-3% of anionic surfactant, 70-90% of carbon dioxide and 0.1-1.5% of deionized water;

s3: mixing treatment: adding fibers and lipophilic particles into a 20ml high-pressure visual reaction kettle, pumping carbon dioxide and deionized water, and starting magnetic stirring at the rotating speed of 800-1500 rpm;

s4: magnetic stirring: pumping the anionic surfactant into the carbon dioxide and deionized water for magnetic stirring at the rotating speed of 800-1500 rpm;

s5: molding: the lipophilic particles and the anionic surfactant rotate at high speed in carbon dioxide and deionized water through magnetic stirring to obtain the W/C reversed micelle.

In a preferred embodiment, the lipophilic particles are 10%, the anionic surfactant is 1%, the carbon dioxide is 88.77%, and the deionized water is 0.23%.

In a preferred embodiment, the lipophilic particles are 10%, the anionic surfactant is 1%, the carbon dioxide is 88.45%, and the deionized water is 0.55%.

The dyeing method for preparing the W/C reversed micelle by using the low-cost Pickering type emulsifier comprises the following operation steps:

s1: magnetic stirring: filling fibers, oleophylic particles and an anionic surfactant into a 20mL visible high-pressure reactor, introducing quantitative carbon dioxide, and magnetically stirring at the rotating speed of 800-1500 rpm;

s2: water bath ratio: dissolving a dye in quantitative deionized water, and injecting the dye into a high-pressure reactor by using a high-pressure injection pump within 5-90 min to obtain a W/C reverse micelle system, wherein the bath ratio is 1: 30-1: 300, and the dye concentration is 0.5-5% o.w.f;

s3: dyeing: controlling the temperature of the high-pressure reactor to be 20-100 ℃, the pressure to be 3-40 MPa, the magnetic stirring rotating speed to be 800-1500 rpm, and dyeing for 30-300 min;

s4: removing floating color: introducing fresh carbon dioxide, and removing the floating color for 10-90 min;

s5: and (3) pressure reduction forming: the high-pressure reactor was depressurized to normal pressure, and the fibers were taken out.

As a preferred technical scheme, the W/C reversed micelle is applied to natural fibers, such as: the dyeing method is characterized in that silk, cotton, cashmere and the like are dyed, and the dye is water-soluble dye, such as direct dye, weak acid dye, reactive dye and the like.

As a preferable technical scheme, the rotation speed in the step S1 is 1300rpm, the high-pressure injection pump in the step S2 is injected into the high-pressure reactor within 30min, the temperature of the high-pressure reactor in the step S3 is controlled at 40 ℃, the pressure is controlled at 10MPa, the magnetic stirring rotation speed is 1300rpm, the dyeing is carried out for 150min, and the flooding is removed for 30min in the step S4.

As a preferable technical scheme, the rotation speed in the step S1 is 1300rpm, the high-pressure injection pump in the step S2 is injected into the high-pressure reactor within 30min, the temperature of the high-pressure reactor is controlled to be 40 ℃, the pressure is controlled to be 10MPa, the magnetic stirring rotation speed is 1300rpm, dyeing is carried out for 70min in the step S3, and flooding is removed for 15min in the step S4.

As a preferable technical scheme, the natural fiber material is made of 21/22D real silk, and the degumming rate of 21/22D real silk is 25%.

(III) advantageous effects

Compared with the prior art, the invention provides the method for preparing the W/C reversed-phase micelle by using the low-cost Pickering type emulsifier and the dyeing method, and the method has the following beneficial effects: the method for preparing the W/C reversed-phase micelle by using the low-cost Pickering type emulsifier and the dyeing method avoid the use of fluorine-containing and silicon-containing high-cost surfactants in the W/C reversed-phase micelle and the complex and difficult-to-control surface modification process of the Pickering emulsifier, are a real low-cost emulsifier system for constructing the W/C reversed-phase micelle by the synergistic compatibility of the Pickering emulsifier and an anionic surfactant, have excellent dyeing effect, avoid the use of a large amount of water in the conventional dyeing, are a chemical process conforming to the green chemical concept, and prepare the W/C reversed-phase micelle by combining the low-cost Pickering granular emulsifier (such as lipophilic titanium dioxide particles and the like) and different low-cost anionic surfactants (such as bis (2-ethylhexyl) sodium sulfosuccinate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and the like), the work in the field is not reported, the technology is applied to supercritical CO2 dyeing (reversed phase micelle), so that the original supercritical dyeing method only applicable to disperse dyes can be applicable to various water-soluble dyes, such as direct dyes, reactive dyes, acid dyes and the like (the traditional dyeing process and the subsequent water washing process are usually completed in a water bath, so that a large amount of water resource is wasted, and a serious environmental problem is caused by a colored compound and a high-consumption electrolyte in waste sewage), so as to realize green chemical innovation in the printing and dyeing field, overcome the defect that the expensive and environmentally unfriendly fluorine-containing or silicon-containing surfactant is required to be adopted for preparing the W/C reversed phase micelle in the prior art, and the Pickering surfactant is singly adopted to firstly carry out complex surface grafting on particles so as to change the wettability of the particles, therefore, uncontrollable factors and cost of the process are increased, the Pickering surfactant and the anionic surfactant are adopted for synergistic compatibility to conveniently adjust the wettability of the Pickering emulsifier and simultaneously reduce the interfacial tension of a CO2-H2O interface, and the formed W/C reversed-phase micelle is used for dissolving water-soluble dye for supercritical dyeing, so that the preparation and dyeing structure of the whole reversed-phase micelle is simple, the operation is convenient, and the using effect is better than that of the traditional mode.

Drawings

FIG. 1 is a schematic diagram of the dyeing depth (K/S) contrast structure of supercritical reverse micelle dyeing by the method for preparing W/C reverse micelle by using low-cost Pickering type emulsifier and the dyeing method of the invention.

Detailed Description

The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

As shown in figure 1, the method for preparing the W/C reversed micelle by using the low-cost Pickering type emulsifier comprises the following operation steps:

s1: preparation of materials: preparing a certain amount of lipophilic particles, wherein the lipophilic particles comprise titanium dioxide, aluminum oxide, polytetrafluoroethylene, carbon black, coal powder ground by coal and the like, preparing a certain amount of anionic surfactant, the anionic surfactant comprises sodium disulfosuccinate, namely 2-ethylhexyl, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and the like, and preparing a certain amount of carbon dioxide and deionized water;

s2: the material ratio is as follows: proportioning 5-20% of lipophilic particles, 0.2-3% of anionic surfactant, 70-90% of carbon dioxide and 0.1-1.5% of deionized water;

s3: mixing treatment: adding fibers and lipophilic particles into a 20ml high-pressure visual reaction kettle, pumping carbon dioxide and deionized water, and starting magnetic stirring at the rotating speed of 800-1500 rpm;

s4: magnetic stirring: pumping the anionic surfactant into the carbon dioxide and deionized water for magnetic stirring at the rotating speed of 800-1500 rpm;

s5: molding: the lipophilic particles and the anionic surfactant rotate at high speed in carbon dioxide and deionized water through magnetic stirring to obtain the W/C reversed micelle.

Further, the content of lipophilic particles was 10%, the content of anionic surfactant was 1%, the content of carbon dioxide was 88.77%, and the content of deionized water was 0.23%.

Further, the content of lipophilic particles is 10%, the content of anionic surfactant is 1%, the content of carbon dioxide is 88.45%, and the content of deionized water is 0.55%.

The dyeing method for preparing the W/C reversed micelle by using the low-cost Pickering type emulsifier comprises the following operation steps:

s1: magnetic stirring: filling fibers, oleophylic particles and an anionic surfactant into a 20mL visible high-pressure reactor, introducing quantitative carbon dioxide, and magnetically stirring at the rotating speed of 800-1500 rpm;

s2: water bath ratio: dissolving a dye in quantitative deionized water, and injecting the dye into a high-pressure reactor by using a high-pressure injection pump within 5-90 min to obtain a W/C reverse micelle system, wherein the bath ratio is 1: 30-1: 300, and the dye concentration is 0.5-5% o.w.f;

s3: dyeing: controlling the temperature of the high-pressure reactor to be 20-100 ℃, the pressure to be 3-40 MPa, the magnetic stirring rotating speed to be 800-1500 rpm, and dyeing for 30-300 min;

s4: removing floating color: introducing fresh carbon dioxide, and removing the floating color for 10-90 min;

s5: and (3) pressure reduction forming: the high-pressure reactor was depressurized to normal pressure, and the fibers were taken out.

Further, the W/C reversed micelle is applied to natural fibers, such as: the dyeing method is characterized in that silk, cotton, cashmere and the like are dyed, and the dye is water-soluble dye, such as direct dye, weak acid dye, reactive dye and the like.

Further, the rotation speed in the step S1 is 1300rpm, a high-pressure injection pump in the step S2 is injected into the high-pressure reactor within 30min, the temperature of the high-pressure reactor is controlled to be 40 ℃, the pressure is 10MPa, the magnetic stirring rotation speed is 1300rpm, the dyeing is carried out for 150min, and the flooding is removed for 30min in the step S4 in the step S3.

Further, the rotation speed in the step S1 is 1300rpm, a high-pressure injection pump in the step S2 is injected into the high-pressure reactor within 30min, the temperature of the high-pressure reactor is controlled to be 40 ℃, the pressure is 10MPa, the magnetic stirring rotation speed is 1300rpm, dyeing is carried out for 70min, and flooding is removed for 15min in the step S4.

Furthermore, the natural fiber material is made of 21/22D real silk, and the degumming rate of 21/22D real silk is 25%.

Example 1

The formula is as follows:

21/22D Silk (degumming rate 25%) 0.2g

Bath ratio: 1:100

Titanium dioxide particles (oleophilic) 10%

Bis (2-ethylhexyl) sodium sulfosuccinate (AOT) 1%

88.77 percent of carbon dioxide

0.2 percent of deionized water

Direct fast pink BK (C.I.direct Red 75) 0.03% (2% o.w.f)

And (3) dyeing:

(1) filling real silk fibers, oleophylic titanium dioxide particles and AOT into a 20mL visible high-pressure reactor, introducing quantitative carbon dioxide, and magnetically stirring at the rotating speed of 1300 rpm;

(2) dissolving direct fast peach red in quantitative deionized water, and injecting into a high-pressure reactor by using a high-pressure injection pump within 30min to obtain a W/C reverse micelle system;

(3) controlling the temperature of the high-pressure reactor to be 40 ℃, the pressure to be 10MPa, the magnetic stirring rotating speed to be 1300rpm, and dyeing for 150 min;

(4) introducing fresh carbon dioxide, and removing floating color for 30 min;

(5) and (4) decompressing the high-pressure reactor to normal pressure, and taking out the real silk fibers.

Example 2

The formula is as follows:

21/22D Silk (degumming rate 25%) 0.2g

Bath ratio: 1:100

Titanium dioxide particles (oleophilic) 10%

Sodium Dodecyl Benzene Sulfonate (SDBS) 1%

88.45 percent of carbon dioxide

0.5 percent of deionized water

Reactive Orange KN-4R (C.I. reactive Orange 7) 0.03% (2% o.w.f)

And (3) dyeing:

(1) filling real silk fibers, oleophylic titanium dioxide particles and SDBS into a 20mL visible high-pressure reactor, introducing quantitative carbon dioxide, and magnetically stirring at the rotating speed of 1300 rpm;

(2) dissolving active orange KN-4R in quantitative deionized water, and injecting the solution into a high-pressure reactor by using a high-pressure injection pump within 30min to obtain a W/C reverse micelle system;

(3) controlling the temperature of the high-pressure reactor to be 40 ℃, the pressure to be 10MPa, the magnetic stirring rotating speed to be 1300rpm, and dyeing for 150 min;

(4) introducing fresh carbon dioxide, and removing floating color for 30 min;

(5) and (4) decompressing the high-pressure reactor to normal pressure, and taking out the real silk fibers.

Example 3

The formula is as follows:

21/22D Silk (degumming rate 25%) 0.2g

Bath ratio: 1:100

Titanium dioxide particles (oleophilic) 10%

Sodium Dodecyl Sulfate (SDS) 1%

88.23 percent of carbon dioxide

0.7 percent of deionized water

Weakly acidic brilliant Red B (C.I.acid Red 249) 0.03% (2% o.w.f)

And (3) dyeing:

(1) real silk fibers, oleophylic titanium dioxide particles and SDS are put into a 20mL visible high-pressure reactor, quantitative carbon dioxide is introduced, and the mixture is magnetically stirred at the rotating speed of 1300 rpm;

(2) dissolving weakly acidic brilliant red B in quantitative deionized water, and injecting the solution into a high-pressure reactor by using a high-pressure injection pump within 30min to obtain a W/C reverse micelle system;

(3) controlling the temperature of the high-pressure reactor to be 40 ℃, the pressure to be 10MPa, the magnetic stirring rotating speed to be 1300rpm, and dyeing for 150 min;

(4) introducing fresh carbon dioxide, and removing floating color for 30 min;

(5) and (4) decompressing the high-pressure reactor to normal pressure, and taking out the real silk fibers.

Comparative example 1

The silk fiber is put into a deionized water dye bath (bath ratio is 1:100), and the direct sun-proof pink BK (C.I.direct Red 75) dye concentration is 2% (o.w.f). The material was dyed in a bath at 40 ℃ for 70min and washed with 5g/l nonionic detergent (Hostapal CL) at 40 ℃ for 15min to remove the floating color. Finally, the dyed fiber is washed by hot water and then cold water, and finally dried;

the soaping fastness of the dyed real silk fibers in the supercritical reverse micelle in the examples 1 to 3 is 4 to 5 grades, which is better than the soaping fastness of the water bath dyed real silk fibers in the comparative example 1 by 3 to 4 grades;

as shown in fig. 1, from the comparison of the results, the color depth of the real silk fiber dyed by the supercritical CO2 reverse micelle is larger than that of the conventional water bath dyeing (K/S ═ 7), and the dyeing depth of the direct dye (K/S ═ 12.0) is larger than that of the reactive dye (K/S ═ 9.3), and the dyeing depths of both are larger than that of the weakly acidic dye (K/S ═ 8.2).

The working principle is as follows: preparing a certain amount of lipophilic particles, wherein the lipophilic particles comprise titanium dioxide, aluminum oxide, polytetrafluoroethylene, carbon black, coal powder ground by coal and the like, preparing a certain amount of anionic surfactant, wherein the anionic surfactant comprises sodium bis (2-ethylhexyl) sulfosuccinate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and the like, preparing a certain amount of carbon dioxide and deionized water, proportioning the lipophilic particles, the anionic surfactant, the carbon dioxide and the deionized water, wherein the lipophilic particles are 5-20%, the anionic surfactant is 0.2-3%, the carbon dioxide is 70-90%, the deionized water is 0.1-1.5%, adding fibers and the lipophilic particles into a 20ml high-pressure visual reaction kettle, pumping the carbon dioxide and the deionized water, starting magnetic stirring, wherein the rotating speed is 800-1500 rpm, pumping the anionic surfactant into the carbon dioxide and the deionized water for magnetic stirring, the method comprises the steps of rotating at a speed of 800-1500 rpm, enabling lipophilic particles and an anionic surfactant to rotate at a high speed in carbon dioxide and deionized water through magnetic stirring to obtain W/C reversed-phase micelles, filling fibers, the lipophilic particles and the anionic surfactant into a 20mL visible high-pressure reactor, introducing quantitative carbon dioxide, conducting magnetic stirring at a speed of 800-1500 rpm, dissolving a dye into quantitative deionized water, injecting the mixture into the high-pressure reactor through a high-pressure injection pump within 5-90 min to obtain a W/C reversed-phase micelle system, controlling the temperature of the high-pressure reactor to be 20-100 ℃ and the pressure to be 3-40 MPa, conducting magnetic stirring at a speed of 800-1500 rpm, dyeing for 30-300 min, introducing fresh carbon dioxide, removing floating color for 10-90 min, reducing the pressure of the high-pressure reactor to normal pressure, and taking out the fibers.

It is noted that, herein, relational terms such as first and second (a, b, etc.) and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.

The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.