Method for hydrophilic modification of polyester based on cooperation of plasma and enzyme catalysis
By using a synergistic modification method combining plasma and enzyme catalysis, grooves or pores are formed on the surface of polyester materials and hydrophilic polyethylene glycol molecules are introduced. This solves the problems of deformability and mechanical property damage in existing polyester fiber modification, and achieves efficient and environmentally friendly hydrophilicity enhancement.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-09-07
- Publication Date
- 2026-04-14
AI Technical Summary
Existing methods for hydrophilic modification of polyester fibers have high requirements for production processes such as shaping and microporousization, which increases costs and causes serious damage to the mechanical properties of the fibers. Commonly used modification methods can lead to immediate effects or environmental pollution.
Plasma treatment is used to form fine grooves or pores on the surface of polyester material, generating active free radicals. Then, hydrophilic polyethylene glycol molecules are introduced by enzyme catalysis. Combined with the reverse catalytic properties of lipase, an ester exchange reaction is carried out in the non-aqueous phase, thereby improving the hydrophilicity of the polyester material.
While ensuring the strength of polyester materials, its hydrophilicity and moisture-wicking properties are significantly improved, making up for the strength loss caused by plasma treatment, and achieving environmentally friendly and efficient hydrophilic modification.
Smart Images
Figure CN121853352A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of polyester modification technology, and in particular to a method for hydrophilic modification of polyester based on plasma and enzyme catalysis. Background Technology
[0002] Research on hydrophilic modification of polyester fibers can be carried out at multiple stages of its processing, including polymer manufacturing, spinning, dyeing and finishing, and post-processing. While existing modification methods can improve the wettability of polyester and impart good hydrophilicity, some problems remain. For example, the production processes of shaped and microporous polyesters require higher precision, increasing both difficulty and cost, and are prone to fuzzing. Commonly used modification methods include plasma irradiation etching and grafting hydrophilic modification, which have immediate effects but lead to a deterioration in fiber mechanical properties; traditional alkali reduction treatment severely damages the mechanical properties of the fibers and easily causes environmental pollution.
[0003] In response to the shortcomings of existing modification methods, enzymatic modification has attracted much attention in recent years due to its high selectivity, high efficiency, mild reaction conditions, and environmental friendliness. The application of enzymatic hydrophilic modification of polyester is a topic worthy of in-depth research. Summary of the Invention
[0004] The purpose of this invention is to disclose a method for hydrophilic modification of polyester based on plasma and enzyme catalysis. First, the surface of the polyester material is physically etched to form fine grooves or holes, while generating active free radicals and improving the moisture-wicking performance of the polyester material. Then, the hydrophilic polyethylene glycol molecules are introduced into the polyester macromolecules by enzyme catalysis, thereby improving the hydrophilicity of the polyester material while ensuring its strength.
[0005] To achieve the above objectives, the present invention provides a method for hydrophilic modification of polyester based on the synergistic effects of plasma and enzyme catalysis, comprising the following steps:
[0006] Plasma treatment: Polyester materials are subjected to plasma treatment to form fine grooves or holes on their surface. During the plasma treatment process, the discharge time is 100s-700s, the discharge power is 100W-600W, and the gas flow rate is 15sccm-55sccm.
[0007] Enzyme-catalyzed hydrophilic modification: Polyester material is immersed in polyethylene glycol solution, and lipase is used as a catalyst to perform hydrophilic modification by sequentially subjecting the material to ultrasonic bath and ordinary water bath.
[0008] In some embodiments, after the enzyme-catalyzed hydrophilic modification reaction is completed, the modified polyester material is washed with an organic solvent to remove the lipase and unreacted polyethylene glycol on the surface, and then air-dried.
[0009] In some embodiments, the lipase loading ranges from 50% to 350% v / w.
[0010] In some embodiments, the lipase is Aspergillus oryzae lipase or Candida antarcticis lipase.
[0011] In some embodiments, the polyester material is impregnated in a polyethylene glycol solution with a bath ratio ranging from 1:50 to 1:400.
[0012] In some embodiments, the ultrasonic bath temperature is 30℃~65℃, and the ultrasonic bath time is 0.5h~1.5h.
[0013] In some implementations, the ordinary water bath temperature is 30℃~65℃, and the ordinary water bath time is 6h~18h.
[0014] In some embodiments, the organic solvent is chloroform, acetone, or tetrahydrofuran.
[0015] In some embodiments, the polyester material is polyester fabric or polyester fiber.
[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: The method for hydrophilic modification of polyester based on plasma and enzyme catalysis provided by the present invention first forms fine grooves or holes on the surface of polyester material by physical etching, while generating active free radicals and improving the moisture-wicking performance of polyester material. Then, by using enzyme catalysis, hydrophilic polyethylene glycol molecules are introduced into polyester macromolecules, thereby improving the hydrophilicity of polyester material while ensuring its strength. Attached Figure Description
[0017] Figure 1 This is a schematic diagram illustrating the principle of hydrophilic modification of polyester based on the synergistic effects of plasma and enzyme catalysis as shown in this invention.
[0018] Figure 2 SEM images of polyester fabrics before and after modification at 5000x magnification;
[0019] Figure 3 The graph shows the mechanical property test results of polyester fabrics before and after modification.
[0020] Figure 4 The diagram shows the equilibrium water absorption of polyester fabrics before and after modification.
[0021] Figure 5 This is a schematic diagram showing the contact angles of polyester fabrics before and after modification.
[0022] Figure 2 and Figure 5In the examples, A - no treatment was performed; B - plasma treatment only (using the experimental conditions in Example 1); C - enzyme catalysis treatment only (using the experimental conditions in Example 1); D - fabric treated with a combination of plasma and enzyme catalysis (using the experimental conditions in Example 1). Detailed Implementation
[0023] The present invention will now be described in detail with reference to the embodiments shown in the accompanying drawings. However, it should be noted that these embodiments are not intended to limit the present invention. Equivalent changes or substitutions in function, method, or structure made by those skilled in the art based on these embodiments are all within the scope of protection of the present invention.
[0024] Example 1:
[0025] This embodiment discloses a method for hydrophilic modification of polyester based on the synergistic effects of plasma and enzyme catalysis, comprising the following steps:
[0026] The first step is plasma treatment: Plasma treatment is applied to polyester fibers to form fine grooves or pores on their surface. On the one hand, this helps to generate active free radicals, which facilitate the introduction of hydrophilic polyethylene glycol molecules. After the active free radicals and polyethylene glycol combine, they are located in the fine grooves or pores, thus keeping the surface of the polyester fibers flat and not affecting their performance. On the other hand, the addition of moisture-wicking grooves or pores on the surface of the polyester fibers improves their moisture-wicking and perspiration-driving performance.
[0027] During the plasma treatment process, the discharge time is 200s, the discharge power is 200W, and the gas flow rate is 20sccm.
[0028] The second step, enzyme-catalyzed hydrophilic modification: Polyester fibers were impregnated in a polyethylene glycol solution at a liquor ratio of 1:50, using Aspergillus oryzae lipase as a catalyst at an enzyme loading of 100% v / w. The mixture was subjected to ultrasonic bath and ordinary water bath sequentially to perform hydrophilic modification on the polyester material. The ultrasonic bath temperature was 30℃, and the ultrasonic bath time was 0.5 h. The ordinary water bath temperature was 30℃, and the ordinary water bath time was 8 h.
[0029] After the enzyme-catalyzed hydrophilic modification reaction is completed, the modified polyester fibers are washed three times with chloroform to remove the lipase and unreacted polyethylene glycol on the surface, and then air-dried at 20°C.
[0030] The above-mentioned hydrophilic modified polyester fibers are woven into polyester fabrics, which are called hydrophilic modified polyester fabrics.
[0031] By utilizing the reverse catalytic properties of lipases—that is, their ability to catalyze transesterification and the formation of polyester groups in polyester molecules in a non-aqueous phase—hydrophilic polyethylene glycol molecules are introduced into polyester macromolecules. This not only improves the hydrophilicity of polyester fibers but also compensates for the strength loss caused during plasma treatment. It fully leverages the environmentally friendly advantages of plasma physical irradiation etching and bio-enzyme catalytic grafting, achieving a complementary effect between the two. While ensuring the strength of polyester fibers, it also imparts a certain degree of hydrophilicity.
[0032] Example 2:
[0033] This embodiment discloses a method for hydrophilic modification of polyester based on the synergistic effects of plasma and enzyme catalysis, comprising the following steps:
[0034] The first step is plasma treatment: Plasma treatment is applied to polyester fibers to form fine grooves or pores on their surface. On the one hand, this helps to generate active free radicals, which facilitate the introduction of hydrophilic polyethylene glycol molecules. After the active free radicals and polyethylene glycol combine, they are located in the fine grooves or pores, thus keeping the surface of the polyester fibers flat and not affecting their performance. On the other hand, the addition of moisture-wicking grooves or pores on the surface of the polyester fibers improves their moisture-wicking and perspiration-driving performance.
[0035] During the plasma treatment process, the discharge time is 200s, the discharge power is 200W, and the gas flow rate is 20sccm.
[0036] The second step, enzyme-catalyzed hydrophilic modification: Polyester fibers were impregnated in a polyethylene glycol solution at a liquor ratio of 1:200. Candida antarctica lipase was used as a catalyst with an enzyme loading of 120% v / w. The mixture was subjected to ultrasonic bath and ordinary water bath sequentially to perform hydrophilic modification on the polyester material. The ultrasonic bath temperature was 50℃, and the ultrasonic bath time was 1 hour. The ordinary water bath temperature was 50℃, and the ordinary water bath time was 10 hours.
[0037] After the enzyme-catalyzed hydrophilic modification reaction is completed, the modified polyester fibers are washed three times with acetone to remove the lipase and unreacted polyethylene glycol on the surface, and then air-dried at 20°C.
[0038] The above-mentioned hydrophilic modified polyester fibers are woven into polyester fabrics, which are called hydrophilic modified polyester fabrics.
[0039] By utilizing the reverse catalytic properties of lipases—that is, their ability to catalyze transesterification and the formation of polyester groups in polyester molecules in a non-aqueous phase—hydrophilic polyethylene glycol molecules are introduced into polyester macromolecules. This not only improves the hydrophilicity of polyester fibers but also compensates for the strength loss caused during plasma treatment. It fully leverages the environmentally friendly advantages of plasma physical irradiation etching and bio-enzyme catalytic grafting, achieving a complementary effect between the two. While ensuring the strength of polyester fibers, it also imparts a certain degree of hydrophilicity.
[0040] Example 3:
[0041] This embodiment discloses a method for hydrophilic modification of polyester based on the synergistic effects of plasma and enzyme catalysis, comprising the following steps:
[0042] The first step is plasma treatment: Plasma treatment is applied to polyester fibers to form fine grooves or pores on their surface. On the one hand, this helps to generate active free radicals, which facilitate the introduction of hydrophilic polyethylene glycol molecules. After the active free radicals and polyethylene glycol combine, they are located in the fine grooves or pores, thus keeping the surface of the polyester fibers flat and not affecting their performance. On the other hand, the addition of moisture-wicking grooves or pores on the surface of the polyester fibers improves their moisture-wicking and perspiration-driving performance.
[0043] During the plasma treatment process, the discharge time is 200s, the discharge power is 200W, and the gas flow rate is 20sccm.
[0044] The second step, enzyme-catalyzed hydrophilic modification: Polyester fibers were impregnated in a polyethylene glycol solution at a liquor ratio of 1:400, using *Candida antarctica* lipase as a catalyst at an enzyme loading of 350% v / w. The mixture was subjected to ultrasonic bath and ordinary water bath sequentially to perform hydrophilic modification on the polyester material. The ultrasonic bath temperature was 65℃, and the ultrasonic bath time was 1.5 hours. The ordinary water bath temperature was 65℃, and the ordinary water bath time was 18 hours.
[0045] After the enzyme-catalyzed hydrophilic modification reaction is completed, the modified polyester fiber is washed three times with tetrahydrofuran to remove the lipase and unreacted polyethylene glycol on the surface, and then air-dried at 20°C.
[0046] The above-mentioned hydrophilic modified polyester fibers are woven into polyester fabrics, which are called hydrophilic modified polyester fabrics.
[0047] By utilizing the reverse catalytic properties of lipases—that is, their ability to catalyze transesterification and the formation of polyester groups in polyester molecules in a non-aqueous phase—hydrophilic polyethylene glycol molecules are introduced into polyester macromolecules. This not only improves the hydrophilicity of polyester fibers but also compensates for the strength loss caused during plasma treatment. It fully leverages the environmentally friendly advantages of plasma physical irradiation etching and bio-enzyme catalytic grafting, achieving a complementary effect between the two. While ensuring the strength of polyester fibers, it also imparts a certain degree of hydrophilicity.
[0048] Analysis of experimental results:
[0049] Figure 1 This is a schematic diagram illustrating the principle of hydrophilic modification of polyester based on the synergistic effects of plasma and enzyme catalysis, as shown in this invention.
[0050] Figure 2The images shown are SEM images of polyester fabrics before and after modification, magnified 5000 times. It is clear from the images that the surfaces of polyester fabrics treated with plasma and enzyme alone are uneven, while the surfaces of polyester fabrics treated with both plasma and enzyme are relatively smooth, as if covered with a thin film. This is because the active free groups of the polyester fibers combine with polyethylene glycol and are located within tiny grooves or pores, thus maintaining the smoothness of the polyester fiber surface and not affecting its performance.
[0051] like Figure 3 The image shows the test results of the mechanical properties of polyester fabrics before and after modification. It can be seen that the mechanical properties of the polyester fabric treated with plasma did not change significantly. This is because plasma etching causes some fibers to break, but due to the short plasma treatment time, its mechanical properties did not decrease significantly. Enzyme-catalyzed transesterification reactions cause some polyester fiber molecular chains to break, resulting in a decrease in mechanical properties. The mechanical properties of the polyester fabric treated with the synergistic effects of plasma and enzymes increased. This is because after plasma treatment, some ester bonds on the fiber surface of the polyester fabric break, providing reaction sites for subsequent enzymatic transesterification reactions, making it easier for polyethylene glycol to graft onto the fiber surface, forming a thin film coating, thereby improving its mechanical properties.
[0052] like Figure 4 The diagram shows the equilibrium water absorption of polyester fabrics before and after modification. It can be seen that the equilibrium water absorption of the polyester fabric treated with plasma and lipase synergistically is greater than that of the polyester fabric treated with plasma and enzyme alone, and significantly higher than that of the untreated polyester fabric. This indicates that the synergistic effect of the two treatments significantly improves the hydrophilicity of the polyester fabric.
[0053] like Figure 5 It can also be clearly seen that the synergistic effect of plasma and enzymes significantly improves the hydrophilicity of polyester fabrics, with a static contact angle of <55°.
[0054] Hydrophilicity testing method: Based on the powder contact angle test method using the penetrant method, the water absorption of polyester fiber fabric was tested for 10 minutes using the Williams plate method on a fully automatic surface tension meter. Before the experiment, the sample was cut into a specified size of 3cm (warp) × 1cm (weft), and excess burrs were removed.
[0055] The detailed descriptions listed above are merely specific descriptions of feasible embodiments of the present invention, and are not intended to limit the scope of protection of the present invention. All equivalent embodiments or modifications made without departing from the spirit of the present invention should be included within the scope of protection of the present invention.
[0056] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.
Claims
1. A method for hydrophilic modification of polyester based on the synergistic effects of plasma and enzyme catalysis, characterized in that, Includes the following steps: Plasma treatment: Polyester materials are subjected to plasma treatment to form fine grooves or holes on their surface. During the plasma treatment process, the discharge time is 100s-700s, the discharge power is 100W-600W, and the gas flow rate is 15sccm-55sccm. Enzyme-catalyzed hydrophilic modification: Polyester material is immersed in polyethylene glycol solution, and lipase is used as a catalyst to perform hydrophilic modification by sequentially subjecting the material to ultrasonic bath and ordinary water bath.
2. The method for hydrophilic modification of polyester based on plasma and enzyme catalysis according to claim 1, characterized in that, After the enzyme-catalyzed hydrophilic modification reaction is completed, the modified polyester material is cleaned with an organic solvent to remove the lipase and unreacted polyethylene glycol on the surface, and then air-dried.
3. The method for hydrophilic modification of polyester based on plasma and enzyme catalysis according to claim 1, characterized in that, The lipase loading range is 50% to 350% v / w.
4. The method for hydrophilic modification of polyester based on plasma and enzyme catalysis according to claim 3, characterized in that, The lipase is either Aspergillus oryzae lipase or Candida antarcticis lipase.
5. The method for hydrophilic modification of polyester based on plasma and enzyme catalysis according to claim 1, characterized in that, Polyester material is impregnated in polyethylene glycol solution with a liquor ratio ranging from 1:50 to 1:
400.
6. The method for hydrophilic modification of polyester based on plasma and enzyme catalysis according to claim 1, characterized in that, The ultrasonic bath temperature is 30℃~65℃, and the ultrasonic bath time is 0.5h~1.5h.
7. The method for hydrophilic modification of polyester based on plasma and enzyme catalysis according to claim 1, characterized in that, The temperature of a normal water bath is 30℃~65℃, and the duration of a normal water bath is 6h~18h.
8. The method for hydrophilic modification of polyester based on plasma and enzyme catalysis according to claim 1, characterized in that, The organic solvent is chloroform, acetone, or tetrahydrofuran.
9. The method for hydrophilic modification of polyester based on plasma and enzyme catalysis according to claim 1, characterized in that, The polyester material is polyester fabric or polyester fiber.