CN118221971A - Preparation method of keratin-polymer mixed solution - Google Patents
Preparation method of keratin-polymer mixed solution Download PDFInfo
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- CN118221971A CN118221971A CN202410321029.3A CN202410321029A CN118221971A CN 118221971 A CN118221971 A CN 118221971A CN 202410321029 A CN202410321029 A CN 202410321029A CN 118221971 A CN118221971 A CN 118221971A
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
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- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- NPKDHFGECKNKBU-UHFFFAOYSA-N acetic acid;2-[2-(2-methoxyethoxy)ethoxy]ethanol Chemical compound CC(O)=O.COCCOCCOCCO NPKDHFGECKNKBU-UHFFFAOYSA-N 0.000 claims description 3
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 claims description 2
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 claims description 2
- CLLLODNOQBVIMS-UHFFFAOYSA-N 2-(2-methoxyethoxy)acetic acid Chemical compound COCCOCC(O)=O CLLLODNOQBVIMS-UHFFFAOYSA-N 0.000 claims description 2
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- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention discloses a preparation method of keratin-polymer mixed solution, which takes proton type ionic liquid as solvent to dissolve keratin and polymer to obtain keratin-polymer mixed solution; wherein the proton type ionic liquid is a proton type ionic liquid containing an ether structure. The method is simple, green and environment-friendly, the solvent is green and recyclable, and the production and recycling cost of the solvent is low; meanwhile, the keratin has high solubility, less solvent consumption and low keratin dissolving cost, and can greatly promote the application of the proton type ionic liquid in the keratin dissolving field.
Description
Technical Field
The invention relates to a processing method of keratin solution, in particular to a preparation method of keratin-polymer mixed solution.
Background
In the present day of green development and clean production, natural bio-based materials are receiving attention, and the sustainable development of the polymer industry can be greatly promoted by using renewable and environment-friendly natural polymers as material sources.
The keratin-polymer mixed solution is a polymer material mixed solution formed by taking keratin and polymers as raw materials and dissolving the keratin and the polymers by using a proper solvent, and has important application value and wide application prospect in the fields of regenerated fibers, regenerated gel, regenerated composite films and the like. A method for preparing silk-polymer mixed solution is disclosed in patent CN 111995772A.
Keratin is a strong fibrin, which is mainly found in hair, skin, nails, and animal materials such as feathers, wool, etc., and has a very wide source of raw materials and renewable characteristics, and has been industrially used very widely at present. The first step of obtaining keratin is to separate and extract keratin from raw materials such as hair, but the keratin has a unique three-dimensional network structure formed by connecting disulfide bonds, especially because of the fact that the keratin contains various acting forces such as hydrogen bonds, salt bonds, hydrophobic effects, van der Waals forces, disulfide bonds and the like, so that the keratin has good chemical stability and mechanical properties, and is difficult to dissolve and use because of being insoluble in common solvents. The most common keratin separation and extraction methods at present comprise a reduction method, an oxidation method, an acid-base hydrolysis method and the like, and the traditional methods can realize separation and extraction of keratin, but due to the process specificity, the structure of the keratin is easily seriously damaged and the keratin is excessively degraded during separation and extraction, so that the quality of the keratin is influenced, a large amount of harmful waste solvents are generated in the extraction process, and the concept of non-green development is realized.
The ionic liquid is a green solvent with great application prospect in recent years, and is widely applied and practically verified in various fields. In recent years, a large number of reports have demonstrated that it also shows excellent promise in dissolving keratin. For example: in 2005, xie et al studied the effect of various ionic liquids on wool keratin dissolution, such as [ Bmim ] Cl, [ ami ] Br, [ Bmim ] [ BF4] and [ Bmim ] [ PF6], on wool keratin dissolution, and showed that [ Bmim ] [ BF4] and [ Bmim ] [ PF6] could not dissolve wool keratin, whereas chloride ionic liquids [ Bmim ] Cl and [ Amim ] Cl exhibited good dissolution ability on wool keratin, and the alpha-helical structure of wool keratin was destroyed by ionic liquid during dissolution, and the regenerated wool keratin had a beta-sheet structure. Chen et al take single wool fiber as an example, and visually observe the dissolution process of the wool fiber in various ionic liquids through a polarizing microscope, find that obvious difference exists in dissolution rate of different ionic liquids, the dissolution rate of [ Bmim ] [ OAc ] is fastest, the single wool fiber can be completely dissolved within 3 minutes, and the time of [ Bmim ] Cl, 1, 3-tetramethylguanidine propionate is longer. Cariny and the like research the solubility of chicken feather in the ionic liquid, successfully realize the recovery of the ionic liquid, and promote the academic research and industrial application of the ionic liquid.
However, the ionic liquids adopted in the prior reports are imidazole quaternary ammonium salt ionic liquids, the preparation cost is high, the separation and purification difficulty is high, the regeneration cost is high, and the viscosity of the obtained keratin solution is high, so that the keratin solution is not beneficial to post-processing.
The proton type ionic liquid is a novel ionic liquid which is completely different from the existing imidazole quaternary ammonium salt ionic liquid, is usually obtained by directly reacting an organic/inorganic acid and an organic amine, has simple preparation process and low cost, can be recycled after being treated by simple means such as distillation, and therefore, has been paid attention.
However, the ionic liquid is completely different from the existing imidazole quaternary ammonium salt ionic liquid, so that the report of preparing keratin solution by using the ionic liquid to dissolve keratin is very rare at present. Patent CN111995772a discloses a preparation method of silk-polymer mixed solution, which prepares a proton type ionic liquid by mixing carboxylic acid compounds such as formic acid and organic amine, and successfully dissolves silk by taking the proton type ionic liquid as a solvent, thus obtaining silk solution. However, the solubility of the ionic liquid in the report on silk and polymers is not high, and the maximum mass concentration of silk in the solvent is only about 7-23%, so that the dosage of the proton type ionic liquid can be greatly increased when the keratin solution is prepared, thereby improving the preparation cost of the keratin solution and preventing the application of the proton type ionic liquid in the field of keratin dissolution.
Therefore, it is necessary to improve the dissolution system of the proton type ionic liquid, improve the solubility of keratin, reduce the dissolution cost and promote the application of the proton type ionic liquid in keratin dissolution, thereby promoting the green development of the polymer industry.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a keratin-polymer mixed solution. The method is simple, green and environment-friendly, the solvent is green and recyclable, and the production and recycling cost of the solvent is low; meanwhile, the keratin-polymer disclosed by the invention has the advantages of high solubility, less solvent consumption and low dissolution cost, and can greatly promote the application of the proton-type ionic liquid in the field of keratin-polymer dissolution.
The technical scheme of the invention is as follows:
a preparation method of keratin-polymer mixed solution, take proton ionic liquid as solvent, dissolve keratin and polymer, get keratin-polymer solution;
wherein the proton type ionic liquid is a proton type ionic liquid containing an ether structure.
Preferably, the method for preparing a keratin-polymer mixed solution comprises the following steps:
s1, degreasing keratin raw materials to obtain degreased keratin;
s2, taking a proton type ionic liquid containing an ether structure, adding defatted keratin and a polymer into the proton type ionic liquid containing the ether structure, and stirring under a heating condition to dissolve the defatted keratin and the polymer to obtain a keratin/polymer mixed solution.
Preferably, in the preparation method of the keratin-polymer mixed solution, the proton-type ionic liquid containing the ether structure is prepared from carboxylic acid compounds containing the ether structure and organic base serving as raw materials.
Preferably, the preparation method of the keratin-polymer mixed solution comprises the following steps: and (3) placing the organic base in a container, introducing nitrogen, and adding a carboxylic acid compound containing an ether structure under the stirring state and ice bath condition to obtain the proton type ionic liquid containing the ether structure.
Preferably, the organic base is one or a mixture of more than one of 1, 3-tetramethyl guanidine, 1, 5-diazabicyclo [4.3.0] -5-nonene, 1, 8-diazabicyclo undec-7-ene, di-n-butylamine or triethylamine.
Preferably, the carboxylic acid compound containing ether structure is one or a mixture of any more of methoxyacetic acid, 2- (2-methoxyethoxy) acetic acid, 2- (2-methoxyethoxy) ethoxy) acetic acid or triethylene glycol monomethyl ether acetic acid.
Preferably, in the preparation method of the keratin-polymer mixed solution, the molar ratio of the organic base to the carboxylic acid compound containing an ether structure is 1:1.
Preferably, the polymer is one or a mixture of more than one of cellulose, chitin, chitosan, polylactic acid, polyacrylonitrile, polyethylene terephthalate, polybutylene terephthalate, polyglycolic acid ester or polycaprolactone.
Preferably, in the aforementioned method for preparing a keratin-polymer mixed solution, the mixing mass ratio of keratin to polymer in step S2 is 1:9 to 9:1.
Preferably, the degreasing treatment in S1 is carried out by soxhlet extracting keratin raw material in soxhlet extracting device with acetone/ethanol mixed solvent with mass ratio of 1:9-9:1 at 50-80deg.C for 24-48 hr, washing with deionized water, and drying.
Preferably, in the preparation method of the keratin-polymer mixed solution, the heating temperature of S2 is 60-180 ℃ and the heating time is 10-180min.
A keratin-polymer mixed solution prepared according to the foregoing method.
The invention has the beneficial effects that:
1. Compared with the prior reported proton type ionic liquid solvent, the solvent of the invention contains a large amount of ether bonds, and experiments prove that when the proton type ionic liquid containing the ether structure is used as the solvent to dissolve keratin and polymer to prepare a mixed solution, the solubility is greatly improved, and the direct benefit brought by the effect is that the use of the solvent can be greatly reduced, the dissolution cost of the keratin-polymer is reduced, and the invention has important significance for promoting the application of the proton type ionic liquid in the preparation of the keratin-polymer mixed solution.
2. The keratin dissolving method is simple, green and environment-friendly, and accords with the concept of green development.
3. The proton type ionic liquid solvent is prepared by adopting green raw materials and a simple process, has low production cost, does not need special process treatment when being recycled, and has simple treatment mode and low recycling cost.
Drawings
FIG. 1 is a graph of apparent viscosity versus shear rate for a 5% mass fraction waste wool keratin/cellulose solution prepared in example six. Referring to fig. 1, the apparent viscosity of the waste wool keratin/cellulose solution prepared according to the technical scheme provided by the invention is reduced along with the increase of the shear rate, and the waste wool keratin/cellulose solution shows the characteristic of shear thinning.
FIG. 2 is a graph of the loss modulus G 'and storage modulus G' versus angular frequency for the 5% by mass fraction waste wool keratin/cellulose solution prepared in example six. Referring to fig. 2, in the old wool keratin/cellulose solution prepared according to the technical scheme provided by the invention, as the angular frequency increases, the storage modulus and the loss modulus both increase, the corresponding angular frequency range can qualitatively represent the entanglement degree inside the solution system, and as the angular frequency increases, the G 'and the G' respectively increase, and then the intersection point occurs.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
Embodiments of the invention
Embodiment one:
Preparation of a sheep keratin/cotton pulp cellulose solution:
(1) Degreasing sheep wool, performing Soxhlet extraction for 48 hours at 80 ℃ in a Soxhlet extraction device by using an acetone/ethanol mixed solvent, and then washing and drying the sheep wool by using deionized water, wherein the mass ratio of the acetone/ethanol mixed solvent is 5:5; obtaining degreased sheep wool;
(2) Cutting absorbent cotton wool into small sections of 1-3cm, tearing cotton pulp cellulose into small blocks, and fully drying, wherein the mass ratio of the absorbent cotton wool to the cotton pulp cellulose is 1:1;
(3) Mixing methoxy acetic acid and l, 5-diazabicyclo [4.3.0] -5-nonene according to a molar ratio of 1:1, fully mixing in a flask, and placing in an ice bath for low-speed stirring to obtain a proton type ionic liquid containing an ether structure;
(4) Dissolving the dry defatted sheep wool and cotton pulp cellulose in the step (2) in the proton type ionic liquid containing the ether structure in the step (3), wherein the dissolving temperature is 120 ℃, and stirring at a low speed for 40min to obtain a sheep wool keratin/cotton pulp cellulose solution.
Embodiment two:
Under the same conditions as in example one, different proton-type ionic liquids were prepared using different carboxylic acid compounds and organic bases, and different keratin/polymer species were dissolved under different conditions. The solubility was compared, and the results are shown in Table 1.
Table 1: solubility of different ionic liquids in different keratin/polymer materials
The result shows that the more the ether structure is contained in the 1, the better the dissolution effect is, for example, the maximum mass concentration of the sheep wool in the proton type ionic liquid without the ether structure with the sequence number of 8 is only 12 percent, which is far lower than the maximum mass concentration of the sheep wool in the proton type ionic liquid prepared by triethylene glycol monomethyl ether acetic acid by 33 percent; 2. the stronger the alkalinity of the organic alkali is, the better the dissolution effect is; 3. as the temperature increases, the keratin/polymer dissolution efficiency tends to increase, with temperatures exceeding 140 ℃, and dissolution efficiency decreases; 4. the maximum dissolved mass concentration also tended to increase with increasing reaction time, and the maximum mass concentration of wool keratin/cellulose did not increase after 180 minutes of reaction.
Embodiment III:
preparation of goat hair keratin/cotton pulp cellulose solution:
(1) Degreasing goat hair, performing Soxhlet extraction for 24 hours at 50 ℃ by using an acetone/ethanol mixed solvent in a Soxhlet extraction device, and then washing and drying the goat hair by using deionized water, wherein the mass ratio of the acetone/ethanol mixed solvent is 1:9;
(2) Cutting the defatted goat hair into 1-3cm small sections, tearing cotton pulp cellulose into small blocks, and fully drying, wherein the mass ratio of the defatted goat hair to the cotton pulp cellulose is 1:1;
(3) Methoxy acetic acid and l, 5-diazabicyclo [4.3.0] -5-nonene (DBN) are taken according to a molar ratio of 1:1, fully mixing in a flask, and stirring in an ice bath at a low speed;
(4) Dissolving the defatted goat hair and cotton pulp cellulose in the step (2) in the ionic liquid in the step (3), wherein the dissolving temperature is 60 ℃, and stirring for 10min at a low speed to obtain goat hair keratin/cotton pulp cellulose solution.
Embodiment four:
preparation of yak wool keratin/cotton pulp cellulose solution:
(1) Degreasing yak hair, performing Soxhlet extraction for 30 hours at 60 ℃ in a Soxhlet extraction device by using an acetone/ethanol mixed solvent, and then washing and drying the yak hair by using deionized water, wherein the mass ratio of the acetone/ethanol mixed solvent is 5:9;
(2) Cutting defatted yak hair into 1-3cm segments, tearing cotton pulp cellulose into small blocks, and fully drying until the mass ratio of the defatted yak hair to the cotton pulp cellulose is 1:1;
(3) Mixing methoxyacetic acid and l, 5-diazabicyclo [4.3.0] -5-nonene (DBN) according to a molar ratio of 1:1, fully mixing in a flask, and stirring in an ice bath at low speed;
(4) Dissolving the defatted yak hair and cotton pulp cellulose in the step (2) in the ionic liquid in the step (3), wherein the dissolving temperature is 100 ℃, and stirring at a low speed for 20min to obtain yak hair keratin/cotton pulp cellulose solution.
Fifth embodiment:
Preparation of a porcine hair keratin/cotton pulp cellulose solution:
(1) Degreasing pig hair, performing Soxhlet extraction for 35 hours at 70 ℃ by using an acetone/ethanol mixed solvent in a Soxhlet extraction device, and then washing and drying the pig hair by using deionized water, wherein the mass ratio of the acetone/ethanol mixed solvent is 1:1;
(2) Cutting defatted pig hair into 1-3cm small sections, tearing cotton pulp cellulose into small blocks, and fully drying, wherein the mass ratio of the defatted goat hair to the cotton pulp cellulose is 1:1;
(3) Mixing methoxyacetic acid and l, 5-diazabicyclo [4.3.0] -5-nonene (DBN) according to a molar ratio of 1:1, fully mixing in a flask, and stirring in an ice bath at low speed;
(4) Dissolving the defatted pig hair in the step (2) in the ionic liquid in the step (3) according to the mass fraction of 5%, wherein the dissolving temperature is 130 ℃, and stirring at a low speed for 80min to obtain pig hair keratin/cotton pulp cellulose solution.
Example six:
preparation of wool keratin/cotton pulp cellulose solution:
(1) Degreasing waste wool textiles, performing Soxhlet extraction for 40 hours at 70 ℃ by using an acetone/ethanol mixed solvent in a Soxhlet extraction device, and then washing and drying the waste wool textiles by using deionized water, wherein the mass ratio of the acetone/ethanol mixed solvent is 9:4;
(2) Cutting the defatted waste wool into small sections of 1-3cm, tearing cotton pulp cellulose into small blocks, and fully drying, wherein the mass ratio of the defatted goat wool to the cotton pulp cellulose is 4:6;
(3) Mixing methoxyacetic acid and l, 5-diazabicyclo [4.3.0] -5-nonene (DBN) according to a molar ratio of 1:1, fully mixing in a flask, and stirring in an ice bath at low speed;
(4) Dissolving the defatted waste wool and cotton pulp cellulose in the step (2) in the ionic liquid in the step (3), wherein the dissolving temperature is 140 ℃, and stirring for 90 minutes at a low speed to obtain waste wool keratin/cotton pulp cellulose solution.
Embodiment seven:
Preparation of fibroin/chitosan solution:
(1) Degreasing the waste silk textiles, performing Soxhlet extraction for 40 hours at 70 ℃ by using an acetone/ethanol mixed solvent in a Soxhlet extraction device, and then washing and drying the waste silk textiles by using deionized water, wherein the mass ratio of the acetone/ethanol mixed solvent is 9:4;
(2) Cutting defatted waste silk into 1-3cm segments, taking chitosan powder, and fully drying, wherein the mass ratio of the defatted silk to the chitosan is 8:2;
(3) Mixing methoxyacetic acid and l, 5-diazabicyclo [4.3.0] -5-nonene (DBN) according to a molar ratio of 1:1, fully mixing in a flask, and stirring in an ice bath at low speed;
(4) Dissolving the defatted waste silk and chitosan obtained in the step (2) in the ionic liquid obtained in the step (3), wherein the dissolving temperature is 120 ℃, and stirring at a low speed for 80min to obtain waste silk protein/chitosan dissolving liquid.
While the invention has been described with reference to the preferred embodiments, it should be understood that the invention is not limited to the embodiments described above, but is intended to cover modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. A method for preparing a keratin-polymer mixed solution, characterized by: taking proton type ionic liquid as a solvent, and obtaining keratin-polymer mixed solution after dissolving keratin and polymer;
wherein the proton type ionic liquid is a proton type ionic liquid containing an ether structure.
2. The method for preparing a keratin-polymer mixed solution according to claim 1, characterized in that it comprises the steps of:
s1, degreasing keratin raw materials to obtain degreased keratin;
s2, taking a proton type ionic liquid containing an ether structure, adding defatted keratin and a polymer into the proton type ionic liquid containing the ether structure, and stirring under a heating condition to dissolve the defatted keratin and the polymer to obtain a keratin-polymer mixed solution.
3. The method for preparing a keratin-polymer mixed solution according to claim 1 or 2, characterized in that: the proton type ionic liquid containing the ether structure is prepared from a carboxylic acid compound containing the ether structure and an organic base serving as raw materials by the following method: and (3) placing the organic base in a container, introducing nitrogen, and adding a carboxylic acid compound containing an ether structure under the stirring state and ice bath condition to obtain the proton type ionic liquid containing the ether structure.
4. A process for the preparation of a keratin-polymer mixed solution as claimed in claim 3, characterized in that: the organic base is one or a mixture of any more of 1, 3-tetramethyl guanidine, 1, 5-diazabicyclo [4.3.0] -5-nonene, 1, 8-diazabicyclo undec-7-ene, di-n-butylamine or triethylamine.
5. A process for the preparation of a keratin-polymer mixed solution as claimed in claim 3, characterized in that: the carboxylic acid compound containing the ether structure is one or a mixture of any more of methoxyacetic acid, 2- (2-methoxyethoxy) acetic acid, 2- (2-methoxyethoxy) ethoxy) acetic acid or triethylene glycol monomethyl ether acetic acid.
6. A process for the preparation of a keratin-polymer mixed solution as claimed in claim 3, characterized in that: the molar ratio of the organic base to the carboxylic acid compound containing the ether structure is 1:1.
7. The method for preparing a keratin-polymer mixed solution according to claim 1 or 2, characterized in that: the polymer is one or a mixture of more than one of cellulose, chitin, chitosan, polylactic acid, polyacrylonitrile, polyethylene terephthalate, polybutylene terephthalate, polyglycolic acid ester or polycaprolactone, wherein the mixing mass ratio of the keratin to the polymer is 1:9-9:1.
8. The method for preparing a keratin-polymer mixed solution according to claim 2, characterized in that: and S1, degreasing, namely performing Soxhlet extraction on the keratin raw material in a Soxhlet extraction device by using an acetone/ethanol mixed solvent with a mass ratio of 1:9-9:1 for 24-48 hours at 50-80 ℃, and then washing by using deionized water and drying.
9. The method for preparing a keratin-polymer mixed solution according to claim 2, characterized in that: and S2, heating at 60-180 ℃ for 10-180min.
10. A keratin-polymer mixed solution prepared according to the method of any one of claims 1 to 9.
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