A silk protein modified polyester material for wigs

Abstract

The present invention relates to the technical field of polyester materials, and in particular to a silk protein modified polyester material for wigs. The present invention adopts reactive dihydroxy monomers prepared from ethanolamine and 1,4-o-phthalaldehyde and 1,3-propylene glycol as diol monomers, and terephthalic acid as dibasic acid monomers to prepare reactive PTT, and then obtains reactive PTT fibers by melt spinning, and uses lithium bromide aqueous solution of phosphonated silk protein as finishing liquid to obtain a silk protein modified polyester material for wigs by impregnation modification. The silk protein modified polyester material for wigs provided by the present invention has excellent mechanical properties and flame retardant properties, and can be used as a new type of wig material.

Description

Technical Field

[0001] The invention relates to the technical field of polyester materials, and in particular to a silk protein modified polyester material for wigs. Background Art

[0002] With the development of society and the improvement of people's living standards, the beauty industry has gradually become an important market. Among them, wigs, as an important beauty product, are favored by more and more consumers. Wigs can not only be used for daily dressing, but also play an important role in special occasions such as stage performances, film and television shooting, etc. There are many types of wigs, and the materials are also different. They are mainly divided into two categories: synthetic fibers and natural fibers.

[0003] Synthetic fiber wigs are usually made of polyester. This type of wig has good strength and durability, can withstand certain stretching and wear, and is suitable for daily wear. However, the breathability and comfort of synthetic fibers are relatively poor, and long-term wearing may cause scalp discomfort. In addition, the appearance and feel of synthetic fibers are often not comparable to natural fibers, which brings certain inadequate user experience to consumers.

[0004] Natural fibers are mainly human hair and silk protein. Human hair wigs are widely popular for their natural look and feel, but they are expensive and require more time and effort to clean and maintain. Silk protein is favored for its excellent comfort and breathability, which can provide a better wearing experience. However, traditional silk protein is easily dissolved in water, resulting in a short service life, and has poor flame retardant properties, posing a safety hazard.

[0005] PTT (polytrimethylene terephthalate) is a new type of polyester material with excellent mechanical properties and heat resistance. Combining silk protein with PTT polyester can give full play to the advantages of both and form a new type of wig material, but it still faces problems such as dissolution in water, insufficient flame retardancy, unbalanced mechanical properties, complex processing technology and poor environmental adaptability. Further optimization is needed to improve the overall performance and promote its application in the wig market. Summary of the invention

[0006] In view of this, the purpose of the present invention is to provide a silk protein modified polyester material for wigs to solve the problems of silk protein modified PTT polyester such as dissolution in water, insufficient flame retardancy and unbalanced mechanical properties.

[0007] Based on the above purpose, the present invention provides a method for preparing a silk protein modified polyester material for a wig, comprising the following steps:

[0008] (1) Ethanolamine and 1,4-o-phthalaldehyde are reacted to obtain a reactive dihydroxy monomer;

[0009] (2) Using terephthalic acid as a dibasic acid monomer, 1,3-propylene glycol and a reactive dihydroxy monomer as diol monomers, the reactive PTT is obtained by reaction;

[0010] (3) melt-extruding and granulating the reactive PTT to obtain reactive PTT masterbatch, and then melt-spinning the reactive PTT masterbatch to obtain reactive PTT fiber;

[0011] (4) Degumming the mulberry silk with a sodium carbonate solution to obtain silk protein;

[0012] (5) treating silk protein with sodium tripolyphosphate and then activating it with lithium aluminum hydride to obtain phosphonated silk protein;

[0013] (6) dissolving the phosphonated silk protein in a lithium bromide aqueous solution to obtain a finishing solution;

[0014] (7) The reactive PTT fiber is immersed in a finishing liquid, heated to 80-90°C, allowed to stand for 20-28 hours, filtered, washed, dried, and then added to a methanol solution, and dried at 40-50°C for 10-14 hours to obtain a silk protein modified polyester material for a wig.

[0015] Preferably, in step (2), the weight ratio of terephthalic acid, 1,3-propylene glycol and reactive dihydroxy monomer is 16.61:6.85:2.2.

[0016] Preferably, in step (5), the weight ratio of sodium tripolyphosphate to silk fibroin is 0.3-0.4:2; and in step (6), the weight ratio of phosphonated silk fibroin to lithium bromide aqueous solution is 1:10.

[0017] Preferably, in step (7), the weight ratio of the reactive PTT fiber, the finishing liquid and the methanol is 10:11:100.

[0018] Preferably, the molar ratio of ethanolamine to 1,4-phthalaldehyde in step (1) is 2:1.

[0019] Preferably, the specific preparation steps of the reactive PTT in step (2) are as follows: terephthalic acid and 1,3-propylene glycol are mixed, and then a stabilizer and a catalyst are added, stirred for 25-65 minutes, and then the temperature is raised to 240-250° C., the pressure is maintained at 0.15-0.25 MPa, and the reaction is carried out for 4-6 hours, and then a reactive dihydroxy monomer and a catalyst are added, and the temperature is raised to 255-265° C., the pressure is maintained at 0.07-0.09 MPa, and the reaction is carried out for 20-40 minutes, and then the pressure is reduced to 80-120 Pa, and the reaction is carried out for 1.5-2.5 hours to obtain reactive PTT.

[0020] Preferably, the concentration of the sodium carbonate solution in step (4) is 0.05wt%-0.15wt%.

[0021] Preferably, in step (4), the weight ratio of mulberry silk to sodium carbonate solution is 1:50.

[0022] Preferably, the specific preparation method of the phosphonated silk protein in step (5) is as follows: disperse the silk protein in deionized water, stir to form a suspension, then adjust the pH to 8-9 with 1 mol / L sodium hydroxide, then add sodium tripolyphosphate, stir and react at room temperature for 40-60 minutes, and use 1 mol / L sodium hydroxide to maintain the pH at 8-9 during the reaction. After the reaction is completed, cool to room temperature, adjust the pH to 6.2-6.7 with 1 mol / L hydrochloric acid, centrifuge to remove the supernatant, dry at 40-50°C for 20-28h, then add to a 3wt% lithium aluminum hydride tetrahydrofuran solution, activate for 20-40min, wash, and dry to obtain the phosphonated silk protein.

[0023] Furthermore, the present invention also provides a silk protein modified polyester material for wigs, which is obtained by the preparation method of the silk protein modified polyester material for wigs.

[0024] Beneficial effects of the present invention:

[0025] The silk protein modified polyester material for wigs provided by the present invention has high breaking strength and breaking elongation, exhibits excellent mechanical properties, is suitable for applications such as wigs that require certain elasticity and strength, and effectively overcomes the problem that traditional silk protein is easily dissolved in water. After soaking in water for 24 hours, the dissolution rate of the material remains below 1%, ensuring stability and durability in a humid environment, and can be used for new wig materials.

[0026] The invention significantly improves the flame retardant properties of the material through phosphonation treatment. The introduction of phosphorus element promotes the formation of a protective carbonized layer at high temperature, reduces heat transfer and the release of combustible gas, and improves safety.

[0027] The reactive dihydroxy monomer of the present invention is obtained by Schiff base reaction of ethanolamine and 1,4-o-phthalaldehyde, and the carbon-nitrogen double bonds therein can be cross-linked with the phosphorus-hydrogen groups in the phosphonated silk protein through addition reaction. This cross-linking effect not only improves the overall strength of the material, but also effectively reduces the dissolution loss rate and strengthens the stability of the material.

[0028] The methanol treatment of the present invention improves the crystallinity of the material, promotes the structural stability of the silk protein, makes the molecules more closely arranged, and thus enhances the mechanical properties of the material. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The synthetic route diagram of the silk protein modified polyester material of the present invention. DETAILED DESCRIPTION

[0030] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

[0031] Example 1: (1) 18.33 g of ethanolamine and 20.12 g of 1,4-phthalaldehyde were added to 250 g of anhydrous ethanol, heated to 85° C., refluxed for 5 h, cooled to room temperature, and evaporated under reduced pressure to obtain a reactive dihydroxy monomer;

[0032] (2) 16.61 g of terephthalic acid and 6.85 g of 1,3-propylene glycol were mixed, and then 0.45 g of stabilizer (trimethyl phosphate) and 0.12 g of catalyst (tetrabutyl titanate) were added, and the mixture was stirred for 30 min, and then the temperature was raised to 245 ° C, the pressure was maintained at 0.2 MPa, and the reaction was carried out for 5 h. Then 2.2 g of reactive dihydroxy monomer and 0.07 g of catalyst (tetrabutyl titanate) were added, the temperature was raised to 260 ° C, the pressure was maintained at 0.08 MPa, and the reaction was carried out for 30 min. Then the pressure was reduced to 100 Pa and the reaction was carried out for 2 h to obtain reactive PTT;

[0033] (3) melt-extruding and granulating the reactive PTT to obtain reactive PTT masterbatch, and then melt-spinning the reactive PTT masterbatch, with the spinning box temperature at 274°C, the side blowing speed at 0.4 m / min, and the spinning speed at 2800 m / min, to obtain reactive PTT fiber;

[0034] (4) Add 5 g of mulberry silk into 250 g of 0.1 wt% sodium carbonate solution, heat to 100 °C, boil for 30 min, and stir with a glass rod to make the degumming uniform, then rinse with deionized water, and then degumming again according to the above method, repeat this three times, and dry to obtain silk protein;

[0035] (5) Disperse 2 g of silk protein in 50 g of deionized water, stir to form a suspension, then adjust the pH to 8.5 with 1 mol / L sodium hydroxide, then add 0.35 g of sodium tripolyphosphate, stir and react at room temperature for 50 min, and use 1 mol / L sodium hydroxide to maintain the pH at 8.5 during the reaction. After the reaction, cool to room temperature, adjust the pH to 6.5 with 1 mol / L hydrochloric acid, centrifuge to remove the supernatant, dry at 45°C for 24 h, then add 20 g of 3 wt% lithium aluminum hydride tetrahydrofuran solution, activate for 20 min, wash, and dry to obtain phosphonated silk protein;

[0036] (6) adding 1 g of phosphonated silk protein to 10 g of 9 M lithium bromide aqueous solution, heating to 80 °C, and stirring for 2 h to obtain a finishing solution;

[0037] (7) Immerse 10 g of reactive PTT fiber in 11 g of finishing liquid, heat it to 85 °C, let it stand for 24 h, filter, wash, dry, add it to 100 g of methanol solution, and dry it at 45 °C for 12 h to obtain a silk protein modified polyester material for wigs.

[0038] Example 2: (1) 18.33 g of ethanolamine and 20.12 g of 1,4-phthalaldehyde were added to 250 g of anhydrous ethanol, the temperature was raised to 85° C., refluxed for 5 h, cooled to room temperature, and vacuum evaporated to obtain a reactive dihydroxy monomer;

[0039] (2) 16.61 g of terephthalic acid and 6.85 g of 1,3-propylene glycol were mixed, and then 0.45 g of stabilizer (trimethyl phosphate) and 0.12 g of catalyst (tetrabutyl titanate) were added, and the mixture was stirred for 30 min, and then the temperature was raised to 240 ° C, the pressure was maintained at 0.15 MPa, and the reaction was continued for 4 h. Then 2.2 g of reactive dihydroxy monomer and 0.07 g of catalyst (tetrabutyl titanate) were added, the temperature was raised to 255 ° C, the pressure was maintained at 0.07 MPa, the reaction was continued for 20 min, and then the pressure was reduced to 80 Pa and the reaction was continued for 1.5 h to obtain reactive PTT;

[0040] (3) melt-extruding and granulating the reactive PTT to obtain reactive PTT masterbatch, and then melt-spinning the reactive PTT masterbatch, with the spinning box temperature being 273°C, the side blowing wind speed being 0.4 m / min, and the spinning speed being 2800 m / min, to obtain reactive PTT fiber;

[0041] (4) Add 5 g of mulberry silk into 250 g of a 0.05 wt% sodium carbonate solution, heat to 100 °C, boil for 40 min, and stir continuously with a glass rod to make the degumming uniform, then rinse with deionized water, and then degumming again according to the above method, repeat this three times, and dry to obtain silk protein;

[0042] (5) Disperse 2 g of silk protein in 50 g of deionized water, stir to form a suspension, then adjust the pH to 8 with 1 mol / L sodium hydroxide, then add 0.3 g of sodium tripolyphosphate, stir and react at room temperature for 40 min, and use 1 mol / L sodium hydroxide to maintain the pH at 8 during the reaction. After the reaction, cool to room temperature, adjust the pH to 6.2 with 1 mol / L hydrochloric acid, centrifuge to remove the supernatant, dry at 4°C for 28 h, then add 20 g of 3 wt% lithium aluminum hydride tetrahydrofuran solution, activate for 30 min, wash, and dry to obtain phosphonated silk protein;

[0043] (6) adding 1 g of phosphonated silk protein to 10 g of 9 M lithium bromide aqueous solution, heating to 80 °C, and stirring for 2 h to obtain a finishing solution;

[0044] (7) Immerse 10 g of reactive PTT fiber in 11 g of finishing liquid, heat it to 80 °C, let it stand for 28 h, filter, wash, dry, add it to 100 g of methanol solution, and dry it at 40 °C for 14 h to obtain a silk protein modified polyester material for wigs.

[0045] Example 3: (1) 18.33 g of ethanolamine and 20.12 g of 1,4-phthalaldehyde were added to 250 g of anhydrous ethanol, the temperature was raised to 85° C., refluxed for 5 h, cooled to room temperature, and vacuum evaporated to obtain a reactive dihydroxy monomer;

[0046] (2) 16.61 g of terephthalic acid and 6.85 g of 1,3-propylene glycol were mixed, and then 0.45 g of stabilizer (trimethyl phosphate) and 0.12 g of catalyst (tetrabutyl titanate) were added, and stirred for 40 min, and then the temperature was raised to 255 ° C, the pressure was maintained at 0.25 MPa, and the reaction was carried out for 6 h. Then 2.2 g of reactive dihydroxy monomer and 0.07 g of catalyst (tetrabutyl titanate) were added, and the temperature was raised to 265 ° C, the pressure was maintained at 0.09 MPa, and the reaction was carried out for 40 min. Then the pressure was reduced to 120 Pa and the reaction was carried out for 2.5 h to obtain reactive PTT;

[0047] (3) melt-extruding and granulating the reactive PTT to obtain reactive PTT masterbatch, and then melt-spinning the reactive PTT masterbatch, with the spinning box temperature at 275°C, the side blowing wind speed at 0.4 m / min, and the spinning speed at 2800 m / min, to obtain reactive PTT fiber;

[0048] (4) Add 5 g of mulberry silk into 250 g of a 0.15 wt% sodium carbonate solution, heat to 100 °C, boil for 20 min, and stir continuously with a glass rod to make the degumming uniform, then rinse with deionized water, and then degumming again according to the above method, repeat this three times, and dry to obtain silk protein;

[0049] (5) Disperse 2 g of silk protein in 50 g of deionized water, stir to form a suspension, then adjust the pH to 9 with 1 mol / L sodium hydroxide, then add 0.4 g of sodium tripolyphosphate, stir and react at room temperature for 60 min, and use 1 mol / L sodium hydroxide to maintain the pH at 9 during the reaction. After the reaction, cool to room temperature, adjust the pH to 6.7 with 1 mol / L hydrochloric acid, centrifuge to remove the supernatant, dry at 50°C for 20 h, then add 20 g of 3 wt% lithium aluminum hydride tetrahydrofuran solution, activate for 40 min, wash, and dry to obtain phosphonated silk protein;

[0050] (6) adding 1 g of phosphonated silk protein to 10 g of 9 M lithium bromide aqueous solution, heating to 80 °C, and stirring for 2 h to obtain a finishing solution;

[0051] (7) Immerse 10 g of reactive PTT fiber in 11 g of finishing liquid, heat it to 90 °C, let it stand for 20 h, filter, wash, dry, add it to 100 g of methanol solution, and dry it at 50 °C for 10 h to obtain a silk protein modified polyester material for wigs.

[0052] Comparative Example 1:

[0053] The difference between Comparative Example 1 and Example 1 is that no reactive dihydroxy monomer is added;

[0054] The specific steps are as follows:

[0055] (1) 16.61 g of terephthalic acid and 6.85 g of 1,3-propylene glycol were mixed, and then 0.45 g of stabilizer (trimethyl phosphate) and 0.12 g of catalyst (tetrabutyl titanate) were added, and stirred for 30 min. The temperature was then raised to 245 ° C, the pressure was maintained at 0.2 MPa, and the reaction was continued for 5 h. Then 0.76 g of 1,3-propylene glycol and 0.07 g of catalyst (tetrabutyl titanate) were added, the temperature was raised to 260 ° C, the pressure was maintained at 0.08 MPa, and the reaction was continued for 30 min. Then the pressure was reduced to 100 Pa and the reaction was continued for 2 h to obtain PTT.

[0056] (2) PTT was melt-extruded and granulated to obtain reactive PTT masterbatch, and then the reactive PTT masterbatch was melt-spun at a spinning box temperature of 274°C, a side blowing speed of 0.4 m / min, and a spinning speed of 2800 m / min to obtain PTT fiber;

[0057] (3) Add 5 g of mulberry silk into 250 g of 0.1 wt% sodium carbonate solution, heat to 100 °C, boil for 30 min, and stir continuously with a glass rod to make the degumming uniform, then rinse with deionized water, and then degumming again according to the above method, repeat this three times, and dry to obtain silk protein;

[0058] (4) Disperse 2 g of silk protein in 50 g of deionized water, stir to form a suspension, then adjust the pH to 8.5 with 1 mol / L sodium hydroxide, then add 0.35 g of sodium tripolyphosphate, stir and react at room temperature for 50 min, and use 1 mol / L sodium hydroxide to maintain the pH at 8.5 during the reaction. After the reaction, cool to room temperature, adjust the pH to 6.5 with 1 mol / L hydrochloric acid, centrifuge to remove the supernatant, dry at 45°C for 24 h, then add 20 g of 3 wt% lithium aluminum hydride tetrahydrofuran solution, wash, dry, and activate for 30 min to obtain phosphonated silk protein;

[0059] (5) adding 1 g of phosphonated silk protein to 10 g of 9 M lithium bromide aqueous solution, heating to 80 °C, stirring for 2 h, to obtain a finishing solution;

[0060] (6) Immerse 10 g of PTT fiber in 11 g of finishing liquid, heat it to 85 °C, let it stand for 24 h, filter, wash, and dry it. Then, add it to 100 g of methanol solution and dry it at 45 °C for 12 h to obtain a silk protein modified polyester material.

[0061] Comparative Example 2:

[0062] The difference between Comparative Example 2 and Example 1 is that the silk protein is not subjected to phosphonation treatment;

[0063] The specific steps are as follows:

[0064] (1) Add 18.33 g of ethanolamine and 20.12 g of 1,4-phthalaldehyde to 250 g of anhydrous ethanol, heat to 85°C, reflux for 5 h, cool to room temperature, and perform vacuum rotary evaporation to obtain a reactive dihydroxy monomer;

[0065] (2) 16.61 g of terephthalic acid and 6.85 g of 1,3-propylene glycol were mixed, and then 0.45 g of stabilizer (trimethyl phosphate) and 0.12 g of catalyst (tetrabutyl titanate) were added, and the mixture was stirred for 30 min, and then the temperature was raised to 245 ° C, the pressure was maintained at 0.2 MPa, and the reaction was carried out for 5 h. Then 2.2 g of reactive dihydroxy monomer and 0.07 g of catalyst (tetrabutyl titanate) were added, the temperature was raised to 260 ° C, the pressure was maintained at 0.08 MPa, and the reaction was carried out for 30 min. Then the pressure was reduced to 100 Pa and the reaction was carried out for 2 h to obtain reactive PTT;

[0066] (3) melt-extruding and granulating the reactive PTT to obtain reactive PTT masterbatch, and then melt-spinning the reactive PTT masterbatch, with the spinning box temperature at 274°C, the side blowing speed at 0.4 m / min, and the spinning speed at 2800 m / min, to obtain reactive PTT fiber;

[0067] (4) Add 5 g of mulberry silk into 250 g of 0.1 wt% sodium carbonate solution, heat to 100 °C, boil for 30 min, and stir with a glass rod to make the degumming uniform, then rinse with deionized water, and then degumming again according to the above method, repeat this three times, and dry to obtain silk protein;

[0068] (5) Add 1 g of silk protein to 10 g of 9 M lithium bromide aqueous solution, heat to 80 °C, and stir for 2 h to obtain a finishing solution;

[0069] (6) Immerse 10 g of reactive PTT fiber in 11 g of finishing solution, heat to 85 °C, let stand for 24 h, filter, wash, dry, add to 100 g of methanol solution, and dry at 45 °C for 12 h to obtain a silk protein modified polyester material.

[0070] Comparative Example 3:

[0071] The difference between Comparative Example 3 and Example 1 is that no reactive dihydroxy monomer is added and the silk protein is not subjected to phosphonation treatment;

[0072] The specific steps are as follows:

[0073] (1) 16.61 g of terephthalic acid and 6.85 g of 1,3-propylene glycol were mixed, and then 0.45 g of stabilizer (trimethyl phosphate) and 0.12 g of catalyst (tetrabutyl titanate) were added, and stirred for 30 min. The temperature was then raised to 245 ° C, the pressure was maintained at 0.2 MPa, and the reaction was continued for 5 h. Then 0.76 g of 1,3-propylene glycol and 0.07 g of catalyst (tetrabutyl titanate) were added, the temperature was raised to 260 ° C, the pressure was maintained at 0.08 MPa, and the reaction was continued for 30 min. Then the pressure was reduced to 100 Pa and the reaction was continued for 2 h to obtain PTT.

[0074] (2) PTT was melt-extruded and granulated to obtain reactive PTT masterbatch, and then the reactive PTT masterbatch was melt-spun at a spinning box temperature of 274°C, a side blowing speed of 0.4 m / min, and a spinning speed of 2800 m / min to obtain PTT fiber;

[0075] (3) Add 5 g of mulberry silk into 250 g of 0.1 wt% sodium carbonate solution, heat to 100 °C, boil for 30 min, and stir continuously with a glass rod to ensure uniform degumming. Rinse with deionized water, and then degumming again according to the above method. Repeat this three times and dry to obtain silk protein.

[0076] (4) adding 1 g of silk protein to 10 g of 9 M lithium bromide aqueous solution, heating to 80 °C, and stirring for 2 h to obtain a finishing solution;

[0077] (5) Immerse 10 g of PTT fiber in 11 g of finishing liquid, heat it to 85 °C, let it stand for 24 h, filter, wash, and dry it. Then add it to 100 g of methanol solution and dry it at 45 °C for 12 h to obtain a silk protein modified polyester material.

[0078] Comparative Example 4:

[0079] The difference between Comparative Example 4 and Example 1 is that: no methanol treatment is used;

[0080] The specific steps are as follows:

[0081] (1) Add 18.33 g of ethanolamine and 20.12 g of 1,4-phthalaldehyde to 250 g of anhydrous ethanol, heat to 85°C, reflux for 5 h, cool to room temperature, and perform vacuum rotary evaporation to obtain a reactive dihydroxy monomer;

[0082] (2) 16.61 g of terephthalic acid and 6.85 g of 1,3-propylene glycol were mixed, and then 0.45 g of stabilizer (trimethyl phosphate) and 0.12 g of catalyst (tetrabutyl titanate) were added, and the mixture was stirred for 30 min, and then the temperature was raised to 245 ° C, the pressure was maintained at 0.2 MPa, and the reaction was carried out for 5 h. Then 2.2 g of reactive dihydroxy monomer and 0.07 g of catalyst (tetrabutyl titanate) were added, the temperature was raised to 260 ° C, the pressure was maintained at 0.08 MPa, and the reaction was carried out for 30 min. Then the pressure was reduced to 100 Pa and the reaction was carried out for 2 h to obtain reactive PTT;

[0083] (3) melt-extruding and granulating the reactive PTT to obtain reactive PTT masterbatch, and then melt-spinning the reactive PTT masterbatch, with the spinning box temperature at 274°C, the side blowing speed at 0.4 m / min, and the spinning speed at 2800 m / min, to obtain reactive PTT fiber;

[0084] (4) Add 5 g of mulberry silk into 250 g of 0.1 wt% sodium carbonate solution, heat to 100 °C, boil for 30 min, and stir with a glass rod to make the degumming uniform, then rinse with deionized water, and then degumming again according to the above method, repeat this three times, and dry to obtain silk protein;

[0085] (5) Disperse 2 g of silk protein in 50 g of deionized water, stir to form a suspension, then adjust the pH to 8.5 with 1 mol / L sodium hydroxide, then add 0.35 g of sodium tripolyphosphate, stir and react at room temperature for 50 min, and use 1 mol / L sodium hydroxide to maintain the pH at 8.5 during the reaction. After the reaction is completed, cool to room temperature, adjust the pH to 6.5 with 1 mol / L hydrochloric acid, centrifuge to remove the supernatant, dry at 45°C for 24 h, then add 20 g of 3 wt% lithium aluminum hydride tetrahydrofuran solution, activate for 30 min, wash, and dry to obtain phosphonated silk protein;

[0086] (6) adding 1 g of phosphonated silk protein to 10 g of 9 M lithium bromide aqueous solution, heating to 80 °C, and stirring for 2 h to obtain a finishing solution;

[0087] (7) Immerse 10 g of reactive PTT fiber in 11 g of finishing liquid, heat to 85 °C, let stand for 24 h, filter, wash, and dry to obtain a silk protein modified polyester material.

[0088] Performance Test:

[0089] Strength test: Referring to GB / T 14337-2008 "Test method for tensile properties of chemical staple fibers", a fiber strength and elongation meter was used to perform strength tests on the silk protein modified polyester materials prepared in the examples and comparative examples. The results are shown in Table 1.

[0090] Dissolution loss rate: The silk protein modified polyester materials prepared in the examples and comparative examples were accurately weighed, and then placed in deionized water at a bath ratio of 1:100, dissolved at 37°C for 24 hours, and weighed after drying. The dissolution loss rate was calculated. The results are shown in Table 1.

[0091] Flame retardant properties: Referring to the test method in GB / T 5455-1997 "Vertical method for determination of flame retardant properties of textile fabrics", the silk protein modified polyester materials prepared in the examples and comparative examples were cut into 60 mm lengths, one end was clamped with a small clip, and the pieces were hung and ignited at room temperature. The afterflaming time, smoldering time and char length were recorded. The results are shown in Table 2.

[0092] Table 1 Test results of fiber diameter, strength and dissolution rate

[0093]

[0094] Data Analysis:

[0095] From the data of Examples 1-3 in Table 1, it can be seen that the silk protein modified polyester material for wigs prepared by the present invention has high breaking strength and breaking elongation. Most importantly, the material overcomes the problem that traditional silk protein is easily dissolved in water. After soaking in water for 24 hours, the dissolution rate remains below 1%.

[0096] The data comparison between Example 1 and Comparative Example 1 in Table 1 shows that the reactive dihydroxy monomer prepared by the present invention significantly improves the breaking strength of the fiber while maintaining the basic level of breaking elongation and effectively reduces the dissolution loss rate.

[0097] From the data of Example 1 and Comparative Example 2 in Table 1, it can be seen that the phosphonation treatment of silk protein plays an important role in improving the breaking strength of the silk protein modified polyester material used for wigs and reducing the dissolution loss rate.

[0098] From the data comparison of Example 1 and Comparative Example 3 in Table 1, it is found that compared with the fiber obtained by directly electrospinning PTT and silk protein, the silk protein modified polyester material for wigs prepared by the present invention exhibits good elongation at break and excellent breaking strength. This superior performance is mainly attributed to the chemical cross-linking between the reactive dihydroxy monomer and the phosphonated silk protein, which enhances the strength of the material and effectively reduces the dissolution loss rate.

[0099] Finally, from the comparative analysis of the data of Example 1 and Comparative Example 4 in Table 1, it can be seen that methanol treatment can effectively improve the strength of the silk protein modified polyester material used for wigs and reduce the dissolution rate. Methanol treatment enhances crystallinity, promotes the transformation of the α-helical conformation of silk protein to the structurally stable β-fold, and makes the molecular arrangement more compact.

[0100] Table 2 Flame retardant performance test results

[0101]

[0102] Data Analysis:

[0103] It can be seen from the data of Examples 1-3 in Table 1 that the silk protein modified polyester material for wigs prepared by the present invention has excellent flame retardant properties.

[0104] It can be seen from the data of Example 1 and Comparative Example 2 in Table 1 that the phosphonation treatment significantly improves the flame retardant properties of the silk protein modified polyester material. The enhanced flame retardant effect is mainly due to the phosphorus element introduced during the phosphonation process, which can promote the formation of a protective carbonized layer at high temperatures, prevent heat transfer and reduce the release of combustible gases.

[0105] Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

Claims

1. A method for preparing a silk protein modified polyester material for a wig, characterized in that: The following steps are involved: (1) Ethanolamine and 1,4-o-phthalaldehyde are reacted to obtain a reactive dihydroxy monomer; (2) Using terephthalic acid as a dibasic acid monomer, 1,3-propylene glycol and a reactive dihydroxy monomer as diol monomers, the reactive PTT is obtained by reaction; (3) melt-extruding and granulating the reactive PTT to obtain reactive PTT masterbatch, and then melt-spinning the reactive PTT masterbatch to obtain reactive PTT fiber; (4) Degumming the mulberry silk with a sodium carbonate solution to obtain silk protein; (5) treating silk protein with sodium tripolyphosphate and then activating it with lithium aluminum hydride to obtain phosphonated silk protein; (6) dissolving the phosphonated silk protein in a lithium bromide aqueous solution to obtain a finishing solution; (7) Immersing the reactive PTT fiber in a finishing solution, heating it to 80-90°C, standing it for 20-28 hours, filtering, washing, drying, and then adding it to a methanol solution, drying it at 40-50°C for 10-14 hours to obtain a silk protein modified polyester material for a wig; In the step (2), the weight ratio of terephthalic acid, 1,3-propylene glycol and reactive dihydroxy monomer is 16.61:6.85:2.2; in the step (5), the weight ratio of sodium tripolyphosphate and silk protein is 0.3-0.4:2; in the step (6), the weight ratio of phosphonated silk protein and lithium bromide aqueous solution is 1:10; in the step (7), the weight ratio of reactive PTT fiber, finishing liquid and methanol is 10:11:

100.

2. The method for preparing the silk protein modified polyester material for wigs according to claim 1, characterized in that: In the step (1), the molar ratio of ethanolamine to 1,4-phthalaldehyde is 2:

1.

3. The method for preparing the silk protein modified polyester material for wigs according to claim 1, characterized in that: The specific preparation steps of the reactive PTT in step (2) are as follows: terephthalic acid and 1,3-propylene glycol are mixed, and then a stabilizer and a catalyst are added, stirred for 25-65 minutes, and then the temperature is raised to 240-250° C., the pressure is maintained at 0.15-0.25 MPa, and the reaction is carried out for 4-6 hours, and then a reactive dihydroxy monomer and a catalyst are added, and the temperature is raised to 255-265° C., the pressure is maintained at 0.07-0.09 MPa, and the reaction is carried out for 20-40 minutes, and then the pressure is reduced to 80-120 Pa, and the reaction is carried out for 1.5-2.5 hours to obtain reactive PTT.

4. The method for preparing the silk protein modified polyester material for wigs according to claim 1, characterized in that: The concentration of the sodium carbonate solution in step (4) is 0.05wt%-0.15wt%.

5. The method for preparing the silk protein modified polyester material for wigs according to claim 1, characterized in that: In the step (4), the weight ratio of mulberry silk to sodium carbonate solution is 1:

50.

6. The method for preparing the silk protein modified polyester material for wigs according to claim 1, characterized in that: The specific preparation method of the phosphonated silk protein in step (5) is as follows: disperse the silk protein in deionized water, stir to form a suspension, then adjust the pH to 8-9 with 1 mol / L sodium hydroxide, then add sodium tripolyphosphate, stir and react at room temperature for 40-60 minutes, and use 1 mol / L sodium hydroxide to maintain the pH at 8-9 during the reaction. After the reaction is completed, cool to room temperature, adjust the pH to 6.2-6.7 with 1 mol / L hydrochloric acid, centrifuge to remove the supernatant, dry at 40-50°C for 20-28h, then add to a tetrahydrofuran solution of lithium aluminum hydride with a concentration of 3wt%, activate for 20-40min, wash, and dry to obtain the phosphonated silk protein.

7. A silk protein modified polyester material for wigs, characterized in that: The wig is obtained by the preparation method of the silk protein modified polyester material for wigs according to any one of claims 1 to 6.

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