CN113512884B - Method for modifying polyester surface by ultrasonic synthase - Google Patents
Method for modifying polyester surface by ultrasonic synthase Download PDFInfo
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- CN113512884B CN113512884B CN202110726804.XA CN202110726804A CN113512884B CN 113512884 B CN113512884 B CN 113512884B CN 202110726804 A CN202110726804 A CN 202110726804A CN 113512884 B CN113512884 B CN 113512884B
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- 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
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- 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
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
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- 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
- D06M2101/32—Polyesters
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Abstract
The invention relates to the technical field of polyester surface modification, in particular to a method for modifying a polyester surface by ultrasonic synthase. The method of the invention comprises the following steps: placing the polyester fabric subjected to refining treatment in a cutinase solution, sealing a reaction system, and carrying out water bath ultrasonic treatment; transferring the obtained reaction system to a shaking table for continuous reaction, and taking out the polyester fabric after the reaction is finished; and washing and drying the obtained polyester fabric to obtain the hydrophilic modified polyester fabric. The method disclosed by the invention is used for hydrophilic modification of the polyester surface by a biological method, the treatment conditions are mild, and compared with a single cutinase modification method in the prior art, the method has the advantages that the reaction rate is obviously improved, the reaction time is greatly shortened, the modification cost is favorably saved, and the modification process is simple, green and environment-friendly.
Description
Technical Field
The invention relates to the technical field of polyester surface modification, in particular to a method for modifying a polyester surface by ultrasonic synthase.
Background
The terylene fiber is one of the most widely used synthetic fibers with the largest output at present, and the proportion of the terylene fiber in the total output of chemical fibers is stably kept above 80 percent for a long time. The reason is that the polyester fiber has many excellent characteristics of high strength, stretch resistance, crease resistance, wear resistance, machine washability and the like, but the polyester fabric has the characteristics of poor hydrophilicity, air permeability, dyeing property and antistatic property due to the low moisture regain (only 0.4% under the standard atmospheric pressure).
At present, the hydrophilicity of polyester fabrics is generally improved by surface modification techniques such as physical coating, plasma treatment, polymer grafting, chemical treatment and the like. However, these methods mainly use high energy input or harsh chemicals, and the treatment process is cumbersome and environmentally unfriendly. For example, plasma treated polyester fabrics are time-sensitive, and the polyester fabrics will regain hydrophobicity within a few days; the alkali weight reduction process requires the consumption of large amounts of alkali and water, the discharge of large amounts of high-concentration alkali, environmental hazards, and severe loss of fabric weight and strength. Compared with the prior art, the polyester fabric surface modification technology by using the enzyme has the advantages of mild action conditions, energy conservation, water conservation, easy biochemical treatment of the treated wastewater, green ecology and environmental protection.
Enzymatic hydrolysis of polyester fibers releases terephthalic acid (TPA) and its derivatives, which have an absorption peak at 240 nm. And measuring the amount of TPA and derivatives thereof generated in the reaction residual liquid by using an ultraviolet spectrophotometer to indirectly react the modification effect of the enzyme on the polyester fiber, wherein the higher the release amount of the hydrolysate is, the better the modification effect of the enzyme on the polyester surface is.
Cutinase is a multifunctional hydrolase used for hydrolyzing short-chain or long-chain fatty acid esters and triglycerides, and degrading plant polymer cutin. The application of cutinases in the field of textile processing mainly includes the biorefining of cotton fabrics and the surface modification of chemical fibers. In the aspect of polyester surface modification, the prior patent application (patent number 2021106174632) of the applicant describes that Humicola insolens cutinase can catalyze ester bonds on the polyester surface to hydrolyze to generate hydrophilic groups, namely hydroxyl and carboxyl, and simultaneously generates hydrolysis products, wherein the main hydrolysis products are terephthalic acid (TPA) and mono (terephthalic acid-2-hydroxyethyl ester) (MHET), so that the polyester achieves the effect of hydrophilization modification on the basis of keeping the advantages of the polyester without changing the performance of the polyester, and the release amount of the hydrolysis product TPA and derivatives thereof of the obtained hydrophilically modified polyester fabric reaches 47.4mg/L (enzyme treatment is carried out for 24 h). However, the above modification method has a limited effect on increasing the amount of the released hydrolysate.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for modifying the surface of the terylene by combining ultrasonic waves with cutinase on the basis of the method for modifying the terylene in a hydrophilic way by using an enzyme method in the prior art, so that the hydrophilicity of the terylene fabric is greatly improved compared with that of the prior art.
The technical idea of the invention is that the enzyme is used as a catalyst with mild property, high selectivity and high specificity, and can accelerate the reaction. From the economical and ecological point of view, the enzyme catalysis reaction has no pollution, mild reaction conditions, high safety and the enzyme can be recycled. On the basis of the existing polyester fiber enzyme method hydrophilic modification, the invention develops research on the problem of poor hydrophilic modification effect of the polyester fiber enzyme method, and utilizes ultrasonic wave to cooperate with cutinase to further improve the hydrophilic modification effect of the polyester surface.
The invention provides a method for modifying the surface of terylene by ultrasonic synthase, which comprises the following steps:
(1) ultrasonic combined enzyme treatment: placing the polyester fabric subjected to refining treatment in a cutinase solution, sealing a reaction system, and carrying out water bath ultrasonic treatment;
(2) and (3) shaking table treatment: transferring the reaction system obtained in the step (1) to a shaking table for continuous reaction, and taking out the polyester fabric after the reaction is finished;
(3) and (3) post-treatment: and (3) washing and drying the polyester fabric obtained in the step (2) to obtain the hydrophilic modified polyester fabric.
Wherein the refining treatment is to remove the surface sizing agent and impurities of the fabric.
In one embodiment of the present invention, the cutinase solution comprises Humicola insolens cutinase and Tris-HCl buffer.
As an embodiment of the invention, the pH value of the Tris-HCl buffer solution is 8, the concentration of the Tris-HCl buffer solution is 5mmol/L, and the effect is to ensure that the pH value of a reaction solution system is stabilized at 7.0-9.0.
In one embodiment of the present invention, the concentration of the Humicola insolens cutinase is 20 to 120U/mL. Preferably 100U/mL. The activity of the Humicola insolens cutinase is as follows: 800-900U/mL.
In one embodiment of the present invention, the cutinase solution has a pH of 7.0 to 9.0, preferably 8.0.
In one embodiment of the present invention, the Humicola insolens cutinase is derived from Humicola insolens, and the nucleotide sequence of the gene of the Humicola insolens cutinase is SEQ ID NO. 1; the amino acid sequence is shown as SEQ ID NO. 2.
As an embodiment of the invention, the temperature of the water bath ultrasound is 55-60 ℃; and/or the temperature of the shaker is 55-60 ℃.
As an embodiment of the invention, the time of the water bath ultrasound is 10-120min, preferably 30-120 min.
As an embodiment of the present invention, the shaking treatment time is 6 to 72 hours.
As an embodiment of the present invention, the rotational speed of the shaker is 150 rpm.
In one embodiment of the present invention, the bath ratio of the polyester fabric in the cutinase solution is 1:30 to 50, more preferably 1: 40.
as an embodiment of the present invention, the refining process specifically includes: putting the polyester fabric into a solution of soap chips and sodium carbonate for desizing and boiling; and (5) cleaning, drying and balancing in a constant temperature and humidity box to obtain the polyester fabric subjected to refining treatment.
As an embodiment of the invention, the concentration of the soap flakes in the refining treatment is 4-6g/L, and the concentration of the sodium carbonate is 3-5 g/L. More preferably: the concentration of the soap flakes is 5g/L, and the concentration of the sodium carbonate is 4 g/L.
In one embodiment of the present invention, the conditions for desizing and scouring in the refining process are as follows: treating at 95-100 deg.C for 25-35min at a bath ratio of 1: 20-40. More preferably: treating at 98 ℃ for 30min, wherein the bath ratio is 1: 30.
as an embodiment of the invention, the cleaning in the refining treatment is water cleaning, and the drying is drying in an oven at 105 ℃; the conditions of the constant temperature and humidity chamber are as follows: 21 +/-1 ℃ and 65 +/-2 percent; the balance time is not less than 24 h.
As an embodiment of the present invention, the washing is specifically: the polyester fabric is firstly put into a lauryl sodium sulfate solution with the mass concentration of 1 percent for ultrasonic cleaning for 30min, and then put into an ethanol solution with the mass concentration of 20 percent for ultrasonic cleaning for 30 min.
As an embodiment of the invention, the drying is drying at 100-105 ℃.
The second purpose of the invention is to provide a hydrophilic modified polyester fabric prepared by the method.
The third purpose of the invention is to provide the application of the hydrophilic modified polyester fabric in the textile field.
The fourth purpose of the invention is to provide a textile prepared from the hydrophilic modified polyester fabric.
The invention has the beneficial effects that:
(1) the invention utilizes ultrasonic wave and cutinase to carry out hydrophilic modification on the surface of the terylene, the cutinase catalyzes ester bond hydrolysis on the surface of the terylene to generate hydrophilic groups, namely hydroxyl and carboxyl, and simultaneously generates hydrolysis products, wherein the main hydrolysis products are TPA (TPA) represented by terephthalic acid (TPA) and mono (terephthalic acid-2-hydroxyethyl ester) (MHET) and derivatives thereof. The modification method of the invention is the same as the type of hydrolysate obtained by singly modifying the polyester fabric with cutinase. The method is a green, environment-friendly, energy-saving, mild and efficient treatment mode, and can achieve the effect of hydrophilic modification on the basis of keeping the advantages and performances of the terylene unchanged.
(2) Compared with the method for treating the polyester fabric by the ultrasonic wave and the cutinase in a two-step method, the release amount of TPA and derivatives thereof for treating the polyester fabric by the ultrasonic wave and the cutinase in a one-step method is obviously improved. The release amount of the TPA and the derivatives thereof treated by the ultrasonic waves and the cutinase is higher than the sum of the release amounts of the TPA and the derivatives thereof treated by the ultrasonic waves and the cutinase, namely, the combined technical effect is more superior to the sum of the effects of the single ultrasonic waves or the single cutinase, and the ultrasonic waves and the cutinase are mutually supported on the aspects of improving the release amount and the hydrophilic modification performance of the TPA and the derivatives thereof and exert a synergistic effect.
(3) The release amount of TPA and the derivatives thereof treated by the ultrasonic wave and cutinase one-step method is equivalent to that of TPA and the derivatives thereof treated by a single enzyme in a shaking table for 18 hours, which shows that compared with the prior art, the method of the invention greatly shortens the reaction time and reduces the experiment cost.
(4) The release amount of TPA and derivatives thereof in the polyester fabric treated by the ultrasonic wave and cutinase one-step method is respectively improved by 165.2 percent, 83.5 percent and 68.8 percent compared with that of the polyester fabric treated by a single enzyme shaking table.
(5) The invention can adopt Humicola insolens cutinase which has mild action, high selectivity and high specificity and can accelerate the reaction; and the enzyme catalysis reaction has no pollution, the reaction condition is mild, the safety is high, and the enzyme can be recycled.
(6) The method for treating the cutinase by using the ultrasonic waves has the advantage that the activity of Humicola insolens cutinase does not decrease within at least 10 hours.
Drawings
FIG. 1 is a high performance liquid chromatogram of the reaction residue in example 1.
FIG. 2 is a scanning electron microscope picture of the polyester fabric before modification treatment in example 1.
FIG. 3 is a scanning electron microscope image of the polyester fabric after modification treatment in example 1.
FIG. 4 is an ATR-FTIR spectrum of polyester fabric obtained by single enzyme table treatment and ultrasonic wave combined with cutinase one-step treatment.
FIG. 5 is a DSC plot of three polyester fabrics, wherein 1-untreated, 2-single enzyme shaker treatment of the polyester fabric; 3-ultrasonic wave and cutinase combined one-step treatment.
FIG. 6 is a graph showing the relationship between the ultrasonic treatment time and the activity of the cutinase by the method of the present invention.
FIG. 7 is a graph showing the results of the release amount of TPA and its derivatives at 0min, 10min, 30min, 60min, 90min and 120min in the step (1) of the sonication enzyme treatment in example 2 as a function of the shaking treatment time.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The raw materials adopted in the embodiment and the comparison example of the invention are 100 percent of polyester filament plain weave fabrics, the density of warp and weft yarns is 2.22tex, the density of warp and weft yarns is 880, 680 pieces/(10 cm) respectively, and the surface density is 56g/m 2 。
Pretreatment of the fabric: the polyester fabric is put into a solution of 5g/L soap chips and 4g/L sodium carbonate and treated for 30min at 98 ℃ for refining (bath ratio is 1: 30). Then washing with deionized water, and drying in a 105 ℃ oven. And finally, placing the polyester fabric in a constant temperature and humidity box (21 +/-1 ℃, 65 +/-2%) to balance for at least 24 hours for subsequent experiments.
The test method comprises the following steps:
1. and (3) qualitative analysis and test of hydrolysate:
the kind of the hydrolysate was identified by analytical testing using an Agilent Technologies 1200Series high performance liquid chromatograph at a wavelength of 240 nm.
2. Quantitative analysis test of TPA and its derivatives concentration:
keeping the reaction residual liquid after the cutinase treatment in boiling water for 30min to inactivate the enzyme, centrifuging the reaction residual liquid, taking the supernatant, taking the cutinase treatment liquid without adding polyester fabrics under the same condition as a reference, measuring the absorbance of the reaction residual liquid under the wavelength of 240nm, and testing each group of samples for three times. According to the relation between the concentration of the TPA serving as a standard substance and the absorbance, the corresponding concentration values of the TPA and the derivatives thereof can be calculated according to different absorbances.
3. And (3) observing the surface appearance of the polyester fabric:
after the surface of the polyester fabric is plated with gold, the surface appearance change of the polyester fiber is observed by using an SU1510 type scanning electron microscope. The accelerating voltage of the electron microscope is 5.0kV, and the magnification is 10000 times.
4. The surface chemical structure of the polyester fabric is characterized:
and (3) carrying out total reflection infrared spectrum test on the surface of the polyester fabric by using a Nicolet is 10 type Fourier transform infrared spectrometer, wherein the scanning range is 4000cm < -1 > to 500cm < -1 >, and the scanning times are 32 times.
5. Activity test of cutinase:
the enzymatic activity of cutinases is determined using a continuous spectrophotometer. The total system volume of the test reaction was 1.5mL, and included 30. mu.L of an appropriately diluted enzyme solution, 30. mu.L of 50mmol/L p-nitrobenzoate (pNPB) and 1440. mu.L of 5mmol/L Tris-HCl buffer (pH 8.0), and the rate of production of p-nitrophenol was recorded at a wavelength of 405 nm. Definition of enzyme activity: at 37 ℃, the enzyme amount for catalyzing the p-nitrobenzoate to hydrolyze to generate 1 mu mol of p-nitrophenol per minute is an enzyme activity unit.
6. Testing the thermal performance of the fabric:
the polyester fabric is cut into pieces, and about 5mg of samples are weighed and placed into a crucible. And thermally analyzing the sample by adopting a DSC-Q200 type differential scanning calorimeter, testing in a nitrogen atmosphere, and increasing the temperature from 30 ℃ to 300 ℃ at the temperature rise speed of 10 ℃/min to obtain the DSC curve of the sample.
Sources of Humicola insolens cutinase:
the preparation method of the Humicola insolens cutinase is derived from patent CN 108753671A, and the nucleotide sequence and the amino acid sequence are shown in Table 1: the Humicola insolens cutinase is added into the reaction system in the form of crude enzyme liquid.
TABLE 1 nucleotide and amino acid sequences of Humicola insolens cutinase
Example 1 one-step treatment of polyester Fabric with ultrasonic waves in combination with Cutinase
A method for modifying the surface of terylene by ultrasonic synthase comprises the following steps:
(1) ultrasonic combined enzyme treatment: placing the refined polyester fabric (0.4g) in a Humicola insolens cutinase solution (Tris-HCl buffer solution with the pH value of 8.05 mmol/L and Humicola insolens cutinase with the concentration of 100U/mL and the activity of 800-;
(2) and (3) shaking table treatment: transferring the reaction system obtained in the step (1) to a shaking table (60 ℃, 150rpm) to continue to react for 24 hours, and taking out the polyester fabric after the reaction is finished;
(3) and (3) post-treatment: ultrasonically cleaning the polyester fabric obtained in the step (2) in a 1% sodium dodecyl sulfate solution for 30min, ultrasonically cleaning the polyester fabric with a 20% ethanol solution for 30min, then placing the polyester fabric into a drying oven at 105 ℃ for drying, and after drying, placing the polyester fabric into a constant temperature and humidity box (21 +/-1 ℃, 65 +/-2%) for balancing for at least 24h to obtain a sample 1: the polyester filament fabric is treated by an ultrasonic wave/cutinase one-step method.
And carrying out high performance liquid chromatography analysis on the reaction residual liquid to identify the type of the hydrolysate. As shown in FIG. 1, the peak-out times of TPA (24.5min) and MHET (26.8min) produced by the single enzyme shaking table treatment of the polyester fabric (single cutinase treatment, see comparative example 2) and the ultrasonic wave combined cutinase one-step treatment (ultrasonic wave/cutinase one-step method, see example 1) are consistent, which indicates that the ultrasonic wave combined cutinase one-step method and the single enzyme shaking table treatment of the polyester fabric produce the same product types. Compared with the product absorption peak of polyester fabric treated by a single enzyme shaking table, the product absorption peak of the ultrasonic wave and cutinase one-step method is higher, which shows that the release amount of a cutinase hydrolysate is improved and the product variety is unchanged under the condition that no chemical solvent is added by ultrasonic wave.
FIGS. 2-3 show scanning electron micrographs of polyester fabric fibers before and after ultrasonic treatment. It can be seen that the surface of the untreated polyester fabric fiber is very smooth, and the surface of the polyester fabric fiber treated by the ultrasonic wave and the cutinase in one step has different etching phenomena, so that the surface of the fiber becomes rough, because the ultrasonic wave and the cutinase hydrolyze ester bonds on the surface of the fabric. In addition, the hydrolysis of the polyester fiber by the enzyme is limited to the surface layer, and the performance of the polyester fabric fiber can not be damaged.
FIG. 4 shows ATR-FTIR spectra of polyester fabric obtained by single enzyme shaker treatment and ultrasonic wave combined with cutinase one-step treatment. It can be seen that the peak patterns and trends of the infrared spectrogram obtained by treating the polyester fabric with the single enzyme shaker (single cutinase treatment, see comparative example 2) and the polyester fabric treated with the ultrasonic wave and cutinase one-step method (ultrasonic/cutinase one-step method, see example 1) have no obvious change, which indicates that the ultrasonic wave and cutinase one-step method does not cause the change of the chemical components of the polyester fabric. Wherein, the thickness is 1710- -1 The position is the stretching vibration peak of C ═ O in the ester bond, and the peak is at 1210- -1 And (b) is a stretching vibration peak of a C-O bond in an ester bond. As can be seen in FIG. 4, at 1712cm -1 And 1242cm -1 The intensity of characteristic peaks C ═ O and C-O of the polyester fabric treated by the ultrasonic waves is reduced, which shows that the ultrasonic waves and the cutinase catalyze the hydrolysis of the polyester fiber to further promote the fracture of surface ester bonds, so that carbonyl groups C ═ O and C-O bonds in the ester bonds are further reduced.
FIG. 5 is a DSC graph of three polyester fabrics, wherein 1-untreated, 2-single enzyme shaker treatment of the polyester fabric (see comparative example 2); 3-sonication in combination with cutinase one step treatment (see example 1). The melting temperature of the untreated polyester fabric is 254.1 ℃, the melting temperature of the polyester fabric treated by the single enzyme shaker is 253.82 ℃, and the melting temperature of the polyester fabric treated by the ultrasonic wave and cutinase one-step method is 253.95 ℃. The thermal properties of the three polyester fabrics have no obvious difference, and the two modes of ultrasonic wave combined cutinase one-step treatment and single enzyme shaking table treatment are proved to be mild, so that the fiber surface of the polyester fabrics can be modified on the premise of not damaging the performance of the polyester.
Comparative example 1-ultrasonic wave-cutinase two-step method for treating polyester fabric
A method for modifying the surface of terylene by ultrasonic synthase refers to example 1, and the difference is that:
1. the cutinase solution (Tris-HCl buffer solution with pH 8.05 mmol/L and Humicola insolens cutinase with concentration of 100U/mL and activity of 800-900U/mL) of the step (1) of the example 1 is replaced by Tris-HCl buffer solution with pH 8.05 mmol/L alone.
2. "addition of Humicola insolens cutinase at a concentration of 100U/mL (the concentration and activity of Humicola insolens cutinase are the same as those in example 1) to the reaction system obtained in step (1)" is added before the shaking table reaction in step (2) in example 1.
Comparative example 2-treatment of polyester Fabric with Single enzyme shaking Table
An enzyme modification method for terylene surface, which is as shown in example 1, and is characterized in that: adjusting the time of the ultrasonic treatment in the 60 ℃ water bath of the ultrasonic water bath cleaning instrument to 0h to prepare a sample 3: and (3) carrying out shaking table treatment on the polyester filament fabric by using a single enzyme.
TABLE 1 relationship between different treatment modes and the amount of TPA and its derivatives released
Table 1 shows the relationship between the different treatment regimes and the amount of TPA and its derivatives released. It can be seen that the release amount of TPA and its derivatives is the largest in the ultrasonic wave combined cutinase one-step treatment of the polyester fabric compared to the ultrasonic wave combined cutinase two-step treatment of the polyester fabric, the single enzyme shaker treatment of the polyester fabric and the single ultrasonic wave treatment of the polyester fabric, for example, the release amount of TPA and its derivatives in the ultrasonic wave combined cutinase one-step treatment of the polyester fabric (sample 1) is increased by 165.2%, 83.5% and 68.8% in the reaction time of 6h, 18h and 24h, respectively, compared to the single enzyme shaker treatment of the polyester fabric (sample 3). This is because the polyester fabric is treated by the ultrasonic wave in combination with the cutinase in one step, on one hand, the ultrasonic wave can improve the activity of the cutinase in the solution to a certain extent (example 2), thereby improving the rate and yield of the enzymatic reaction; on the other hand, the ultrasonic wave can disperse the cutinase aggregates in the solution, so that the cutinase is more dispersed and is easily and fully contacted with the polyester fabric, and the cavitation of the ultrasonic wave can discharge the air remained in warp and weft interlacing points of the fabric, so that the enzyme solution is favorably and fully contacted with the polyester fiber, and the hydrolysis effect of the cutinase on the polyester fabric is improved.
Comparing the release amount data of the TPA and the derivative thereof of the samples 1 and 2, the release amount improvement of the TPA and the derivative thereof of the polyester fabric treated by the ultrasonic wave and the cutinase one-step method is obvious compared with that of the TPA and the derivative thereof treated by the ultrasonic wave and the cutinase two-step method, which shows that the ultrasonic action on the enzyme can generate a synergistic effect and can obviously improve the release amount of the TPA and the derivative thereof.
Example 2 comparative study of ultrasonic treatment with Cutinase, ultrasonic treatment, and Cutinase treatment
Example 2-1: a method for modifying the surface of terylene by ultrasonic synzyme, referring to example 1, except that the shaking table treatment step (2) is omitted, and the terylene fabric obtained in the step (1) is directly subjected to the post-treatment of the step (3), so as to prepare a sample 4: and (3) polyester filament fabric treated by ultrasonic waves and cutinase.
Comparative example 2-2: a method for modifying the surface of terylene by ultrasonic waves refers to example 2-1, and is characterized in that the cutinase solution (Tris-HCl buffer solution with pH 8.05 mmol/L and Humicola insolens cutinase with concentration of 100U/mL and activity of 800U/mL) in the step (1) of example 2-1 is replaced by single Tris-HCl buffer solution with pH 8.05 mmol/L to prepare a sample 5: and (3) independently processing the polyester filament yarn fabric by ultrasonic waves.
Comparative examples 2 to 3: a method for modifying polyester surface by cutinase, which is described in example 2-1, except that no ultrasonic treatment is performed, and only a cutinase is subjected to shaking table treatment for 2 hours, so as to prepare a sample 6: and (3) the cutinase is independently treated on the polyester filament fabric.
TABLE 2 ultrasonic + Cutinase, ultrasonic treatment, Cutinase treatment comparative study
Table 2 shows the relationship between the ultrasonic treatment and the cutinase treatment and the release amount of TPA and its derivatives. It can be seen that at 2h of reaction, the production of the polyester filament fabric treated with ultrasonic wave alone (sample 5) was the lowest, while the production of the polyester filament fabric treated with ultrasonic wave + cutinase (sample 4) was the highest, which was 161.55% higher than that of the polyester filament fabric treated with cutinase alone (sample 6). The release amount of TPA and its derivatives treated with ultrasonic wave and cutinase is 34.76 mg.L -1 Higher than the sum of the release amount of TPA and the derivative thereof which are treated by ultrasonic wave and cutinase alone (15.2 mg.L) -1 ) That is, the technical effect after combination is superior to the sum of the effects of the ultrasonic waves alone or the cutinase alone, and the mutual support of the ultrasonic waves and the cutinase in the aspects of improving the release amount of TPA and derivatives thereof and the hydrophilic modification performance is proved to play a synergistic effect.
Example 3 variation of the Activity of Cutinases at different sonication times
A method for ultrasonically treating a Humicola insolens cutinase solution, which is described in example 1, except that the time for the ultrasonic-linked enzyme treatment in the step (1) is adjusted to 0-10h, and no polyester fabric is added. And (3) finishing the ultrasonic enzyme combination treatment in the step (1), and measuring the activity of the cutinase of the Humicola insolens cutinase solution. The test results are shown in fig. 6.
FIG. 6 shows the relationship between the ultrasonic treatment time and the activity of cutinase. It can be seen that the activity of Humicola insolens cutinase does not decrease with the prolonging of the ultrasonic action time, the activity can be basically maintained within 10h of the ultrasonic action, and sometimes the activity is even improved, for example, the activity of the cutinase is improved by 35.1% at the time of 30min of ultrasonic action. This is because the energy released by the ultrasound waves changes the conformation of the enzyme molecules in the solution, which is positive, and the biological function of the cutinase is enhanced under the action of the ultrasound waves, so that the conformation of the enzyme molecules is more rational, and the activity of the Humicola insolens cutinase is improved.
The results of the release amounts of TPA and its derivatives corresponding to 0min, 10min, 30min, 60min, 90min and 120min of the sonication conjugant enzyme treatment of step (1) in example 3 are shown in FIG. 7.
As can be seen from FIG. 7, the amount of TPA and its derivatives released at the end of the sonication (0 h in FIG. 7) gradually increased with the increase of the sonication time. The release amount of TPA and the derivatives thereof treated by the ultrasonic wave and cutinase one-step method for 120min (2h) is equivalent to the release amount of TPA and the derivatives thereof treated by a single enzyme shaker for 18h, which shows that compared with the prior art, the method disclosed by the invention greatly shortens the reaction time and reduces the experiment cost. After 30min of the ultrasonic treatment, the yield increase rate of TPA and the derivatives thereof in the shaking table treatment is gradually reduced along with the increase of the ultrasonic treatment time, which shows that the increasing effect on the release amount of TPA and the derivatives thereof is reduced when the continuous ultrasonic treatment time is too long. Therefore, the time for the ultrasonic conjugase treatment in step (1) in the preferred embodiment 2 is 30min-120 min.
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 (2)
1. A method for modifying the surface of terylene by ultrasonic synthase is characterized by comprising the following steps:
(1) ultrasonic combined enzyme treatment: placing 0.4g of polyester fabric subjected to refining treatment in a cutinase solution at a bath ratio of 1:40, sealing a reaction system, carrying out water bath ultrasonic treatment for 2h, and controlling the water bath ultrasonic temperature to be 60 ℃; wherein the cutinase solution comprises Humicola insolens cutinase and a Tris-HCl buffer solution; the pH value of the Tris-HCl buffer solution is 8.0, and the concentration is 5 mmol/L; the concentration of the Humicola insolens cutinase is 100U/mL, the activity is 800-900U/mL, the Humicola insolens cutinase is from Humicola insolens, the nucleotide sequence of the gene of the Humicola insolens cutinase is SEQ ID NO.1, and the amino acid sequence is SEQ ID NO. 2;
(2) and (3) shaking table treatment: transferring the reaction system obtained in the step (1) to a shaking table at 60 ℃, continuously reacting for 24h at 150rpm, and taking out the polyester fabric after the reaction is finished;
(3) and (3) post-treatment: and (3) ultrasonically cleaning the polyester fabric obtained in the step (2) for 30min by using a 1% sodium dodecyl sulfate solution, ultrasonically cleaning the polyester fabric for 30min by using a 20% ethanol solution, then drying the polyester fabric in a drying oven at 105 ℃, and balancing the polyester fabric in a constant temperature and humidity box at 21 +/-1 ℃ and 65 +/-2% for at least 24h after drying to obtain the hydrophilic modified polyester fabric.
2. The method for modifying the surface of the terylene by the ultrasonic synthase according to claim 1, wherein the refining treatment in the step (1) comprises the following steps:
putting the polyester fabric into a solution of 5g/L soap chips and 4g/L sodium carbonate, and refining at 98 ℃ for 30min at a bath ratio of 1: 30; then washing with deionized water, and drying in a 105 ℃ oven; finally, the polyester fabric is placed in a constant temperature and humidity box at 21 +/-1 ℃ and 65 +/-2% for balancing for at least 24 hours.
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