CN115584637A - Method for carrying out hydrophilic modification on chinlon fabric based on protease and laccase - Google Patents
Method for carrying out hydrophilic modification on chinlon fabric based on protease and laccase Download PDFInfo
- Publication number
- CN115584637A CN115584637A CN202211232897.1A CN202211232897A CN115584637A CN 115584637 A CN115584637 A CN 115584637A CN 202211232897 A CN202211232897 A CN 202211232897A CN 115584637 A CN115584637 A CN 115584637A
- Authority
- CN
- China
- Prior art keywords
- protease
- fabric
- solution
- laccase
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/11—Compounds containing epoxy groups or precursors thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a method for carrying out hydrophilic modification on a chinlon fabric based on protease and laccase, and belongs to the technical field of functional textiles. The invention discloses a method for carrying out hydrophilic modification on a chinlon fabric based on protease and laccase, which comprises the following steps: (1) Immersing the refined chinlon fabric into absolute ethyl alcohol for pretreatment, taking out and drying; (2) Uniformly mixing protease, an activating agent and a buffer solution to obtain a protease modified solution; then immersing the pretreated chinlon fabric into a protease modification solution for reaction; after the reaction is finished, cleaning, drying and balancing; (3) Uniformly mixing laccase, TEMPO, trehalose and a buffer solution to obtain a mixed solution; then soaking the polyamide fabric modified by the protease into the mixed solution for reaction; and after the reaction is finished, cleaning, drying and balancing to obtain the hydrophilic modified nylon fabric. The method has the advantages of low energy consumption, safety, environmental protection and good durability of hydrophilic modification.
Description
Technical Field
The invention relates to a method for carrying out hydrophilic modification on a chinlon fabric based on protease and laccase, and belongs to the technical field of functional textiles.
Background
Chinlon is the earliest synthetic fiber variety in the world, and has excellent performance and rich material resource, so that it is always the variety with the highest synthetic fiber yield. The nylon has the greatest characteristics of high strength and good wear resistance, and the strength and the wear resistance of the nylon are the first of all fibers. However, the disadvantages of nylon are the same as those of terylene, and the moisture absorption and permeability are poor; in a dry environment, the nylon is easy to generate static electricity, and the short-fiber nylon fabric is easy to fluff and pill. Therefore, in order to further improve the performance of the nylon fabric, the nylon fabric is often required to be modified.
At present, the commonly used chinlon functionalization modification method comprises the following steps: acid-base treatment, graft copolymerization modification, plasma treatment, dopamine polymerization and enzymolysis; the acid-base treatment is to remarkably increase the surface roughness by combining additional chemical bonds, so that the hydrophilicity and the reactivity of the nylon fabric can be improved, but the use of acid and base can generate adverse effects on the tensile property of the nylon; the graft copolymerization modification is generally carried out by adopting the graft copolymerization of acrylamide and acrylic acid to enhance the hydrophilicity of the nylon fabric, but the softness of the nylon fabric is obviously reduced due to high grafting ratio; the plasma treatment is to enhance the wettability and capillary transmission of fluid through a channel by increasing the surface roughness and introducing hydrophilic groups, but the plasma hydrophilization requires textile enterprises to purchase special equipment, so the cost is high; dopamine polymerization can endow polyamide fabric with excellent hydrophilic and antistatic effects, but the hydrophilic functionalization speed is too slow; enzymolysis has been proved to be effective in promoting the hydrophilicity of chinlon without damaging the strength of the fabric, and the functional treatment is relatively environment-friendly and safe, but the enzymolysis is weak.
Disclosure of Invention
[ problem ] to
The chemical method is adopted to carry out hydrophilic modification on the nylon fabric, so that the performance of the nylon fabric is greatly influenced; the method for carrying out hydrophilic modification on the chinlon fabric by adopting an enzyme method has the problem of unobvious hydrophilic effect.
[ solution ]
In order to solve the problems, the invention combines absolute ethyl alcohol pretreatment, protease surface modification and trehalose catalytic oxidation by a laccase/TEMPO system to realize hydrophilic modification of the polyamide fabric. The method has the advantages of low energy consumption, safety, environmental protection and good durability of hydrophilic modification.
The invention provides a method for carrying out hydrophilic modification on a chinlon fabric by protease and laccase, which comprises the following steps:
(1) Pretreatment of absolute ethyl alcohol:
immersing the nylon fabric after refining treatment into absolute ethyl alcohol for pretreatment, taking out and drying to obtain the pretreated nylon fabric;
(2) Modification of protease:
uniformly mixing protease, an activating agent and a buffer solution to obtain a protease modified solution; then immersing the pretreated chinlon fabric into a protease modification solution for reaction; after the reaction is finished, cleaning, drying and balancing to obtain the polyamide fabric modified by the protease;
(3) laccase/TEMPO graft modification:
uniformly mixing laccase, TEMPO, trehalose and a buffer solution to obtain a mixed solution; then soaking the polyamide fabric modified by the protease into the mixed solution for reaction; and after the reaction is finished, cleaning, drying and balancing to obtain the hydrophilic modified nylon fabric.
In one embodiment of the present invention, the preparation method of the chinlon fabric after the refining treatment in the step (1) is as follows:
placing the chinlon fabric into a refining solution, treating for 30min at 60 ℃, then desizing, boiling, cleaning, drying and balancing to obtain the chinlon fabric after refining treatment; wherein, the concentration of the soap flakes in the refining solution is 4-6g/L, the concentration of the sodium carbonate is 3-5g/L, and the balance is water; the bath ratio of the nylon fabric to the refining solution is 1:10-100 parts of; the bath ratio of desizing and scouring is 1:10-100 parts of; the cleaning is carried out by water, and the drying is carried out at 70-90 ℃; the balance is carried out in a constant temperature and humidity box (21 +/-1 ℃,65 +/-2%) for at least 24h.
In one embodiment of the invention, the pretreatment in step (1) is soaking at normal temperature (20-30 ℃) for 5-60min, and the bath ratio is 1:20-50.
In one embodiment of the present invention, the concentration of the protease in the protease-modified solution in step (2) is 4 to 40g/L, the concentration of the activating agent is 1 to 10g/L, and the pH of the buffer solution is 5.5 to 8.0.
In one embodiment of the invention, the protease in the step (2) is bromelain, and the enzyme activity of the bromelain is 600U/mg; the activating agent is one or two of L-cysteine and trehalose; the buffer solution is phosphoric acid-sodium phosphate buffer solution.
In one embodiment of the present invention, the bath ratio of the protease modification in step (2) is 1:20-60.
In one embodiment of the present invention, the reaction in step (2) is carried out at a pH of 5.5 to 8.0 and a temperature of 25 to 50 ℃ for 1 to 10 hours.
In one embodiment of the invention, the cleaning in step (2) is performed by using an aqueous sodium carbonate solution (2% by mass), then by using water, and finally by performing ultrasonic cleaning.
In one embodiment of the present invention, the drying in step (2) is drying in an oven at 80-100 ℃.
In one embodiment of the invention, the balancing in step (2) is performed by placing in a constant temperature and humidity chamber (21 + -1 deg.C, 65 + -2%) for at least 24h.
In one embodiment of the invention, the concentration of laccase in the mixed solution in the step (3) is 0.2-1.0g/L, the concentration of TEMPO is 1-5g/L, the concentration of trehalose is 5-10g/L, and the pH value of the buffer solution is 4-5; the enzyme activity of the laccase is 2000U/g.
In one embodiment of the present invention, the buffer solution in step (3) is a phosphate-sodium phosphate buffer solution.
In one embodiment of the present invention, the bath ratio of the reaction in step (3) is 1:100-250.
In one embodiment of the present invention, the reaction in step (3) is carried out at pH 4-5 and 30-40 ℃ for 3-9h.
In one embodiment of the present invention, the washing in step (3) is performed by washing with absolute ethanol and then with water.
In one embodiment of the present invention, the drying in step (3) is drying in an oven at 80-100 ℃.
In one embodiment of the invention, the balancing in step (3) is performed for at least 24h in a constant temperature and humidity chamber (21 + -1 deg.C, 65 + -2%).
The second purpose of the invention is to obtain the hydrophilic modified chinlon fabric by the method.
The third purpose of the invention is the application of the hydrophilic modified chinlon fabric in the preparation of functional textiles.
In one embodiment of the invention, the functional textile comprises a household textile and an industrial textile.
[ advantageous effects ]
(1) The invention adopts absolute ethyl alcohol for pretreatment, improves the accessibility of protease to chinlon, and can further reduce the contact angle under the action of the same enzyme concentration.
(2) The invention utilizes protease to hydrolyze amido bond on the surface of the chinlon, can generate more amino and carboxyl, and achieves the effect of hydrophilic modification on the basis of keeping the advantages and performances of the chinlon unchanged.
(3) The method utilizes a laccase/TEMPO system to catalyze and oxidize primary hydroxyl in a trehalose structure, and then aldehyde groups are obtained; and then, the amino on the surface of the nylon and the aldehyde group in the oxidized trehalose are subjected to Schiff base reaction, and the trehalose is grafted to the surface of the nylon to endow the nylon with hydrophilicity.
(4) The method has the advantages of low energy consumption and safe and environment-friendly treatment process, and avoids the defects of strict chemical grafting reaction conditions and easy environmental pollution.
(5) The release amount percentage of free amino of the hydrophilic modified nylon fabric prepared by the invention is more than 163.58% and as high as 341.72%, and the reduction percentage of the contact angle is more than 12.2% and as high as 48.5%.
Drawings
FIG. 1 shows the results of the test of the contact angle of the hydrophilic modified nylon fabric obtained in example 1 and the nylon fabric after the refining treatment adopted in comparative example 1; wherein (a) is comparative example 1 and (b) is example 1.
FIG. 2 shows the results of ATR-FTIR tests of the polyamide fabrics obtained in comparative examples 1 and 5.
FIG. 3 shows the K/S test results of the dyed nylon fabrics obtained in example 1, comparative example 3 and comparative example 4.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
The test method comprises the following steps:
1. testing of contact Angle:
placing the nylon fabric under a standard atmospheric pressure (21 + -1 deg.C, relative humidity 65 + -2%) for balancing for at least 24h, cutting the selvedge neatly, and cutting to obtain 1 × 1cm 2 The fabric of (2) is attached to a glass slide by a double-sided adhesive tape and then placed on a platform of a DSA 25 contact angle measuring instrument. Deionized water (10 mu L) is dropped at a height of 10mm from the cloth surface, and the contact angle is measured after 1min photographing. Each set of 3 replicates was measured 1 time and averaged.
2. Quantitative analysis and test of hydrolysate:
centrifuging residual liquid after protease modification treatment to obtain supernatant; taking 50 mu L of supernatant diluted by 100 times, uniformly mixing the supernatant with 1mL of OPA reagent for reaction for 2min, and testing the absorbance at 340 nm; respectively taking 50 mu L of enzyme solution and 50 mu L of deionized water as a comparison sample and a blank sample; and measuring the absorbance of reaction residual liquid under the wavelength of 340nm by using a TU-1900 type double-beam ultraviolet-visible spectrophotometer, and measuring each group of samples for 3 times.
3. Fabric K/S value:
and (3) adopting a Datacolor color measuring and matching instrument to test the dyeing performance of the polyamide fabric before and after treatment. The nylon fabric to be measured needs to be folded in half for 4 times, the tristimulus values X, Y and Z of the sample are measured in a visible region by a 10-degree standard observer under a light source D65, the wavelength range is 360-700nm, and the K/S value of the fabric is calculated by utilizing the reflectivity at the maximum absorption wavelength (lambda max).
4. And (3) infrared spectrum characterization:
and (3) carrying out total reflection infrared spectrum test on the surface of the nylon fabric by using a Nicola is 10 type Fourier transform infrared spectrometer, wherein the scanning range is 4000-500cm < -1 >, and the scanning times are 32 times.
5. And (3) wear resistance characterization:
a Y522 fabric abrasion tester is adopted, a 280-mesh grinding wheel and a 250g pressurizing heavy hammer are selected. Fixing a fabric sample on a working disc with the diameter of 90mm, making the disc perform constant-speed rotary motion at 70r/min, making the sample and a grinding wheel and grinding disc perform relative motion, and making the sample wear in multiple directions to form a wear ring. And observing the required friction times when the yarns on the surface of the sample are broken to generate holes under the same experimental conditions, taking the friction times as evaluation basis, and testing each group of samples for 3 times to obtain an average value.
The raw materials used in the examples:
the nylon fabric is a 100% nylon filament plain fabric, and the specification of the fabric is 20D/380T;
the bromelain has enzyme activity of 600U/mg, and is purchased from Beijing Sorbao science and technology Limited;
the laccase has enzyme activity of 2000U/g, and is purchased from Jiangsu Ruiyang biotechnology limited company.
The dyeings mentioned in the examples are in particular as follows:
concentration of methylene blue dye 0.5% owf, bath ratio 1; washing the dyed sample with water, and drying at room temperature; obtaining the dyed hydrophilic modified nylon fabric.
Example 1
A method for carrying out hydrophilic modification on a chinlon fabric by protease and laccase comprises the following steps:
(1) Pretreatment of absolute ethyl alcohol:
the nylon fabric is prepared by mixing the following raw materials in a bath ratio of 1:100 placing in refining solution (soap flake concentration is 5g/L, sodium carbonate concentration is 4g/L, and the rest is water), and treating at 60 deg.C for 30min; then, according to the following steps of 1: desizing and boiling at a bath ratio of 100, cleaning with water, and drying in a drying oven at 90 ℃; finally, the mixture is placed in a constant temperature and humidity box (21 +/-1 ℃,65 +/-2%) to be balanced for 24 hours, and the refined chinlon fabric is obtained;
and (3) carrying out refining treatment on the nylon fabric according to a bath ratio of 1:20, soaking in absolute ethyl alcohol at normal temperature for 30min, taking out, and naturally airing to obtain a pretreated nylon fabric;
(2) Modification of protease:
uniformly mixing 3.2g of bromelain, 0.3g L-cysteine and 100mL of phosphoric acid-sodium phosphate buffer solution (pH is 6) to obtain a protease modified solution; then, the pretreated nylon fabric is subjected to a bath reaction according to a bath ratio of 1:30 immersing in a protease modified solution to react for 5 hours at the temperature of 40 ℃ and the pH value of 6; after the reaction is finished, firstly washing for 10min by using a sodium carbonate aqueous solution with the mass concentration of 2%, then washing for 10min by using flowing deionized water, then ultrasonically washing for 30min, finally drying in a 90 ℃ oven, and balancing for 24h in a constant temperature and humidity box (21 +/-1 ℃,65 +/-2%) to obtain the protease modified polyamide fabric;
(3) laccase/TEMPO graft modification:
uniformly mixing 25mg of laccase, 120mg of TEMPO, 0.7g of trehalose and 100mL of phosphoric acid-sodium phosphate buffer solution (pH is 4) to obtain a mixed solution; then, carrying out enzyme modification on the polyamide fabric according to a bath ratio of 1:200 are immersed in the mixed solution to react for 4 hours at the temperature of 30 ℃ and the pH value of 4; after the reaction is finished, washing with absolute ethyl alcohol for 5min, then washing with deionized water for 5min, drying in a 90 ℃ oven after the reaction is finished, and balancing in a constant temperature and humidity box (21 +/-1 ℃,65 +/-2%) for 24h to obtain the hydrophilic modified nylon fabric.
Comparative example 1
The refined chinlon fabric is directly adopted.
The hydrophilic modified nylon fabric obtained in example 1 and the nylon fabric after refining treatment adopted in comparative example 1 were subjected to performance tests, and the test results were as follows:
FIG. 1 shows the results of the test of the contact angle of the hydrophilic modified nylon fabric obtained in example 1 and the nylon fabric after the refining treatment adopted in comparative example 1; wherein (a) is comparative example 1 and (b) is example 1. As can be seen from fig. 1: the contact angle of the nylon fabric after the refining treatment adopted in comparative example 1 was 102.5 °, the contact angle of the hydrophilic modified nylon fabric obtained in example 1 was 52.7 °, and it can be seen that the contact angle was reduced by 48.5% after the treatment by the method of the present invention.
Table 1 shows the results of the abrasion resistance test of the hydrophilic modified nylon fabric obtained in example 1 and the nylon fabric after the refining treatment adopted in comparative example 1, and the results are compared with the nylon fabric subjected to the alkali weight reduction treatment; the alkali weight reduction treatment nylon fabric is obtained by reacting in a sodium hydroxide solution with the concentration of 5g/L for 1h at the temperature of 90 ℃ at the bath ratio of 1.
As can be seen from table 1: after the hydrophilic modified nylon fabric is abraded to the same degree, the abrasion resistance of the hydrophilic modified nylon fabric is reduced to a certain extent. But the abrasion resistance loss is relatively reduced compared with the alkali weight reduction treated nylon fabric.
TABLE 1
| Example (b) | Comparative example 1 | Example 1 | Alkali weight reduction treatment chinlon |
| Number of friction turns/circle | 31 | 24 | 18 |
Example 2
The dosages of the bromelain in the step (2) of the example 1 are adjusted to be 0.8, 1.6, 2.4, 3.2 and 4.0g, the concentrations in the protease modification solution are 8, 16, 24, 32 and 40g/L, and the hydrophilic modified chinlon fabric is obtained in the same way as the example 1.
And (3) carrying out performance test on the obtained hydrophilic modified fabric, wherein the test result is as follows:
TABLE 2
| Concentration of enzyme (g/L) | 8 | 16 | 24 | 32 (example 1) | 40 |
| Contact Angle/° | 76.0 | 72.5 | 58.5 | 52.7 | 50.5 |
As can be seen from table 2: in the initial reaction stage, the contact angle of the surface of the nylon fabric is smaller and smaller along with the increase of the concentration of the protease. The contact angle change gradually becomes gentle with increasing enzyme concentration, and the contact angle drops to 50.5 ° at a concentration of 40g/L. The protease can act on the surface of the nylon fabric, effectively catalyzes the hydrolysis of amido bonds on the surface of the fiber, and increases the hydrophilicity.
TABLE 3
| Concentration of enzyme (g/L) | 8 | 16 | 24 | 32 (example 1) | 40 |
| Amount of free amino groups/%) | 163.58 | 223.18 | 229.14 | 341.72 | 292.38 |
As can be seen from table 3: the free amino release amount percentage of the prepared hydrophilic modified nylon fabric is more than 163.58 percent and is as high as 341.72 percent.
Example 3
The pH values in the step (2) of the example 1 are adjusted to 6, 6.5, 7, 7.5 and 8, and the rest is kept consistent with the example 1, so that the hydrophilic modified nylon fabric is obtained.
The obtained hydrophilic modified fabric is subjected to performance test, and the test result is as follows:
TABLE 4
| Reaction pH | 6.0 (example 1) | 6.5 | 7.0 | 7.5 | 8.0 |
| Contact angle/° | 52.7 | 66.5 | 74.5 | 74.0 | 75.0 |
As can be seen from table 4: with the increase of the reaction pH value, the change of the contact angle of the nylon fabric shows the trend of increasing firstly and then stabilizing, and when the pH value is 6.0, the contact angle of the nylon fabric is the minimum. The pH of the reaction system affects the binding and catalysis of the enzyme to the substrate, and thus the catalytic activity of the enzyme changes with the change in the pH of the reaction system. When the pH deviates from the optimum pH, the catalytic hydrolysis capacity of the protease decreases.
Comparative example 2
The ethanol pretreatment in the embodiment 1 is omitted, and the chinlon fabric after the refining treatment is directly subjected to protease modification to obtain the protease-modified chinlon fabric.
The protease reaction residual liquids obtained in example 1 and comparative example 2 were subjected to quantitative analysis of hydrolysates, and the results were as follows:
TABLE 5
| Example (b) | Residual liquid of protease reaction | Same concentration enzyme solution (control sample) | Deionized water (blank sample) |
| Comparative example 2 | 1.925 | 1.409 | 0.151 |
| Example 1 | 1.95125 | 1.409 | 0.151 |
As can be seen from table 5: compared with the polyamide fabric only treated by protease, the free amino release amount of the reaction residual liquid after the pretreatment by absolute ethyl alcohol is increased by 17.39%.
Comparative example 3
The steps (1) and (2) in the example 1 are omitted, the chinlon fabric after refining treatment is directly subjected to laccase/TEMPO grafting modification, and the rest is consistent with the step (1) to obtain the modified chinlon fabric.
Comparative example 4
The ethanol pretreatment in the example 1 is omitted, the chinlon fabric after the refining treatment is directly subjected to protease modification and laccase/TEMPO grafting modification, and the rest is consistent with the step 1, so that the modified chinlon fabric is obtained.
Comparative example 5
The step (3) in the example 1 is omitted, ethanol pretreatment and protease modification are adopted, and the steps are consistent with those in the example 1, so that the modified nylon fabric is obtained.
The modified nylon fabrics obtained in the example 1 and the comparative examples 1 and 3-5 are subjected to performance tests, and the test results are as follows:
TABLE 6
As can be seen from table 6: the independent absolute ethyl alcohol pretreatment, protease modification treatment and laccase/TEMPO grafting treatment have certain influence on contact angles, and the contact angles of the nylon fabric can be obviously reduced and the hydrophilicity can be improved after the three are combined.
FIG. 2 shows the results of ATR-FTIR tests of the polyamide fabrics obtained in comparative example 1 and comparative example 5. As can be seen from fig. 2: the infrared spectrum of the chinlon fabric is not obviously changed before and after the protease treatment, which shows that the chemical components of the chinlon fabric are not changed by the protease treatment; wherein 1590-1700cm -1 Is amide I belt, 1500-1580cm -1 Is an amide II belt, and the length of the polyamide fabric is 1633cm after protease treatment -1 、1536cm -1 The strength of the characteristic peak is reduced, which indicates that the protease catalyzes the hydrolysis of the polyamide fiber and leads to the breakage of the amide bond on the surface of the polyamide fiber.
FIG. 3 shows the results of K/S measurements after dyeing of the nylon fabrics obtained in example 1, comparative example 3 and comparative example 4. As can be seen from fig. 3: after methylene blue dyeing, the K/S value of the dyed hydrophilic modified nylon fabric is obviously increased under the wavelength of 550650nm, which shows that COO on the surface of the nylon fabric — The increase of the number of groups indicates that the egg is eggThe white enzyme hydrolyzes amido bonds on the surface of the fabric, so that the hydrophilic performance of the nylon fabric is improved.
Comparative example 6
The L-cysteine in the step (1) of the example 1 is omitted, and the rest is consistent with the example 1, so that the modified nylon fabric is obtained.
The modified nylon fabrics obtained in example 1 and comparative example 6 were subjected to performance tests, and the test results were as follows:
TABLE 7
| Example (b) | Comparative example 6 | Example 1 |
| Contact angle/° | 59.5 | 52.7 |
As can be seen from table 7: the addition of L-cysteine reduces the contact angle to a certain extent, so that L-cysteine has a promoting effect on the modification treatment of protease.
Comparative example 7
The absolute ethanol in the absolute ethanol pretreatment of the step (1) in the example 1 is adjusted to be a deep eutectic solvent A (the deep eutectic solvent A is a compound obtained by reacting choline chloride and oxalic acid at 60 ℃ for 1 hour), and the rest is consistent with that in the example 1, so that the modified nylon fabric is obtained.
The contact angles of the polyamide fabric pretreated by the deep eutectic solvent A after protease modification and after two-step modification are respectively tested, and the test results are as follows:
TABLE 8
As can be seen from table 8: the deep eutectic solvent has a gain effect on the hydrophilic modification of the protease, but is not beneficial to the two-step enzyme method modification, and the absolute ethyl alcohol pretreatment plays a promoting role in the two-step enzyme method hydrophilic modification.
Comparative example 8
The laccase dosage in the example 1 is adjusted to 12.5mg, and the others are consistent with the example 1, so that the modified nylon fabric is obtained.
Comparative example 9
The laccase dosage in the example 1 is adjusted to 12.5mg, the absolute ethyl alcohol pretreatment and the protease modification treatment are omitted, and the rest is consistent with the example 1, so that the modified nylon fabric is obtained.
The modified nylon fabrics obtained in the example 1, the comparative example 8 and the comparative example 9 are subjected to performance tests, and the test results are as follows:
TABLE 9
| Example (b) | Comparative example 8 | Comparative example 9 | Example 1 |
| Contact Angle/° | 57 | 70 | 52.7 |
As can be seen from table 9: after half of the laccase dosage is reduced, the contact angle of the chinlon fabric subjected to the two-step modification treatment is slightly increased, and the contact angle (70 ℃) of the chinlon fabric subjected to the anhydrous ethanol pretreatment and the protease modification treatment is not changed compared with the contact angle (70 ℃) of the chinlon fabric obtained by only adopting laccase/TEMPO grafting modification in comparative example 3. The best effect of the laccase/TEMPO modification treatment on the chinlon fabric is achieved under the treatment condition, the grafting sites are increased due to the increase of the amino content of the protease modification treatment, the modification effect can be increased due to the increase of the laccase content, and the hydrophilic effect of the chinlon fabric can be optimal on the basis of the current two-step modification treatment.
Example 4
Washing the hydrophilic modified nylon fabric obtained in the embodiment 1 with absolute ethyl alcohol for 5min, then washing with deionized water for 5min, and repeatedly washing for 10 times; then the mixture is put into a 90 ℃ oven for drying and is put into a constant temperature and humidity box (21 +/-1 ℃,65 +/-2%) for balancing for 24 hours.
And (3) carrying out performance test on the obtained washed hydrophilic modified polyamide fabric, wherein the test result is as follows:
watch 10
| Example (B) | Example 4 | Example 1 |
| Contact Angle/° | 61° | 52.7 |
As can be seen from Table 10, the nylon fabric can still maintain good hydrophilicity after being washed for several times, and the durability of hydrophilic modification is good.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for carrying out hydrophilic modification on a chinlon fabric by protease and laccase is characterized by comprising the following steps:
(1) Pretreatment of absolute ethyl alcohol:
immersing the refined nylon fabric into absolute ethyl alcohol for pretreatment, taking out and drying to obtain the pretreated nylon fabric;
(2) And (3) protease modification:
uniformly mixing protease, an activating agent and a buffer solution to obtain a protease modified solution; then immersing the pretreated chinlon fabric into a protease modification solution for reaction; after the reaction is finished, cleaning, drying and balancing to obtain the polyamide fabric modified by the protease;
(3) laccase/TEMPO graft modification:
uniformly mixing laccase, TEMPO, trehalose and a buffer solution to obtain a mixed solution; then soaking the chinlon fabric modified by the protease into the mixed solution for reaction; and after the reaction is finished, cleaning, drying and balancing to obtain the hydrophilic modified nylon fabric.
2. The method according to claim 1, wherein the protease in step (2) is bromelain, and the enzymatic activity of the bromelain is 600U/mg; the activator is one or two of L-cysteine and trehalose; the buffer solution is phosphoric acid-sodium phosphate buffer solution.
3. The method according to claim 1, wherein the concentration of the protease in the protease-modified solution in the step (2) is 4 to 40g/L.
4. The method according to claim 1, wherein the reaction in step (2) is carried out at a pH of 5.5 to 8.0 and a temperature of 25 to 50 ℃ for 1 to 10 hours.
5. The method of claim 1, wherein the concentration of laccase in the mixed solution of step (3) is 0.2-1.0g/L, the concentration of TEMPO is 1-5g/L, the concentration of trehalose is 5-10g/L, and the pH of the buffer is 4-5; the enzyme activity of the laccase is 2000U/g.
6. The method according to claim 1, wherein the reaction in step (3) is carried out at a pH of 4 to 5 and a temperature of 30 to 40 ℃ for 3 to 9 hours.
7. The method according to claim 1, wherein the chinlon fabric after the refining treatment in the step (1) is prepared by the following method:
placing the chinlon fabric into a refining solution, treating for 30min at 60 ℃, then desizing, boiling, cleaning, drying and balancing to obtain the chinlon fabric after refining treatment; wherein, the concentration of the soap flakes in the refining solution is 4-6g/L, the concentration of the sodium carbonate is 3-5g/L, and the balance is water; the bath ratio of the nylon fabric to the refining solution is 1:10-100 parts of; the bath ratio of desizing and scouring is 1:10-100 parts of; the cleaning is carried out by adopting water, and the drying is carried out at 70-90 ℃; equilibration is carried out in a constant temperature and humidity chamber (21 + -1 deg.C, 65 + -2%) for at least 24h.
8. The method as claimed in claim 1, wherein the pretreatment in step (1) is dipping at normal temperature (20-30 ℃) for 5-60min, and the bath ratio is 1:20-50.
9. A hydrophilically modified nylon fabric produced by the process of any one of claims 1 to 8.
10. Use of the hydrophilically modified polyamide fabric as claimed in claim 9 for the production of functional textiles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211232897.1A CN115584637B (en) | 2022-10-10 | 2022-10-10 | Method for carrying out hydrophilic modification on nylon fabric based on protease and laccase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211232897.1A CN115584637B (en) | 2022-10-10 | 2022-10-10 | Method for carrying out hydrophilic modification on nylon fabric based on protease and laccase |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115584637A true CN115584637A (en) | 2023-01-10 |
| CN115584637B CN115584637B (en) | 2023-07-25 |
Family
ID=84779182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211232897.1A Active CN115584637B (en) | 2022-10-10 | 2022-10-10 | Method for carrying out hydrophilic modification on nylon fabric based on protease and laccase |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115584637B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002233362A (en) * | 2001-02-05 | 2002-08-20 | Lion Corp | Method for stabilizing laccase activity and stabilized laccase composition |
| JP2003247174A (en) * | 2002-02-21 | 2003-09-05 | Aichi Prefecture | Method for modifying fiber containing polyester by enzyme |
| US20080289120A1 (en) * | 2004-06-11 | 2008-11-27 | Valtion Teknillinen Tutkimuskeskus | Method for Modifying Polyamide |
| US20090311931A1 (en) * | 2006-02-17 | 2009-12-17 | Valtion Teknillinen Tutkimuskeskus | Process For Pretreatment of Cellulose-Based Textile Materials |
| WO2010046542A1 (en) * | 2008-10-24 | 2010-04-29 | Oy Keskuslaboratorio - Centrallaboratorium Ab | Method for preparing modified fiber products |
| CN105951436A (en) * | 2016-05-18 | 2016-09-21 | 江南大学 | Antibacterial finishing method for grafting beta-cyclodextrin onto wool fabric under catalysis of laccase |
| CN107059413A (en) * | 2017-04-19 | 2017-08-18 | 江苏腾盛纺织科技集团有限公司 | Cutinase and laccase Combined Treatment carry out the function modified method of terylene |
| CN108193479A (en) * | 2018-01-29 | 2018-06-22 | 福建省德奥针织科技有限公司 | A kind of production method of hydrophilic terylene and its blended fabric |
-
2022
- 2022-10-10 CN CN202211232897.1A patent/CN115584637B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002233362A (en) * | 2001-02-05 | 2002-08-20 | Lion Corp | Method for stabilizing laccase activity and stabilized laccase composition |
| JP2003247174A (en) * | 2002-02-21 | 2003-09-05 | Aichi Prefecture | Method for modifying fiber containing polyester by enzyme |
| US20080289120A1 (en) * | 2004-06-11 | 2008-11-27 | Valtion Teknillinen Tutkimuskeskus | Method for Modifying Polyamide |
| US20090311931A1 (en) * | 2006-02-17 | 2009-12-17 | Valtion Teknillinen Tutkimuskeskus | Process For Pretreatment of Cellulose-Based Textile Materials |
| WO2010046542A1 (en) * | 2008-10-24 | 2010-04-29 | Oy Keskuslaboratorio - Centrallaboratorium Ab | Method for preparing modified fiber products |
| CN105951436A (en) * | 2016-05-18 | 2016-09-21 | 江南大学 | Antibacterial finishing method for grafting beta-cyclodextrin onto wool fabric under catalysis of laccase |
| CN107059413A (en) * | 2017-04-19 | 2017-08-18 | 江苏腾盛纺织科技集团有限公司 | Cutinase and laccase Combined Treatment carry out the function modified method of terylene |
| CN108193479A (en) * | 2018-01-29 | 2018-06-22 | 福建省德奥针织科技有限公司 | A kind of production method of hydrophilic terylene and its blended fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115584637B (en) | 2023-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kiumarsi et al. | Enzymatic hydrolysis of nylon 6 fiber using lipolytic enzyme | |
| MXPA04006876A (en) | Method of producing fabric. | |
| Zhang et al. | Study on the natural dyeing of wool modified with enzyme | |
| Jovanĉić et al. | Shrinkage properties of peroxide-enzyme-biopolymer treated wool | |
| Bai et al. | Effect of laccase on dyeing properties of polyphenol-based natural dye for wool fabric | |
| Periyasamy | Natural dyeing of cellulose fibers using syzygium cumini fruit extracts and a bio-mordant: A step toward sustainable dyeing | |
| Kan et al. | Optimizing color fading effect of cotton denim fabric by enzyme treatment | |
| CN109440499B (en) | Reactive dye dyeing auxiliary for linen fabric and application thereof | |
| CN108894012A (en) | A method of passing through two step method Modified lift protein fibre product dyeability | |
| CN113338044A (en) | Method for modifying terylene based on Humicola insolens cutinase | |
| Salem et al. | Plasma-assisted surface modification of polyester fabric for developing halochromic properties | |
| Shen et al. | Development of durable shrink-resist coating of wool with sol-gel polymer processing | |
| Jia et al. | Laccase-mediated in situ oxidation of dopamine for dyeing of human hair | |
| Xia et al. | Efficient cationization of cotton fabric via oxidative pretreatment for salt-free reactive dyeing with low chemical consumption | |
| CN115584637B (en) | Method for carrying out hydrophilic modification on nylon fabric based on protease and laccase | |
| Dong et al. | Dyeing and finishing of cotton fabric in a single bath with reactive dyes and citric acid | |
| CN101280526A (en) | Method for dyeing mercerization baffeta with deep color on reactive dyes | |
| Wong et al. | Effect of plasma and subsequent enzymatic treatments on linen fabrics | |
| CN113512884A (en) | Method for modifying polyester surface by ultrasonic synthase | |
| CN111945425A (en) | Strongly hydrophobic real silk fabric and preparation method thereof | |
| Kumar et al. | Biopolishing of cellulosic fabrics: A study on low-stress mechanical properties, microstructure, and dye uptake | |
| Avcı et al. | The effect of glucose oxidase enzyme on wool fibres | |
| Liu et al. | Preparation of a cationic environment-friendly fixing agent | |
| Lee et al. | Cutinase treatment of cotton fabrics | |
| Zhang et al. | An ethoxylated alkyl phosphate (anionic surfactant) for the promotion of activities of proteases and its potential use in the enzymatic processing of wool |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |