CN113249984A - Deep eutectic solvent and high-energy ball milling technology-based red and yellow natural dye color matching dyeing method - Google Patents
Deep eutectic solvent and high-energy ball milling technology-based red and yellow natural dye color matching dyeing method Download PDFInfo
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- 239000000978 natural dye Substances 0.000 title claims abstract description 54
- 238000000713 high-energy ball milling Methods 0.000 title claims abstract description 39
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 239000000975 dye Substances 0.000 claims description 27
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- 238000003756 stirring Methods 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 9
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 6
- 244000020518 Carthamus tinctorius Species 0.000 claims description 6
- 235000019743 Choline chloride Nutrition 0.000 claims description 6
- 241000123069 Ocyurus chrysurus Species 0.000 claims description 6
- 241000219784 Sophora Species 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 229960003178 choline chloride Drugs 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
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- 229940126062 Compound A Drugs 0.000 claims description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 5
- 241000405414 Rehmannia Species 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 229960003237 betaine Drugs 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
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- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000001044 red dye Substances 0.000 claims description 3
- 239000001043 yellow dye Substances 0.000 claims description 3
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 240000001972 Gardenia jasminoides Species 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 11
- 238000009941 weaving Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- 230000000694 effects Effects 0.000 description 12
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- 239000004480 active ingredient Substances 0.000 description 5
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- 230000009471 action Effects 0.000 description 4
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- -1 compound choline chloride Chemical class 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
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- 238000002474 experimental method Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
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- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
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- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
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- 239000002608 ionic liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/34—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using natural dyestuffs
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/36—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using mordant dyes ; using metallisable dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/647—Nitrogen-containing carboxylic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/653—Nitrogen-free carboxylic acids or their salts
- D06P1/6533—Aliphatic, araliphatic or cycloaliphatic
Abstract
The invention relates to the technical field of dyeing, in particular to a color matching and dyeing method of a red-yellow natural dye based on a eutectic solvent and a high-energy ball milling technology, which comprises the following steps: 1) preparing a eutectic solvent; 2) preparing natural dye plant dry powder; 3) extracting natural dye liquor; 4) and (5) color matching and dyeing of the fabric. The color matching dyeing method of the red and yellow natural dye based on the eutectic solvent and the high-energy ball milling technology can be used for dyeing various fabrics, and has very important practical significance for the development of the dyeing and weaving industry in China.
Description
Technical Field
The invention relates to the technical field of dyeing, in particular to a color matching and dyeing method of a red-yellow natural dye based on a eutectic solvent and a high-energy ball milling technology.
Background
The history of Chinese dyeing technology is long, and as early as a thousand years ago, ancient people learn the technology of obtaining natural pigments from animals and plants to dye fabrics. The fabric dyed by the natural pigment has soft color and luster, good biodegradability and no great harm to the environment, and has wide application prospect in the fields of cultural products, high-grade clothes, home textile articles and the like.
The traditional natural dye has the defects of single color and low color fastness, and the problem can be effectively solved by the color matching dyeing technology assisted by a novel mordant at present. Mechanochemical methods are methods for preparing new materials or modifying materials by using mechanical energy to induce chemical reactions, so that the tissues, structures and properties of the materials are changed. High energy ball milling is one of the mechanochemical methods that uses grinding and impact between high speed rotating grinding balls and material to generate mechanical energy. The high-energy ball milling method has the advantages of low cost, low energy consumption, high efficiency and wide application.
Eutectic mixtures, which are a combination of hydrogen bond acceptors and hydrogen bond donors in stoichiometric proportions, are called eutectic solvents because their freezing points are significantly below the melting points of the pure materials of the individual components. As a novel ionic liquid, the eutectic solvent is easy to prepare, has the advantages of no toxicity and no pollution, and is often applied to various fields of gas absorption, organic synthesis, drug slow release and the like. Meanwhile, the eutectic solvent can effectively improve the solubility of the extract in the aqueous solution, so that the eutectic solvent is widely researched in the field of bioactive extraction.
Disclosure of Invention
In order to solve the technical problems, the invention provides a color matching and dyeing method of a red-yellow natural dye based on a eutectic solvent and a high-energy ball milling technology. The invention extracts natural dyeing components from plants based on a eutectic solvent and a high-energy ball milling technology, and performs color matching and dyeing by using an improved technology. Not only has good extraction and dyeing effects, but also uses materials and solutions with biological safety in the whole preparation process, so that the mordant and the dyed fabric are safe and environment-friendly and do not hurt the skin.
The specific technical scheme of the invention is as follows: a color matching and dyeing method of red and yellow natural dyes based on a eutectic solvent and a high-energy ball milling technology comprises the following steps:
1) uniformly mixing the hydrogen bond donor compound A, the hydrogen bond acceptor compound B and deionized water, and stirring in a high-temperature water bath to obtain a eutectic solvent C;
2) drying natural dye plant D at low temperature until weight is unchanged, placing into a traditional Chinese medicine powder grinding machine, crushing into powder, and screening out natural dye plant dry powder E with uniform particle size by using a vibrating screen;
3) mixing the eutectic solvent C obtained in the step 1) and the natural dye plant dry powder E obtained in the step 2), putting the mixture into a ball milling tank, adding grinding beads, grinding the mixture on a planetary ball mill at a low speed, and performing suction filtration to obtain a dye solution F;
4) mixing the dye solution F obtained in the step 3) with the dyeing assistant G to obtain a mordant H, putting the dyed object into the mordant H, boiling and dyeing at a high temperature, taking out the dyed object, cooling at room temperature, washing off loose colors with cold water, and naturally drying in the sun to finish dyeing.
The preparation of the eutectic solvent is generally carried out by stirring the hydrogen bond donor and the hydrogen bond acceptor at room temperature. The two types of substances are bonded together through hydrogen bonds during stirring, and have relatively high polarity. The invention skillfully combines the high-energy ball milling technology with the high-energy ball milling technology, and can generate the synergistic effect: under the action of high-energy ball milling, on one hand, the low cosolvent generates greater reaction activity and greatly increases polarity due to the high-energy effect provided by the high-energy ball milling, so that the binding capacity of the solvent and the effective components is enhanced, and the effective components of the dye are easier to extract; on the other hand, the strong mechanochemical action generated by the high-energy ball milling and the chemical action of the eutectic solvent generate a synergistic effect to act on the cell walls of the dye plants, which is more favorable for promoting the cell wall breaking and releasing the active ingredients in the sample matrix from the cells. In addition, the released active ingredients can generate more reaction sites under the action of high-energy ball milling, so that the subsequent dyeing reaction is facilitated, and the color fastness is improved.
Preferably, the hydrogen bond donor compound a in step 1) may be any one of choline chloride and betaine, and the hydrogen bond acceptor compound B may be any one of glycerol, ethylene glycol, oxalic acid, malic acid, and carbamide. The molar ratio of the compound A to the compound B to the deionized water is (0.9-1.1) to (1.8-2.2) to 3.
The addition of the deionized water can effectively improve the mixing efficiency of the compounds A and B, reduce the preparation time of the eutectic solvent, reduce the viscosity of the solvent and improve the stability of the solvent. The higher the percentage of deionized water, the lower the viscosity of the eutectic solvent. We found experimentally that the lower the viscosity of the eutectic solvent, the higher the extraction efficiency.
Preferably, in the preparation process of the eutectic solvent C in the step 1), the water bath temperature is controlled to be 78-82 ℃, and the stirring time is controlled to be 2-6 h.
The higher the temperature, the shorter the time required to prepare the solvent, which is generally controlled to within 100 ℃.
Preferably, the natural dye plant D in the step 2) is a mixture of safflower, gardenia, sophora flower, rehmannia root and madder root, and the mass ratio of the natural dye plant D to the natural dye plant D is 3: 1.1-1.4: 1.9-2: 0-0.6: 0-1.
The color of the dye can be richer and is rich in layering sense by matching the multiple plants. Safflower and madder root are red dye raw materials, gardenia, sophora flower and rehmannia root are yellow dye raw materials, and the color of the dye can be changed by adjusting the proportion of the raw materials.
Preferably, in the drying process in the step 2), the temperature should be controlled to be 40-60 ℃, and the time should be controlled to be within 20 hours.
The higher the temperature is, the higher the drying efficiency is, and the shorter the required time is, but the dye component is more easily subjected to thermal denaturation; we have found through experimentation that the above temperature range is preferred.
Preferably, in the screening process in the step 2), the granularity is controlled to be 0.5-1 mm, and the time is controlled to be 15-20 min.
The smaller the particle size of the dry powder is, the more beneficial the extraction of the dye component is.
Preferably, in the step 3), the dosage ratio of the eutectic solvent C to the natural dye plant dry powder E is 45-55 mL: 2g, and the total volume of the solution should not exceed 1/2 of the volume of the ball milling tank.
The addition of the eutectic solvent can effectively improve the solubility of the bioactive components, and the research shows that the plant pigment is more stable and not easy to denature in the eutectic solvent. The larger the amount of solvent used, the larger the amount of dye component extracted per unit dry powder, but the higher the extraction cost.
Preferably, the grinding beads in the step 3) have three types, the diameters of the grinding beads are respectively 2mm, 6mm and 10mm, the quantity ratio of the grinding beads is (5.9-6.1): (1.4-1.6): 1, and the total volume of the grinding beads is not more than 1/6 of the volume of the ball milling tank.
The big grinding ball can effectively generate grinding and collision effects, and the small grinding ball can fill the gap of the big grinding ball. The more hard and fibrous components in the dry powder, the more large grinding beads are needed.
Preferably, in the ball milling process in the step 3), the rotating speed of the ball mill is controlled to be 195-205 r/min, and the ball milling time is controlled to be 10-12 min.
The higher the rotation speed, the less time is required, and the effective components of the dye can be damaged by high rotation speed and long-time ball milling.
The high-energy ball milling treatment can not only improve the extraction efficiency of the plant active ingredients, but also more importantly can improve the activity of surface groups of the active ingredients, obviously improve the mordant dyeing efficiency of the dye solution, and obviously improve the color fastness after dyeing. Preferably, the dyeing assistant G in the step 4) is a mixture of citric acid, acetic acid and 2- [ bis (carboxymethyl) amino ] acetic acid, and the molar ratio of the dyeing assistant G to the dyeing assistant G is 3 to (1.8-2.1) to (1.1-1.5). Citric acid and acetic acid are traditional acidic mordants, and 2- [ bis (carboxymethyl) amino ] acetic acid is used as a chelating agent to assist mordanting.
Preferably, in the step 4) of preparing the mordant, a dyeing assistant G is added until the pH value of the solution is 3-5.
The stable acidic solution environment can improve mordant dyeing efficiency.
Preferably, in the boiling and dyeing process in the step 4), the temperature is controlled to be 70-75 ℃, and the time is controlled to be within 40 min.
The temperature rise and the time extension are beneficial to finishing dyeing, but the too high temperature and the too long mordant dyeing time can damage the fabric strength and influence the mordant dyeing effect.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention uses eutectic solvent auxiliary extraction method and high energy ball milling technology to extract natural dye, the invention finds that the two technologies have synergistic interaction after being coupled, and the technical effect that 1+1 is more than 2 is generated: the dye extraction efficiency is obviously improved, and the consumption is lower; and the high-energy ball milling can also improve the activity of surface groups of active ingredients, the mordant dyeing efficiency of the dye liquor is obviously improved, and the color fastness after dyeing is also obviously improved.
2. The invention uses citric acid, acetic acid and 2- [ bis (carboxymethyl) amino ] acetic acid for auxiliary split dyeing, can improve dyeing effect, improve dyeing efficiency, and has brighter color and higher fabric color fastness.
3. The technology and the reagent used by the invention do not cause harm to human bodies and environment, and are environment-friendly.
4. Due to the existence of low eutectic solvent in mordant dyeing liquid, the antibacterial property of the dyed fabric is also improved to a certain extent.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
a color matching and dyeing method of red and yellow natural dyes based on a eutectic solvent and a high-energy ball milling technology comprises the following steps:
1) uniformly mixing a hydrogen bond donor compound choline chloride, a hydrogen bond acceptor compound glycerol and deionized water according to a molar ratio of 0.9: 1.8: 3, and stirring in a water bath at 78 ℃ for 6 hours to obtain a eutectic solvent C1;
2) mixing natural dye plants including Carthami flos, flos Gardeniae and flos Sophorae Immaturus at a mass ratio of 3: 1.1: 1.9, oven drying at 40 deg.C for 20h, pulverizing into powder, and sieving with sieving machine for 20min to obtain natural dye plant dry powder E1 with particle size of about 0.5 mm;
3) mixing 45mL of eutectic solvent C1 obtained in the step 1) with 2g of natural dye plant dry powder E1 obtained in the step 2), putting the mixture into a ball milling tank, adding 59 grinding beads with the diameter of 2mm, 14 grinding beads with the diameter of 6mm and 10 grinding beads with the diameter of 10mm, grinding the mixture on a planetary ball mill at a low speed at the rotating speed of 195r/min for ball milling time of 12min, and performing suction filtration to obtain a dye solution F1;
4) mixing the dye solution F1 obtained in the step 3) with a dyeing assistant G1 until the pH of the solution is 3, so as to obtain a mordant H1. The dyeing assistant G1 is a mixture of citric acid, acetic acid and 2- [ bis (carboxymethyl) amino ] acetic acid, and the molar ratio is 3: 1.8: 1.1. And (3) putting the dyed object into a mordant dyeing solution H1, boiling and dyeing for 40min at 70 ℃, taking out, cooling at room temperature, washing off loose color with cold water, and naturally drying in the sun to finish dyeing.
Example 2:
a color matching and dyeing method of red and yellow natural dyes based on a eutectic solvent and a high-energy ball milling technology comprises the following steps:
1) uniformly mixing a hydrogen bond donor compound choline chloride, a hydrogen bond acceptor compound ethylene glycol and deionized water according to the mol ratio of 1.1: 2.2: 3, and stirring in a water bath at 82 ℃ for 2 hours to obtain a eutectic solvent C2;
2) drying natural dye plants such as safflower, gardenia, sophora flower, rehmannia root and madder root for 10h at the temperature of 60 ℃ in a mass ratio of 3: 1.4: 2: 0.6: 1, crushing the mixture into powder by a traditional Chinese medicine powder grinding machine, and screening the powder for 15min by using a sieving machine to obtain natural dye plant dry powder E2 with the particle size of about 1 mm;
3) mixing 110mL of eutectic solvent C2 obtained in the step 1) with 4g of natural dye plant dry powder E2 obtained in the step 2), putting the mixture into a ball milling tank, adding 61 grinding beads with the diameter of 2mm, 16 grinding beads with the diameter of 6mm and 10 grinding beads with the diameter of 10mm, grinding the mixture on a planetary ball mill at a low speed, rotating speed of 205r/min, ball milling time of 10min, and carrying out suction filtration to obtain a dye solution F2;
4) mixing the dye solution F2 obtained in the step 3) with a dyeing assistant G2 until the pH of the solution is 5 to obtain a mordant H2. The dyeing assistant G2 is a mixture of citric acid, acetic acid and 2- [ bis (carboxymethyl) amino ] acetic acid, and the molar ratio is 3: 2.1: 1.5. And (3) putting the dyed object into a mordant liquid H2, boiling and dyeing for 30min at 75 ℃, cooling at room temperature after taking out, washing off loose color by cold water, and naturally drying in the sun to finish dyeing.
Example 3:
a color matching and dyeing method of red and yellow natural dyes based on a eutectic solvent and a high-energy ball milling technology comprises the following steps:
1) uniformly mixing a hydrogen bond donor compound choline chloride, a hydrogen bond acceptor compound oxalic acid and deionized water according to the mol ratio of 1: 2: 3, and stirring in a water bath at the temperature of 80 ℃ for 4 hours to prepare a eutectic solvent C3;
2) drying natural dye plant safflower, gardenia, sophora flower, rehmannia root and madder root for 11h at 50 ℃ in a mass ratio of 3: 1.2: 2: 0.5: 1, putting the mixture into a traditional Chinese medicine powdering machine, crushing the powder into powder, and screening the powder for 17min by using a sieving machine to obtain natural dye plant dry powder E3 with the particle size of about 0.7 mm;
3) mixing 50mL of eutectic solvent C3 obtained in the step 1) with 2g of natural dye plant dry powder E3 obtained in the step 2), putting the mixture into a ball milling tank, adding 60 grinding beads with the diameter of 2mm, 15 grinding beads with the diameter of 6mm and 10 grinding beads with the diameter of 10mm, grinding the mixture on a planetary ball mill at a low speed, rotating speed of 200r/min, ball milling time of 10min, and filtering to obtain a dye solution F3;
4) mixing the dye solution F3 obtained in the step 3) with a dyeing assistant G3 until the pH of the solution is 5 to obtain a mordant H3. The dyeing assistant G3 is a mixture of citric acid, acetic acid and 2- [ bis (carboxymethyl) amino ] acetic acid, and the molar ratio is 3: 2: 1.4. And (3) putting the dyed object into a mordant dyeing solution H3, boiling and dyeing for 30min at 72 ℃, cooling at room temperature after taking out, washing off loose color with cold water, and naturally drying in the sun to finish dyeing.
Example 4:
a color matching and dyeing method of red and yellow natural dyes based on a eutectic solvent and a high-energy ball milling technology comprises the following steps:
1) uniformly mixing a hydrogen bond donor compound choline chloride, a hydrogen bond acceptor compound malic acid and deionized water according to a molar ratio of 1: 2: 3, and stirring in a water bath at 82 ℃ for 5 hours to obtain a eutectic solvent C4;
2) drying natural dye plants such as safflower, gardenia, sophora flower and madder root for 12h at the mass ratio of 3: 1.3: 1.9: 0.4 at 55 ℃, putting the mixture into a traditional Chinese medicine powder grinding machine, crushing the powder into powder, and screening the powder for 18min by using a vibrating screen machine to obtain natural dye plant dry powder E4 with the particle size of about 0.6 mm;
3) mixing 100mL of eutectic solvent C4 obtained in the step 1) with 4g of natural dye plant dry powder E4 obtained in the step 2), putting the mixture into a ball milling tank, adding 120 grinding beads with the diameter of 2mm, 30 grinding beads with the diameter of 6mm and 20 grinding beads with the diameter of 10mm, grinding the mixture on a planetary ball mill at a low speed, rotating speed of 205r/min, ball milling time of 12min, and filtering to obtain a dye solution F4;
4) mixing the dye solution F4 obtained in the step 3) with a dyeing assistant G4 until the pH value of the solution is 4 to obtain a mordant H4. The dyeing assistant G4 is a mixture of citric acid, acetic acid and 2- [ bis (carboxymethyl) amino ] acetic acid, and the molar ratio is 3: 1.9: 1.1. And (3) putting the dyed object into a mordant dyeing solution H4, boiling and dyeing for 35min at 70 ℃, taking out, cooling at room temperature, washing off loose color with cold water, and naturally drying in the sun to finish dyeing.
Example 5:
a color matching and dyeing method of red and yellow natural dyes based on a eutectic solvent and a high-energy ball milling technology comprises the following steps:
1) uniformly mixing a hydrogen bond donor compound betaine, a hydrogen bond acceptor compound carbamide and deionized water according to the mol ratio of 0.9: 1.9: 3, and stirring in a water bath at 79 ℃ for 3 hours to obtain a eutectic solvent C5;
2) mixing natural dye plants including Carthami flos, flos Gardeniae, flos Sophorae Immaturus, and radix rehmanniae at a mass ratio of 3: 1.2: 2: 0.5, oven drying at 50 deg.C for 15 hr, pulverizing into powder, and sieving with sieving machine for 15min to obtain natural dye plant dry powder E5 with particle size of 1 mm;
3) mixing 80mL of eutectic solvent C5 obtained in the step 1) with 3g of natural dye plant dry powder E5 obtained in the step 2), putting the mixture into a ball milling tank, adding 90 grinding beads with the diameter of 2mm, 23 grinding beads with the diameter of 6mm and 15 grinding beads with the diameter of 10mm, grinding the mixture on a planetary ball mill at a low speed, rotating speed of 200r/min, ball milling time of 11min, and carrying out suction filtration to obtain a dye solution F5;
4) mixing the dye solution F5 obtained in the step 3) with a dyeing assistant G5 until the pH of the solution is 3, so as to obtain a mordant H5. The dyeing assistant G5 is a mixture of citric acid, acetic acid and 2- [ bis (carboxymethyl) amino ] acetic acid, and the molar ratio is 3: 2: 1.1. And (3) putting the dyed object into a mordant dyeing solution H5, boiling and dyeing for 40min at 74 ℃, cooling at room temperature after taking out, washing off loose color by cold water, and naturally drying in the sun to finish dyeing.
The examples 1-5 were compared with conventional dyed samples (comparative examples 1-6) that did not use a eutectic solvent, a high-energy ball milling technique, and a dye-assist chelating agent, but used a conventional boil-dyeing technique. Example 1 was compared to the use of a eutectic solvent alone (comparative example 7), high energy ball milling technology alone (comparative example 8) and no dye-assist chelating agent (comparative example 9). The performance test results are as follows.
Table 1 characterization of properties of stained samples
Note: the selected staphylococcus aureus is used in the antibacterial experiment, and the size of the inhibition zone is judged after coating, wherein 'good' means the effect that the inhibition zone is larger than 15 mm; the general inhibition zone is less than 9 mm.
Table 2 characterization of properties of the dyed samples of the comparative examples
Note: the selected staphylococcus aureus is used in the antibacterial experiment, and the size of the inhibition zone is judged after coating, wherein 'good' means the effect that the inhibition zone is larger than 15 mm; the general inhibition zone is less than 9 mm.
As can be seen from the data analysis in tables 1-2, through the technical improvement of the invention, the dye extraction time and the fabric boiling-dyeing time of the embodiment are obviously reduced, and the use of the eutectic solvent and the high-energy ball milling technology can effectively improve the weaving-dyeing efficiency. The apparent color of the fabric is obviously changed, the color is richer and is rich in layering, and the color fastness is improved to a certain degree. And the eutectic solvent and the high-energy ball milling technology are combined, so that the effect is better compared with the case that the eutectic solvent (comparative example 7) and the high-energy ball milling technology (comparative example 8) are singly adopted.
In addition, through bacteriostasis experiments, the antibacterial property of the fabric is found to be improved to a certain extent, which is probably because the eutectic solvent in the mordant dyeing solution also plays a role in sterilization.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A color matching and dyeing method of red and yellow natural dyes based on a eutectic solvent and a high-energy ball milling technology is characterized by comprising the following steps:
1) uniformly mixing the hydrogen bond donor compound A, the hydrogen bond acceptor compound B and deionized water, and stirring in a high-temperature water bath to obtain a eutectic solvent C;
2) drying the natural dye plant D at low temperature until the weight is unchanged, crushing the natural dye plant D into powder, and screening out natural dye plant dry powder E with uniform particle size;
3) mixing the eutectic solvent C obtained in the step 1) and the natural dye plant dry powder E obtained in the step 2), putting the mixture into a ball milling tank, adding grinding beads, grinding the mixture on a planetary ball mill at a low speed, and performing suction filtration to obtain a dye solution F;
4) mixing the dye solution F obtained in the step 3) with the dyeing assistant G to obtain a mordant H, putting the dyed object into the mordant H, boiling and dyeing at a high temperature, taking out the dyed object, cooling at room temperature, washing off loose colors with cold water, and naturally drying in the sun to finish dyeing.
2. The color matching and dyeing method of natural red and yellow dyes based on eutectic solvent and high energy ball milling technology according to claim 1, characterized in that in step 1), the hydrogen bond donor compound A is any one of choline chloride and betaine, and the hydrogen bond acceptor compound B is any one of glycerol, ethylene glycol, oxalic acid, malic acid and carbamide; the mol ratio of the compound A to the compound B to the deionized water is (0.9-1.1): 1.8-2.2): 3.
3. The method for color matching and dyeing of natural red and yellow dyes based on the eutectic solvent and high-energy ball milling technology as claimed in claim 1, wherein the water bath temperature is controlled at 78-82 ℃ and the stirring time is controlled at 2-6h in the preparation process of the eutectic solvent C in step 1).
4. The method for color matching and dyeing of red and yellow natural dyes based on the eutectic solvent and the high-energy ball milling technology as claimed in claim 1, wherein the natural dye plant D in the step 2) is a mixture of safflower, gardenia, sophora flower, rehmannia root and madder root, and the mass ratio of the natural dye plant D to the natural dye plant D is 3 (1.1-1.4): 1.9-2): 0-0.6): 0-1.
5. The color matching and dyeing method of the red and yellow natural dyes based on the eutectic solvent and the high-energy ball milling technology as claimed in claim 1, characterized in that, in the drying process of the step 2), the temperature is controlled to be 40-60 ℃, and the time is controlled to be within 20 h; in the screening process, the granularity is controlled to be 0.5-1 mm, and the time is controlled to be 15-20 min.
6. The color matching and dyeing method of the red and yellow natural dyes based on the eutectic solvent and high-energy ball milling technology as claimed in claim 1, characterized in that in the step 3), the dosage ratio of the eutectic solvent C and the natural dye plant dry powder E is 45-55 mL: 2g, and the total volume of the solution does not exceed 1/2 of the volume of the ball milling tank.
7. The color matching and dyeing method of the red and yellow natural dyes based on the eutectic solvent and the high-energy ball milling technology as claimed in claim 1, wherein in the step 3), the grinding beads comprise three types, the diameters of the three types are respectively 2mm, 6mm and 10mm, the number ratio of the three types is (5.9-6.1): 1.4-1.6): 1, and the total volume of the grinding beads does not exceed 1/6 of the volume of the ball milling tank.
8. The color matching dyeing method of the red and yellow natural dyes based on the eutectic solvent and the high-energy ball milling technology as claimed in claim 1, characterized in that in the ball milling process of the step 3), the rotating speed of the ball mill is controlled to be 195-205 r/min, and the ball milling time is controlled to be 10-12 min.
9. The method for color matching and dyeing of red and yellow natural dyes based on the eutectic solvent and the high-energy ball milling technology as claimed in claim 1, wherein in the step 4), the dyeing assistant G is a mixture of citric acid, acetic acid and 2- [ bis (carboxymethyl) amino ] acetic acid, and the molar ratio is 3 (1.8-2.1): 1.1-1.5.
10. The method for color matching and dyeing of red and yellow natural dyes based on the eutectic solvent and the high-energy ball milling technology as claimed in claim 1, wherein in the preparation process of the mordant liquid in the step 4), a dyeing assistant G is added until the pH of the solution is = 3-5; in the boiling and dyeing process, the temperature is controlled to be 70-75 ℃, and the time is controlled to be within 40 min.
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