Modification method for improving crease resistance of real silk fabric

Abstract

The invention discloses a modification method for improving crease resistance of a real silk fabric. The modification method comprises the following steps: S1, preparing a modified hyperbranched polymer MHBP; s2, preparing a hyperbranched polymer nano zinc oxide aqueous solution; s3, performing microwave anti-wrinkle finishing on the real silk fabric, namely soaking the real silk fabric in a hyperbranched polymer nano zinc oxide aqueous solution at room temperature for treatment, then taking out the real silk fabric, performing microwave treatment, standing and cooling at room temperature, and finally, washing with deionized water and naturally airing. The stable hyperbranched polymer nano-zinc oxide solution prepared from the Zn (NO3) 2 solution and the modified hyperbranched polymer serves as anti-wrinkle finishing liquid, amino in the modified hyperbranched polymer reacts with carboxyl in the real silk, a cross-linked structure is formed on the surface of the fiber, and therefore the anti-wrinkle performance of the real silk is improved.

Description

Technical Field

[0001] The invention relates to the technical field of functional finishing of textiles, and in particular to a modification method for improving the wrinkle resistance of silk fabrics. Background Art

[0002] As people's living standards continue to improve, the quality requirements for daily necessities are getting higher and higher, especially the requirements for the quality of textiles. Not only are textiles required to have a high aesthetics, but there is also more attention paid to the impact of textiles on health. Silk fabrics have the characteristics of soft and smooth feel, but silk fabrics have poor wrinkle resistance, and generally require anti-wrinkle finishing. In addition, the main component of silk fabrics is protein fiber, so bacteria breed, which affects the quality of silk and harms human health. Silk fabrics have many excellent properties, such as breathability and hygroscopicity, as well as excellent drape, soft luster, and special silk sound. They are soft and comfortable to wear and are deeply loved by people.

[0003] With the continuous emergence of new chemical fibers in recent years, the inherent defects of silk itself have become more and more obvious, and traditional silk products have been seriously challenged. Improving its anti-wrinkle performance and giving it a variety of special functions, and increasing the added value of silk are urgent needs for silk production companies to remain invincible. Improving the anti-wrinkle performance of silk fabrics is conducive to improving the appearance and beauty. Silk fabrics that have been anti-wrinkle finished can better maintain flatness even when subjected to external forces during wearing or use, reducing the generation of wrinkles, thereby improving the overall appearance and beauty. This is particularly important for high-end clothing, home decoration and other fields, which can meet consumers' pursuit of high-quality life. At the same time, anti-wrinkle finishing can be customized according to different needs, such as different anti-wrinkle levels, feel requirements, etc., to meet the personalized needs of different consumers. Anti-wrinkle finishing of silk fabrics is of great significance in improving the appearance and beauty, expanding the scope of application, improving durability, enhancing market competitiveness and meeting diversified needs. Therefore, in the post-processing process of silk fabrics, anti-wrinkle finishing is an indispensable and important process.

[0004] There are two ways to improve the wrinkle resistance of silk: one is physical method, which is to change the physical form of silk by changing the raw materials and weaving methods or by external force to improve and enhance the wrinkle resistance; the other is chemical method, which is to use chemical additives to finish silk to achieve the wrinkle resistance. The existing anti-wrinkle method is not effective, so the development of a new anti-wrinkle method has become an urgent problem to be solved. Summary of the invention

[0005] The purpose of the present invention is to provide a modification method for improving the wrinkle resistance of silk fabric, so that the wrinkle resistance of silk is greatly improved.

[0006] The technical solution adopted by the present invention to solve the technical problem is: A modification method for improving the wrinkle resistance of silk fabric comprises the following steps: S1. Preparation of modified hyperbranched polymer MHBP: S11: Place diethylenetriamine in a three-necked flask, cool in an ice-water bath, and 2 Under protection, a mixed solution of methyl acrylate and methanol was slowly added dropwise using a constant pressure funnel. After the addition was completed, the mixture was reacted at room temperature for 4-5 hours, and then transferred to a rotary evaporator, the methanol was removed under reduced pressure, the temperature was raised to 150±5℃, and the reaction was continued under reduced pressure for 4-5 hours. The reaction was stopped to obtain HBP-NH 2 ; S12: HBP-NH 2 Dissolved in methanol to form HBP-NH with a concentration of 4-6 g / L 2 Methanol solution was added dropwise to HBP-NH 2 The methanol solution was then removed under reduced pressure, and the temperature was raised to 150±5°C and the reaction was continued under reduced pressure for 4-5 hours to obtain a modified hyperbranched polymer MHBP; S2. Preparation of hyperbranched polymer nano zinc oxide aqueous solution: Take 1-7 g / L Zn(NO 3 ) 2 The solution is added dropwise into a 1-6 g / L modified hyperbranched polymer MHBP methanol solution while stirring, and the mixture is stirred continuously until the mixture is uniformly mixed. After the mixture is stirred completely, the mixture is heated to boiling and kept boiling for 2-3 minutes, and the solution gradually changes from colorless to milky white to obtain a hyperbranched polymer nano zinc oxide aqueous solution crude product, and then sodium dodecyl sulfate is added to the hyperbranched polymer nano zinc oxide aqueous solution crude product, and ultrasonic dispersion is performed to obtain a hyperbranched polymer nano zinc oxide aqueous solution; S3. Microwave anti-wrinkle finishing of silk fabric: immerse the silk fabric in an aqueous solution of hyperbranched polymer nano zinc oxide at room temperature, then take out the silk fabric, perform microwave treatment, let it stand and cool at room temperature, finally, wash it with deionized water and dry it naturally.

[0007] By modifying the hyperbranched polymer, the activity of the external groups of the MHBP macromolecule is reduced, while the activity of the internal secondary amine groups and tertiary amine groups is relatively increased. Therefore, the complexing ability of the secondary amine groups and tertiary amine groups with zinc oxide ions is relatively enhanced, so that the reaction of zinc oxide ions occurs more inside the MHBP, and the generated nano zinc oxide particles are well wrapped by the MHBP, achieving effective protection of the nano zinc oxide particles by MHBP, thereby effectively inhibiting the agglomeration of the nano zinc oxide particles, and preparing a hyperbranched polymer nano zinc oxide solution with excellent stability.

[0008] The present invention utilizes Zn(NO 3 )2 A stable hyperbranched polymer nano zinc oxide solution is prepared by mixing the solution and modified hyperbranched polymer (MHBP) as an anti-wrinkle finishing solution, so that the amino groups in the modified hyperbranched polymer (MHBP) react with the carboxyl groups in the silk to form a cross-linked structure on the fiber surface, thereby improving the wrinkle resistance of the silk.

[0009] In S11, the volume ratio of diethylenetriamine:methyl acrylate:methanol is 50-55:40-45:100.

[0010] Preferably, in S11, the volume ratio of diethylenetriamine:methyl acrylate:methanol is 52:43:100.

[0011] Preferably, in S12, methyl acrylate: HBP-NH 2 The volume ratio of methanol solution = 1:4.

[0012] Preferably, in S2, Zn(NO 3 ) 2 The volume ratio of solution: modified hyperbranched polymer MHBP methanol solution = 8:3.

[0013] Preferably, in S2, Zn(NO 3 ) 2 The solution concentration is 3g / L.

[0014] Preferably, in S2, the concentration of the modified hyperbranched polymer MHBP methanol solution is 2 g / L.

[0015] Preferably, in S2, the amount of sodium dodecyl sulfate used is 0.5% by weight of the crude hyperbranched polymer nano zinc oxide aqueous solution.

[0016] Preferably, in S3, the silk fabric is immersed in an aqueous solution of hyperbranched polymer nano zinc oxide at room temperature, with a bath ratio of 1:50 and an immersion time of 30-35 min.

[0017] Preferably, in S3, the microwave power is 200-300 W, and the microwave treatment time is 2-3 min.

[0018] The beneficial effects of the present invention are: (1) The microwave method has the advantages of fast heating speed, short reaction time, simultaneous heating inside and outside, uniform heating, high efficiency, and energy saving; (2) The hyperbranched polymer nano zinc oxide aqueous solution prepared by the present invention greatly improves the anti-wrinkle effect of silk. As a functional material, hyperbranched polymer nano zinc oxide shows many special and excellent properties compared with ordinary zinc oxide, such as piezoelectricity, fluorescence, non-toxicity and other properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a schematic diagram of the HBP-NH2 synthesis. DETAILED DESCRIPTION

[0020] The technical solution of the present invention is further described in detail below through specific embodiments.

[0021] In the present invention, unless otherwise specified, the raw materials and equipment used can be purchased from the market or are commonly used in the art. The methods in the following embodiments, unless otherwise specified, are all conventional methods in the art.

[0022] In the present invention, diethylenetriamine (Jining Green Union Chemical Technology Co., Ltd.), methyl acrylate (Jining Juyue New Materials Co., Ltd.), methanol (Jining Juyue New Materials Co., Ltd.), Zn(NO 3 ) 2 (Jining Juyue New Materials Co., Ltd.). The synthetic route of HBP-NH2 is as follows Figure 1 shown.

[0023] Embodiment 1: A modification method for improving the wrinkle resistance of silk fabric comprises the following steps: S1. Preparation of modified hyperbranched polymer MHBP: S11: Place 52 mL of diethylenetriamine in a 250 mL three-necked flask, cool in an ice-water bath, and 2 Under the protection of the reactor, a mixed solution of 43 mL of methyl acrylate and 100 mL of methanol was slowly added dropwise using a constant pressure funnel. After the addition was completed, the mixture was reacted at room temperature for 4 h, and then transferred to an eggplant-shaped flask of a rotary evaporator. The methanol was removed under reduced pressure, and the temperature was raised to 150 ° C. The reaction was continued under reduced pressure for 4 h, and the reaction was stopped to obtain a viscous light yellow amino-terminated hyperbranched compound: HBP-NH 2 ; S12: HBP-NH 2 Dissolved in methanol to form HBP-NH 2 Methanol solution, add 10 ml of methyl acrylate to 40 ml of HBP-NH 2 The methanol was removed under reduced pressure in a methanol solution, and the temperature was raised to 150°C and the reaction was continued under reduced pressure for 4 hours to obtain a modified hyperbranched polymer MHBP; S2. Preparation of hyperbranched polymer nano zinc oxide aqueous solution: Take 1 g / L Zn(NO 3 ) 280 mL of the solution was added dropwise into 30 mL of a 2 g / L modified hyperbranched polymer MHBP methanol solution while stirring, and the mixture was stirred continuously until uniformly mixed. After the mixture was stirred completely, the mixture was heated to boiling on an electric furnace and kept boiling for 2 min until the solution gradually changed from colorless to milky white. Then, 0.5 wt % of sodium dodecyl sulfate (SDS) was added to the milky white solution, and ultrasonic dispersion was performed for 30 min to ensure uniform dispersion, thereby obtaining a hyperbranched polymer nano zinc oxide aqueous solution. S3. Microwave anti-wrinkle finishing of silk fabric: The silk fabric was immersed in a hyperbranched polymer nano zinc oxide aqueous solution at room temperature, with a bath ratio of 1:50 and an immersion time of 30 minutes; then the silk fabric was taken out, placed in a 200W microwave oven and heated for 3 minutes, and allowed to cool at room temperature for 10 minutes. Finally, it was washed with deionized water for 5 minutes to remove incompletely reacted ions and dried naturally.

[0024] Embodiment 2: The difference between this embodiment and embodiment 1 is that: in S2, Zn(NO 3 ) 2 The solution concentration becomes 2 g / L.

[0025] Embodiment 3: The difference between this embodiment and embodiment 1 is that: in S2, Zn(NO 3 ) 2 The solution concentration became 3 g / L.

[0026] Embodiment 4: The difference between this embodiment and embodiment 1 is that: in S2, Zn(NO 3 ) 2 The solution concentration becomes 4 g / L.

[0027] Embodiment 5: The difference between this embodiment and embodiment 1 is that: in S2, Zn(NO 3 ) 2 The solution concentration became 5 g / L.

[0028] Embodiment 6: The difference between this embodiment and embodiment 1 is that: in S2, Zn(NO 3 ) 2 The solution concentration became 6 g / L.

[0029] Embodiment 7: The difference between this embodiment and embodiment 1 is that: in S2, Zn(NO 3 ) 2 The solution concentration became 7 g / L.

[0030] Embodiment 8: The difference between this embodiment and embodiment 3 is that in S2, the concentration of the modified hyperbranched polymer MHBP methanol solution is changed to 1 g / L.

[0031] Example 9: This example is different from Example 3 in that: in S2, the concentration of the modified hyperbranched polymer MHBP methanol solution is changed to 3 g / L.

[0032] Example 10: This example is different from Example 3 in that: in S2, the concentration of the modified hyperbranched polymer MHBP methanol solution is changed to 4 g / L.

[0033] Example 11: This example is different from Example 3 in that: in S2, the concentration of the modified hyperbranched polymer MHBP methanol solution is changed to 5 g / L.

[0034] Example 12: This example is different from Example 3 in that: in S2, the concentration of the modified hyperbranched polymer MHBP methanol solution is changed to 6 g / L.

[0035] Comparative Example 1: Microwave anti-wrinkle finishing of silk fabric: Silk fabric was immersed in 3g / L Zn(NO 3 ) 2 The solution was 1:50 and the immersion time was 30 minutes. Then the silk fabric was taken out, heated in a 200W microwave oven for 3 minutes, and then taken out and left to stand at room temperature for 10 minutes. Finally, it was washed with deionized water for 5 minutes to remove the unreacted ions, and dried naturally to obtain the final fabric.

[0036] Comparative Example 2: S1. Preparation of modified hyperbranched polymer MHBP: S11: Place 52 mL of diethylenetriamine in a 250 mL three-necked flask, cool in an ice-water bath, and 2 Under the protection of the reactor, a mixed solution of 43 mL of methyl acrylate and 100 mL of methanol was slowly added dropwise using a constant pressure funnel. After the addition was completed, the mixture was reacted at room temperature for 4 h, and then transferred to an eggplant-shaped flask of a rotary evaporator. The methanol was removed under reduced pressure, and the temperature was raised to 150 ° C. The reaction was continued under reduced pressure for 4 h, and the reaction was stopped to obtain a viscous light yellow amino-terminated hyperbranched compound: HBP-NH 2 ; S12: HBP-NH 2 Dissolved in methanol to form HBP-NH 2 Methanol solution, add 10 ml of methyl acrylate to 40 ml of HBP-NH 2 The methanol was removed under reduced pressure in a methanol solution, and the temperature was raised to 150°C and the reaction was continued under reduced pressure for 4 hours to obtain a modified hyperbranched polymer MHBP; S2. Microwave anti-wrinkle finishing of silk fabric: The silk fabric was immersed in 2g / L modified hyperbranched polymer MHBP solution at room temperature, with a bath ratio of 1:50 and an immersion time of 30min. Then the silk fabric was taken out, placed in a 200W microwave oven for heating for 3min, and then taken out and allowed to stand at room temperature for 10min. Finally, it was washed with deionized water for 5min to remove the incompletely reacted ions, and dried naturally to obtain the final fabric.

[0037] Comparative Example 3 Microwave anti-wrinkle finishing of silk fabric: The silk fabric was immersed in 3g / L nano zinc oxide solution at room temperature, with a bath ratio of 1:50, and the immersion time was 30 minutes. Then the silk fabric was taken out, heated in a 200W microwave oven for 3 minutes, and then taken out and left to stand at room temperature for 10 minutes. Finally, it was washed with deionized water for 5 minutes to remove the unreacted ions, and dried naturally to obtain the final fabric.

[0038] The main parameters in the preparation process of the embodiments and comparative examples of the present invention and the various properties of the prepared anti-wrinkle silk fabrics are shown in the following table: From Examples 1 to 7 and Comparative Example 2, it can be seen that Zn(NO 3 ) 2 The solution has an important effect on the improvement of the anti-wrinkle performance of silk fabrics. 3 ) 2 When the solution concentration is 3g / L, the anti-wrinkle performance of silk fabric can be improved to the maximum. At the same time, when the concentration is greater than 3g / L, the anti-wrinkle performance of silk fabric gradually decreases. 3 ) 2 When the solution was added, it was found that the anti-wrinkle performance of silk fabric was relatively poor.

[0039] From Examples 3, 8 to 12, it can be seen that the modified hyperbranched polymer MHBP solution has an important influence on the anti-wrinkle properties of silk fabrics. 3 ) 2 When the mass fraction of the solution is constant, the mass concentration of the modified hyperbranched polymer MHBP solution is 2g / L, and the anti-wrinkle performance of the silk fabric is the best. See Comparative Examples 1 and 3, when the modified hyperbranched polymer MHBP solution is not used, it can be found that the anti-wrinkle performance of the silk fabric is relatively poor.

[0040] The above-described embodiment is only a preferred solution of the present invention and does not limit the present invention in any form. There are other variations and modifications without exceeding the technical solution described in the claims.

Claims

1. A modification method for improving the wrinkle resistance of silk fabric, characterized in that: The steps include: S1. Preparation of modified hyperbranched polymer MHBP: S11: Place diethylenetriamine in a three-necked flask, cool in an ice-water bath, and slowly drop a mixed solution of methyl acrylate and methanol using a constant pressure funnel under N2 protection. After the dropwise addition is completed, react at room temperature for 4-5 hours, then transfer to a rotary evaporator, remove methanol under reduced pressure, heat to 150±5°C, continue to react under reduced pressure for 4-5 hours, and stop the reaction to obtain HBP-NH2; S12: HBP-NH2 is dissolved in methanol to form a HBP-NH2 methanol solution with a concentration of 4-6 g / L, methyl acrylate is added dropwise to the HBP-NH2 methanol solution at room temperature, and then the methanol is removed under reduced pressure, and the temperature is raised to 150±5°C and the reduced pressure reaction is continued for 4-5 hours to obtain a modified hyperbranched polymer MHBP; S2, preparing a hyperbranched polymer nano zinc oxide aqueous solution: taking 1-7g / L Zn(NO3)2 solution, dripping it into 1-6g / L modified hyperbranched polymer MHBP methanol solution while stirring, continuing to stir until the mixture is uniform, after stirring completely, heating to boiling and keeping boiling for 2-3min, until the solution gradually changes from colorless to milky white to obtain a hyperbranched polymer nano zinc oxide aqueous solution crude product, then adding sodium dodecyl sulfate to the hyperbranched polymer nano zinc oxide aqueous solution crude product, ultrasonically dispersing, to obtain a hyperbranched polymer nano zinc oxide aqueous solution; S3. Microwave anti-wrinkle finishing of silk fabric: immerse the silk fabric in an aqueous solution of hyperbranched polymer nano zinc oxide at room temperature, then take out the silk fabric, perform microwave treatment, let it stand and cool at room temperature, finally, wash it with deionized water and dry it naturally.

2. The modification method according to claim 1, characterized in that: In S11, the volume ratio of diethylenetriamine:methyl acrylate:methanol is 50-55:40-45:

100.

3. The modification method according to claim 2, characterized in that: In S11, the volume ratio of diethylenetriamine:methyl acrylate:methanol=52:43:

100.

4. The modification method according to claim 1, characterized in that: In S12, the volume ratio of methyl acrylate:HBP-NH2 methanol solution is 1:

4.

5. The modification method according to claim 1, characterized in that: In S2, the volume ratio of Zn(NO3)2 solution:modified hyperbranched polymer MHBP methanol solution = 8:

3.

6. The modification method according to claim 1, characterized in that: In S2, the concentration of Zn(NO3)2 solution is 3g / L.

7. The modification method according to claim 1, characterized in that: In S2, the concentration of the modified hyperbranched polymer MHBP methanol solution is 2 g / L.

8. The modification method according to claim 1, characterized in that: In S2, the amount of sodium dodecyl sulfate used is 0.5% by weight of the crude hyperbranched polymer nano zinc oxide aqueous solution.

9. The modification method according to claim 1, characterized in that: In S3, the silk fabric is immersed in a hyperbranched polymer nano zinc oxide aqueous solution at room temperature, with a bath ratio of 1:50 and an immersion time of 30-35 minutes.

10. The modification method according to claim 1, characterized in that: In S3, the microwave power is 200-300 W, and the microwave treatment time is 2-3 min.

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