CN115821580B - Modified silk fiber and preparation method and application thereof - Google Patents
Modified silk fiber and preparation method and application thereof Download PDFInfo
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- CN115821580B CN115821580B CN202211584127.3A CN202211584127A CN115821580B CN 115821580 B CN115821580 B CN 115821580B CN 202211584127 A CN202211584127 A CN 202211584127A CN 115821580 B CN115821580 B CN 115821580B
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Abstract
The invention relates to a modified silk fiber and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, adding dicyclopentadienyl acrylate, dibenzoyl peroxide and naringin into an ethanol/water mixed solvent to obtain a first mixed solution, performing grafting reaction under a protective gas atmosphere, and then washing and drying to obtain modified dicyclopentadienyl acrylate; s2, adding modified dicyclopentadienyl acrylate and tert-butyl peroxypivalate into ethanol to obtain a second mixed solution; swelling silk fiber, placing the silk fiber in a second mixed solution under a protective gas atmosphere for grafting reaction, and then shaping, washing and drying to obtain modified silk fiber.
Description
Technical Field
The invention relates to the technical field of textiles, in particular to a modified silk fiber, and a preparation method and application thereof.
Background
The silk fiber is also called natural silk, and is continuous filament yarn formed by solidifying liquid silk protein secreted by mature silkworms during cocoon formation. The silk fiber is the lightest, softest and thinnest natural protein fiber in nature, and can be easily restored after external force is removed. The silk fiber product is soft and elegant, has fine and soft hand feeling, is smooth, has high elasticity and good moisture absorption and air permeability, is an important textile raw material, and is commonly used for manufacturing household textiles such as silk quilts and the like.
The silk fiber comprises silk fibroin and sericin as main components, wherein the silk fibroin and sericin mainly comprise glycine, alanine, valine, leucine, isoleucine, serine, threonine, tyrosine, phenylalanine, proline, tryptophan, lysine, histidine, arginine, aspartic acid, glutamic acid and other amino acids. Researches show that fibroin mainly composed of amino acids has antibacterial effect.
However, the antibacterial effect of silk fiber products needs to be further improved and the antibacterial time period needs to be further prolonged.
Disclosure of Invention
Accordingly, the invention aims to provide a modified silk fiber, a preparation method and application thereof, so as to improve the antibacterial effect of silk fiber products and prolong the antibacterial aging of the silk fiber products.
In a first aspect, the present invention provides a method for preparing a modified silk fiber, comprising the steps of:
S1, adding dicyclopentadienyl acrylate, dibenzoyl peroxide and naringin into an ethanol/water mixed solvent to obtain a first mixed solution, performing grafting reaction under a protective gas atmosphere, and then washing and drying to obtain modified dicyclopentadienyl acrylate;
S2, adding modified dicyclopentadienyl acrylate and tert-butyl peroxypivalate into ethanol to obtain a second mixed solution; and (3) swelling the silk fiber, placing the silk fiber in a second mixed solution under the atmosphere of protective gas for grafting reaction, and then shaping, washing and drying to obtain the modified silk fiber.
In the present application, the shielding gas includes nitrogen, helium, argon, neon, and the like.
Further, in the ethanol/water mixed solvent in step S1, the mass ratio of ethanol to water is 1:1-3:1, preferably 1:1-2:1.
Further, in step S1, the mass ratio of naringin to dicyclopentanyl acrylate is 2:100-5:100, preferably 3:100-5:100.
Further, in the step S1, the mass ratio of dibenzoyl peroxide to dicyclopentadienyl acrylate is 0.25:100-0.5:100, preferably 0.3:100-0.5:100.
Further, the concentration of the dicyclopentadienyl acrylate in the first mixed solution in the step S1 is 45-60g/L, preferably 50-60g/L.
Further, in step S1, the temperature of the grafting reaction is 70-85 ℃, preferably 75-85 ℃; the grafting reaction time is 45 to 90min, preferably 50 to 90min.
Further, in step S1, the drying temperature is 50-70 ℃, preferably 60-70 ℃; the drying time is 15-30min, preferably 20-30min.
Further, N-dimethylaniline is added to the first mixed solution in step S1.
Further, in the step S1, the mass ratio of the N, N-dimethylaniline to the dicyclopentadienyl acrylate is 0.1:1-0.3:1, preferably 0.15:1-0.3:1.
Further, ethyl acetate is also added to the first mixed solution in step S1.
Further, in step S1, the mass ratio of the ethyl acetate to the dicyclopentadienyl acrylate is 0.05:1-0.08:1, preferably 0.06:1-0.08:1.
Further, in the step S2, the mass ratio of the tert-butyl peroxypivalate to the modified dicyclopentadienyl acrylate is 2:100-4:100, preferably 3:100-4:100.
Further, in the second mixed solution in the step S2, the concentration of the tert-butyl peroxypivalate is 20-30g/L, preferably 25-30g/L.
Further, in the swelling process in step S2, the swelling agent is a calcium chloride solution.
Further, in step S2, the swelling temperature is 65-75 ℃, preferably 70-75 ℃; the swelling time is 30-60min, preferably 45-60min.
Further, in step S2, the concentration of the calcium chloride solution is 2wt% to 3.5wt%, preferably 2.5wt% to 3.5wt%.
Further, in step S2, the mass ratio of the silk fiber to the second mixed solution is 1:5-1:10, preferably 1:6-1:10.
Further, in step S2, the temperature of the grafting reaction is 95-105 ℃, preferably 100-105 ℃; the grafting reaction time is 30 to 45min, preferably 35 to 45min.
Further, in step S2, the temperature of the drying is 50-60 ℃, preferably 55-60 ℃; the drying time is 20-30min, preferably 25-30min.
In a second aspect, the present invention also aims to provide a modified silk fiber prepared by the preparation method.
In a third aspect, the present invention also aims to provide the modified silk fiber prepared by the preparation method or the application of the modified silk fiber in the quilt filling material.
The invention has the beneficial effects that:
(1) According to the invention, dibenzoyl peroxide can initiate a grafting reaction, naringin is grafted onto dicyclopentanyl acrylate through the grafting reaction to obtain modified dicyclopentanyl acrylate, and the modified dicyclopentanyl acrylate is grafted onto silk fiber through the grafting reaction, namely naringin with an antibacterial function is introduced into the silk fiber through a chemical bonding mode, so that the antibacterial effect of silk fiber products is improved, and the antibacterial ageing of the silk fiber products is prolonged.
(2) According to the invention, the N, N-dimethylaniline and dibenzoyl peroxide are compounded for use, so that the antibacterial performance of the fabric made of the modified silk fiber can be further improved.
(3) According to the invention, the ethyl acetate can activate dibenzoyl peroxide, promote the grafting reaction, improve the grafting rate and further improve the antibacterial performance of the fabric made of the modified silk fiber.
Detailed Description
The present invention will be further described with reference to the following specific examples, but it should be noted that the specific material ratios, process conditions, results, etc. described in the embodiments of the present invention are only for illustrating the present invention, and are not intended to limit the scope of the present invention, and all equivalent changes or modifications according to the spirit of the present invention should be included in the scope of the present invention. It is to be noted that "wt%" as shown in the description herein means "mass fraction", unless otherwise specified.
The invention provides a preparation method of modified silk fiber, which comprises the following steps:
S1, adding dicyclopentadienyl acrylate, dibenzoyl peroxide and naringin into an ethanol/water mixed solvent to obtain a first mixed solution with the concentration of the dicyclopentadienyl acrylate of 45-60g/L, wherein the mass ratio of the ethanol to the water in the ethanol/water mixed solvent is 1:1-3:1, the mass ratio of naringin to dicyclopentanyl acrylate is 2:100-5:100, the mass ratio of dibenzoyl peroxide to dicyclopentenyl acrylate is 0.25:100-0.5:100;
Then carrying out grafting reaction for 45-90min at 70-85 ℃ in a protective gas atmosphere, then washing, and then drying for 15-30min at 50-70 ℃ to obtain modified dicyclopentadienyl acrylate;
S2, adding modified dicyclopentanyl acrylate and tert-butyl peroxypivalate into ethanol to obtain a second mixed solution with the concentration of the tert-butyl peroxypivalate being 20-30g/L, wherein the mass ratio of the tert-butyl peroxypivalate to the modified dicyclopentanyl acrylate is 2:100-4:100;
Swelling silk fiber in calcium chloride solution with concentration of 2-3.5 wt% at 65-75deg.C for 30-60min;
Then placing silk fiber in a second mixed solution under the protective gas atmosphere for grafting reaction for 30-45min at the temperature of 95-105 ℃, wherein the mass ratio of the silk fiber to the second mixed solution is 1:5-1:10; and then shaping and washing, and then drying at 50-60 ℃ for 20-30min to obtain the modified silk fiber.
In another embodiment of the present invention, the first mixed solution is further added with N, N-dimethylaniline, wherein the mass ratio of the N, N-dimethylaniline to the dicyclopentadienyl acrylate is 0.1:1-0.3:1.
In another embodiment of the present invention, ethyl acetate is further added to the first mixed solution, and a mass ratio of the ethyl acetate to the dicyclopentadienyl acrylate is 0.05:1-0.08:1.
The invention also provides the modified silk fiber prepared by the preparation method.
The invention also provides the modified silk fiber prepared by the preparation method or the application of the modified silk fiber in the quilt filling material.
The present invention will be described in detail with reference to specific exemplary examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, as many insubstantial modifications and variations are within the scope of the invention as would be apparent to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
The modified silk fiber is prepared by the following steps:
S1, adding dicyclopentadienyl acrylate, dibenzoyl peroxide and naringin into an ethanol/water mixed solvent to obtain a first mixed solution with 45g/L of dicyclopentadienyl acrylate, wherein the mass ratio of ethanol to water in the ethanol/water mixed solvent is 1:1, the mass ratio of naringin to dicyclopentanyl acrylate is 2:100, the mass ratio of dibenzoyl peroxide to dicyclopentenyl acrylate is 0.5:100;
Then carrying out grafting reaction for 45min under nitrogen atmosphere at the temperature of 85 ℃, then washing with absolute ethyl alcohol, and then drying for 15min at the temperature of 70 ℃ to obtain modified dicyclopentadienyl acrylate;
S2, adding modified dicyclopentadienyl acrylate and tert-butyl peroxypivalate into ethanol to obtain a second mixed solution with the concentration of the tert-butyl peroxypivalate of 20g/L, wherein the mass ratio of the tert-butyl peroxypivalate to the modified dicyclopentadienyl acrylate is 2:100;
swelling silk fiber in calcium chloride solution with mass 10 times of that of the silk fiber at 65deg.C and concentration of 2wt% for 30min;
Then placing silk fiber in a second mixed solution under nitrogen atmosphere for grafting reaction for 30min at 105 ℃, wherein the mass ratio of the silk fiber to the second mixed solution is 1:5, a step of; and then shaping and washing, and then drying at 60 ℃ for 20min to obtain the modified silk fiber.
Example 2
The modified silk fiber is prepared by the following steps:
S1, adding dicyclopentadienyl acrylate, dibenzoyl peroxide and naringin into an ethanol/water mixed solvent to obtain a first mixed solution with the concentration of the dicyclopentadienyl acrylate of 60g/L, wherein the mass ratio of the ethanol to the water in the ethanol/water mixed solvent is 3:1, the mass ratio of naringin to dicyclopentanyl acrylate is 5:100, the mass ratio of dibenzoyl peroxide to dicyclopentenyl acrylate is 0.25:100;
Then carrying out grafting reaction for 90min in nitrogen atmosphere at 70 ℃, then washing with absolute ethyl alcohol, and then drying for 30min at 50 ℃ to obtain modified dicyclopentadienyl acrylate;
S2, adding modified dicyclopentadienyl acrylate and tert-butyl peroxypivalate into ethanol to obtain a second mixed solution with the concentration of tert-butyl peroxypivalate of 30g/L, wherein the mass ratio of the tert-butyl peroxypivalate to the modified dicyclopentadienyl acrylate is 4:100;
Swelling silk fiber in calcium chloride solution with a mass 6 times of that of silk fiber at 75deg.C and a concentration of 3.5wt% for 60min;
Then placing silk fiber in a second mixed solution under nitrogen atmosphere for grafting reaction for 45min at the temperature of 95 ℃, wherein the mass ratio of the silk fiber to the second mixed solution is 1:10; and then shaping and washing, and then drying at 50 ℃ for 30min to obtain the modified silk fiber.
Example 3
The modified silk fiber is prepared by the following steps:
s1, adding dicyclopentadienyl acrylate, dibenzoyl peroxide and naringin into an ethanol/water mixed solvent to obtain a first mixed solution with 554g/L of dicyclopentadienyl acrylate, wherein the mass ratio of ethanol to water in the ethanol/water mixed solvent is 1:2, the mass ratio of naringin to dicyclopentanyl acrylate is 4:100, the mass ratio of dibenzoyl peroxide to dicyclopentenyl acrylate is 0.3:100;
then carrying out grafting reaction for 60min under nitrogen atmosphere at the temperature of 75 ℃, then washing with absolute ethyl alcohol, and then drying for 25min at the temperature of 60 ℃ to obtain modified dicyclopentadienyl acrylate;
S2, adding modified dicyclopentadienyl acrylate and tert-butyl peroxypivalate into ethanol to obtain a second mixed solution with the concentration of the tert-butyl peroxypivalate of 25g/L, wherein the mass ratio of the tert-butyl peroxypivalate to the modified dicyclopentadienyl acrylate is 3:100;
swelling silk fiber in calcium chloride solution with a mass of 8 times of that of the silk fiber at 70 ℃ and a concentration of 3wt% for 48min;
Then placing silk fiber in a second mixed solution under nitrogen atmosphere for grafting reaction at 100 ℃ for 36min, wherein the mass ratio of the silk fiber to the second mixed solution is 1:8, 8; and then shaping and washing, and then drying at 54 ℃ for 26min to obtain the modified silk fiber.
Example 4
Modified silk fibers were prepared in the same manner as in example 1, except for the following conditions:
S1, adding dicyclopentadienyl acrylate, dibenzoyl peroxide, naringin and N, N-dimethylaniline into an ethanol/water mixed solvent to obtain a first mixed solution with the concentration of 45g/L of dicyclopentadienyl acrylate, wherein the mass ratio of ethanol to water in the ethanol/water mixed solvent is 1:1, the mass ratio of naringin to dicyclopentanyl acrylate is 2:100, the mass ratio of dibenzoyl peroxide to dicyclopentenyl acrylate is 0.5: the mass ratio of 100, N-dimethylaniline to dicyclopentenyl acrylate is 0.1:1, a step of;
Then, the grafting reaction is carried out for 45min under the protection gas atmosphere at the temperature of 85 ℃, then the modified dicyclopentadienyl acrylate is obtained after washing with absolute ethyl alcohol and then drying for 15min at the temperature of 70 ℃.
Example 5
Modified silk fibers were prepared in the same manner as in example 1, except for the following conditions:
s1, adding dicyclopentadienyl acrylate, dibenzoyl peroxide, naringin and N, N-dimethylaniline into an ethanol/water mixed solvent to obtain a first mixed solution with the concentration of 45g/L of dicyclopentadienyl acrylate, wherein the mass ratio of ethanol to water in the ethanol/water mixed solvent is 1:1, the mass ratio of naringin to dicyclopentanyl acrylate is 2:100, the mass ratio of dibenzoyl peroxide to dicyclopentenyl acrylate is 0.5: the mass ratio of 100, N-dimethylaniline to dicyclopentenyl acrylate is 0.3:1, a step of;
Then, the grafting reaction is carried out for 45min under the protection gas atmosphere at the temperature of 85 ℃, then the modified dicyclopentadienyl acrylate is obtained after washing with absolute ethyl alcohol and then drying for 15min at the temperature of 70 ℃.
Example 6
Modified silk fibers were prepared in the same manner as in example 1, except for the following conditions:
S1, adding dicyclopentadienyl acrylate, dibenzoyl peroxide, naringin and ethyl acetate into an ethanol/water mixed solvent to obtain a first mixed solution with 45g/L of dicyclopentadienyl acrylate, wherein the mass ratio of ethanol to water in the ethanol/water mixed solvent is 1:1, the mass ratio of naringin to dicyclopentanyl acrylate is 2:100, the mass ratio of dibenzoyl peroxide to dicyclopentenyl acrylate is 0.5:100, the mass ratio of the ethyl acetate to the dicyclopentadienyl acrylate is 0.05:1, a step of;
Then, the grafting reaction is carried out for 45min under the protection gas atmosphere at the temperature of 85 ℃, then the modified dicyclopentadienyl acrylate is obtained after washing with absolute ethyl alcohol and then drying for 15min at the temperature of 70 ℃.
Example 7
Modified silk fibers were prepared in the same manner as in example 1, except for the following conditions:
s1, adding dicyclopentadienyl acrylate, dibenzoyl peroxide, naringin and ethyl acetate into an ethanol/water mixed solvent to obtain a first mixed solution with 45g/L of dicyclopentadienyl acrylate, wherein the mass ratio of ethanol to water in the ethanol/water mixed solvent is 1:1, the mass ratio of naringin to dicyclopentanyl acrylate is 2:100, the mass ratio of dibenzoyl peroxide to dicyclopentenyl acrylate is 0.5:100, the mass ratio of the ethyl acetate to the dicyclopentadienyl acrylate is 0.08:1, a step of;
Then, the grafting reaction is carried out for 45min under the protection gas atmosphere at the temperature of 85 ℃, then the modified dicyclopentadienyl acrylate is obtained after washing with absolute ethyl alcohol and then drying for 15min at the temperature of 70 ℃.
Performance detection
The modified silk fibers prepared in examples 1-7 and silk fibers (hereinafter referred to as a control group) which are the same as those of example 1 are respectively processed into fabrics, cut into fragments with the size of 5mm x 5mm, and 0.75g of a sample is weighed, and according to the part 3 of evaluation of the antibacterial property of GBT 20944.3-2008 textiles: the oscillation method detects the bacteriostasis rate of the sample (namely before being placed);
the antimicrobial properties of textiles were then evaluated according to GBT 20944.3-2008, section 3, after 60 days of indoor placement: the test pieces were tested for their antibacterial activity (i.e., after being placed) by the method of oscillation, and the results are shown in Table 1.
TABLE 1 detection results
As can be seen from Table 1, the antibacterial rates of the fabrics processed from the modified silk fibers of examples 1-7 are not significantly different before and after the placement, and the results show that the antibacterial aging of silk fiber products is effectively prolonged.
Compared with the fabric processed by the modified silk fibers in the embodiment 1 (after being placed), the antibacterial rate of the modified silk fibers in the embodiment 4 and the embodiment 5 on staphylococcus aureus is improved by about 22.8% and about 24.2%, and the antibacterial rate on escherichia coli is improved by about 22.3% and about 23.9%, respectively.
Compared with the fabric processed by the modified silk fibers of the embodiment 1 (after being placed), the antibacterial rate of the modified silk fibers of the embodiment 6 and the embodiment 7 on staphylococcus aureus is respectively improved by about 22.6% and about 24.8%, and the antibacterial rate of the modified silk fibers on escherichia coli is respectively improved by about 23.2% and about 23.5%, and the result shows that the ethyl acetate can activate dibenzoyl peroxide, promote the grafting reaction, improve the grafting rate and further improve the antibacterial performance of the fabric made of the modified silk fibers.
In summary, dibenzoyl peroxide can initiate grafting reaction, and then naringin is grafted onto dicyclopentadienyl acrylate through grafting reaction to obtain modified dicyclopentadienyl acrylate, and then the modified dicyclopentanyl acrylate is grafted onto silk fiber through grafting reaction, namely naringin with antibacterial function is introduced into silk fiber through chemical bonding mode, so that antibacterial effect of silk fiber products is improved, and antibacterial aging of silk fiber products is prolonged. The N, N-dimethylaniline and dibenzoyl peroxide are compounded for use, so that the antibacterial performance of the fabric made of the modified silk fiber can be further improved. The ethyl acetate can activate dibenzoyl peroxide, promote the grafting reaction, improve the grafting rate and further improve the antibacterial performance of the fabric made of the modified silk fiber. In conclusion, the antibacterial performance durability of the fabric processed by the modified silk fiber is effectively improved.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (8)
1. The preparation method of the modified silk fiber is characterized by comprising the following steps of:
S1, adding dicyclopentadienyl acrylate, dibenzoyl peroxide, ethyl acetate and naringin into an ethanol/water mixed solvent to obtain a first mixed solution, performing grafting reaction under a protective gas atmosphere, and then washing and drying to obtain modified dicyclopentadienyl acrylate;
The mass ratio of the ethyl acetate to the dicyclopentadienyl acrylate is 0.05:1-0.08:1, a step of;
S2, adding modified dicyclopentadienyl acrylate and tert-butyl peroxypivalate into ethanol to obtain a second mixed solution; and (3) swelling the silk fiber, placing the silk fiber in a second mixed solution under the atmosphere of protective gas for grafting reaction, and then shaping, washing and drying to obtain the modified silk fiber.
2. The preparation method according to claim 1, wherein in the ethanol/water mixed solvent in step S1, the mass ratio of ethanol to water is 1:1-3:1, a step of;
And/or, in the step S1, the mass ratio of the naringin to the dicyclopentanenyl acrylate is 2:100-5:100;
And/or, in the step S1, the mass ratio of the dibenzoyl peroxide to the dicyclopentadienyl acrylate is 0.25:100-0.5:100;
And/or, in the first mixed solution in the step S1, the concentration of the dicyclopentadienyl acrylate is 45-60g/L;
And/or in the step S1, the temperature of the grafting reaction is 70-85 ℃, and the time of the grafting reaction is 45-90min;
and/or in the step S1, the drying temperature is 50-70 ℃ and the drying time is 15-30min.
3. The method according to claim 1, wherein N, N-dimethylaniline is further added to the first mixture in step S1.
4. The method according to claim 3, wherein in the step S1, the mass ratio of the N, N-dimethylaniline to the dicyclopentadienyl acrylate is 0.1:1-0.3:1.
5. The preparation method according to claim 1, wherein in the step S2, the mass ratio of the tert-butyl peroxypivalate to the modified dicyclopentadienyl acrylate is 2:100-4:100;
and/or, in the second mixed solution in the step S2, the concentration of the tert-butyl peroxypivalate is 20-30g/L;
And/or, in the swelling process in the step S2, the swelling agent is calcium chloride solution;
and/or in the step S2, the swelling temperature is 65-75 ℃, and the swelling time is 30-60min;
and/or, in the step S2, the concentration of the calcium chloride solution is 2wt% to 3.5wt%.
6. The method according to claim 1, wherein in step S2, the mass ratio of the silk fiber to the second mixed solution is 1:5-1:10;
And/or in the step S2, the temperature of the grafting reaction is 95-105 ℃, and the time of the grafting reaction is 30-45min;
And/or in the step S2, the drying temperature is 50-60 ℃ and the drying time is 20-30min.
7. Modified silk fibre produced by the production process according to any one of claims 1 to 6.
8. Use of modified silk fibres produced by a process according to any one of claims 1 to 6 in a quilt filling.
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