Preparation process of silk fibroin grafted PET (polyethylene terephthalate) regenerated fiber
阅读说明：本技术 一种丝素蛋白接枝pet再生纤维制备工艺 (Preparation process of silk fibroin grafted PET (polyethylene terephthalate) regenerated fiber ) 是由 庄群 方婷 李继丰 闫文静 杜兆芳 于 2019-09-30 设计创作，主要内容包括：本发明公开了一种丝素蛋白接枝PET再生纤维制备工艺,包括以下步骤：(1)将PET再生纤维加入到HNO<Sub>3</Sub>溶液中,浸渍,烘干,得到硝化PET再生纤维；(2)将硝化PET再生纤维置于Na<Sub>2</Sub>S溶液和Na<Sub>2</Sub>CO<Sub>3</Sub>溶液中反应,得到硝化还原的PET再生纤维；(3)将硝化还原的PET再生纤维放入丝素蛋白溶液中接枝反应,预烘、干燥,即得到丝素蛋白接枝PET再生纤维。与现有技术相比,本发明的有益效果为：本发明方法获得的丝素蛋白改性PET再生纤维,对PET纤维损伤较小,机械性能并没有较大的变化,但复合纤维的吸湿性较普通再生纤维有所提高。丝素蛋白改性PET再生纤维具有抗静电、高吸湿性、亲肤性、保健功能,提高PET再生纤维的服用舒适性以及可加工性。(The invention discloses a preparation process of silk fibroin grafted PET regenerated fibers, which comprises the following steps: (1) adding PET regenerated fiber into HNO 3 Dipping and drying in the solution to obtain the nitrated PET regenerated fiber; (2) putting the nitrated PET regenerated fiber in Na 2 S solution and Na 2 CO 3 Reacting in the solution to obtain the PET regenerated fiber subjected to nitration and reduction; (3) and (3) placing the nitrated and reduced PET regenerated fiber into a silk fibroin solution for grafting reaction, and pre-drying and drying to obtain the silk fibroin grafted PET regenerated fiber. Compared with the prior art, the invention has the beneficial effects that: the method of the inventionThe obtained silk fibroin modified PET regenerated fiber has small damage to the PET fiber, the mechanical property is not greatly changed, but the hygroscopicity of the composite fiber is improved compared with that of the common regenerated fiber. The silk fibroin modified PET regenerated fiber has the functions of static resistance, high hygroscopicity, skin friendliness and health care, and improves the wearing comfort and the processability of the PET regenerated fiber.)
1. A preparation process of silk fibroin grafted PET regenerated fiber is characterized by comprising the following steps: the method comprises the following steps:
(1) adding PET regenerated fiber into HNO3Dipping and drying in the solution to obtain the nitrated PET regenerated fiber;
(2) putting the nitrated PET regenerated fiber in Na2S solution and Na2CO3Reacting in the solution to obtain the PET regenerated fiber subjected to nitration and reduction;
(3) and (3) placing the nitrated and reduced PET regenerated fiber into a silk fibroin solution for grafting reaction, and pre-drying and drying to obtain the silk fibroin grafted PET regenerated fiber.
2. The preparation process of the silk fibroin grafted PET regenerated fiber according to claim 1, which is characterized in that: the HNO in the step (1)3The concentration of the fiber is 15-35g/L, the dipping temperature is room temperature, the dipping time is 5-20min, and the fiber bath ratio is 1: 10-50.
3. The preparation process of the silk fibroin grafted PET regenerated fiber according to claim 1, which is characterized in that: in the step (1), the drying temperature is 50-100 ℃, and the drying time is 10-50 min.
4. The preparation process of the silk fibroin grafted PET regenerated fiber according to claim 1, which is characterized in that: na in step (2)2S and Na2CO3The concentration of the catalyst is 10-40g/L, the reaction time is 10-50min, and the reaction temperature is 80-120 ℃.
5. The preparation process of the silk fibroin grafted PET regenerated fiber according to claim 1, which is characterized in that: in the step (3), the concentration of the silk fibroin solution is 1% -5%, the impregnation temperature of the nitrated PET regenerated fiber is room temperature, the reaction time is 5-20min, and the fiber bath ratio is 1: 50-100.
6. The preparation process of the silk fibroin grafted PET regenerated fiber according to claim 1, which is characterized in that: the pre-drying temperature is 100-150 ℃, the pre-drying time is 1-5min, and the drying temperature is 50-100 ℃.
Technical Field
The invention relates to a process method of modified PET fibers, in particular to a process for preparing silk fibroin grafted PET regenerated fibers.
Background
Because the PET fiber has the advantages of high modulus, high strength, high elasticity, good shape retention, good heat resistance and the like, the PET fiber becomes the most widely applied synthetic fiber with the most consumption in the textile field. However, polyethylene terephthalate lacks active groups, and only contains-OH at two molecular ends, which not only makes polyester textiles non-hydrophilic and has poor hygroscopicity to cause discomfort in wearing, but also limits the application of PET fibers in many fields, such as prevention of functional graft modification of PET fibers. Therefore, the activation of the surface of the polyester fiber by providing the surface of the PET fiber with active groups is an effective method for modifying the PET fiber by experts and scholars at home and abroad in recent years, and common methods for activating the surface of the PET fiber include chemical oxidation, ammonolysis, alkali weight reduction treatment, plasma treatment, ultraviolet irradiation and the like.
In order to improve the wearing comfort and biocompatibility of the polyester fabric, experts and scholars at home and abroad graft some substances with hydrophilic groups or with hydrophilicity and biocompatibility on the surface of the PET fiber, wherein the grafting of some proteins, such as soybean protein, sericin, silk fibroin, silkworm pupa protein, milk protein, wool keratin and the like, on the surface of the PET fiber is included. The grafted protein can improve the moisture absorption performance of the PET fiber, and after the protein is grafted on the surface of the PET fiber, the protein is contacted with the skin when the PET fiber is worn, and the wearability and the health care performance are good, so that the protein is grafted on the surface of the PET fiber, which is popular with a plurality of researchers.
The silk fibroin is natural polymer fibrin extracted from silk, the content of the natural polymer fibrin accounts for about 70-80% of the silk, and the silk fibroin contains 18 amino acids, wherein glycine, alanine and serine account for more than 80% of the total composition. The fibroin has good mechanical property and physicochemical property, such as good flexibility, tensile strength, air permeability, moisture permeability, slow release property and the like, and can be processed into different forms, such as fiber, solution, powder, film, gel and the like. The invention discloses a method for preparing PET regenerated fiber, which comprises introducing a large amount of amino groups into macromolecules after the PET regenerated fiber is modified by nitration and reduction, wherein silk fibroin can be firmly grafted on the PET regenerated fiber through the combination of covalent bonds, and the PET regenerated fiber grafted with silk fibroin has good washability, improved hygroscopicity, antistatic property and correspondingly improved wearability.
Disclosure of Invention
The invention aims to provide a preparation process of silk fibroin grafted PET regenerated fibers, which aims to overcome the defects in the prior art, and can improve the moisture absorption of the PET regenerated fibers by grafting silk fibroin on the surfaces of the PET regenerated fibers, so that the PET regenerated fibers have the functions of static resistance, high moisture absorption, skin friendliness and health care, and the taking comfort of the PET regenerated fibers is improved.
The invention provides a preparation process of silk fibroin grafted PET regenerated fibers, which comprises the following steps:
(1) adding PET regenerated fiber into HNO3Dipping and drying in the solution to obtain the nitrated PET regenerated fiber;
(2) putting the nitrated PET regenerated fiber in Na2S solution and Na2CO3Reacting in the solution to obtain the PET regenerated fiber subjected to nitration and reduction;
(3) and (3) placing the nitrated and reduced PET regenerated fiber into a silk fibroin solution for grafting reaction, and pre-drying and drying to obtain the silk fibroin grafted PET regenerated fiber.
Preferably, the HNO in step (1)3The concentration of the fiber is 15-35g/L, the dipping temperature is room temperature, the dipping time is 5-20min, and the fiber bath ratio is 1: 10-50.
Preferably, the drying temperature in the step (1) is 50-100 ℃, and the drying time is 10-50 min.
Preferably, the Na in step (2)2S and Na2CO3The concentration of the catalyst is 10-40g/L, the reaction time is 10-50min, and the reaction temperature is 80-120 ℃.
Preferably, the concentration of the silk fibroin solution in the step (3) is 1% -5%, the impregnation temperature of the nitrated PET regenerated fiber is room temperature, the reaction time is 5-20min, and the fiber bath ratio is 1: 50-100.
Preferably, the pre-drying temperature is 100-.
Compared with the prior art, the invention has the beneficial effects that: the silk fibroin modified PET regenerated fiber obtained by the method has small damage to the PET fiber, the mechanical property is not greatly changed, but the hygroscopicity of the composite fiber is improved compared with that of the common regenerated fiber. The silk fibroin modified PET regenerated fiber has the functions of static resistance, high hygroscopicity, skin friendliness and health care, and improves the wearing comfort and the processability of the PET regenerated fiber.
Drawings
Fig. 1 is a flow chart of the preparation of the silk fibroin grafted PET regenerated fiber of the present invention.
Detailed Description
The embodiments described below with reference to the drawings are illustrative only and should not be construed as limiting the invention.
A preparation process of silk fibroin grafted PET regenerated fibers comprises the following steps:
(1) adding PET regenerated fiber into HNO3Dipping and drying in the solution to obtain the nitrated PET regenerated fiber;
(2) putting the nitrated PET regenerated fiber in Na2S solution and Na2CO3Reacting in the solution to obtain the PET regenerated fiber subjected to nitration and reduction;
(3) and (3) placing the nitrated and reduced PET regenerated fiber into a silk fibroin solution for grafting reaction, and pre-drying and drying to obtain the silk fibroin grafted PET regenerated fiber.
The HNO in the step (1)3The concentration of the fiber is 15-35g/L, the dipping temperature is room temperature, the dipping time is 5-20min, and the fiber bath ratio is 1: 10-50.
In the step (1), the drying temperature is 50-100 ℃, and the drying time is 10-50 min.
Step (a)2) Wherein Na is as defined in2S and Na2CO3The concentration of the catalyst is 10-40g/L, the reaction time is 10-50min, and the reaction temperature is 80-120 ℃.
In the step (3), the concentration of the silk fibroin solution is 1% -5%, the impregnation temperature of the nitrated PET regenerated fiber is room temperature, the reaction time is 5-20min, and the fiber bath ratio is 1: 50-100.
The pre-drying temperature is 100-150 ℃, the pre-drying time is 1-5min, and the drying temperature is 50-100 ℃.
Example 1 of the invention:
a preparation process of silk fibroin grafted PET regenerated fibers comprises the following steps:
(1) adding PET regenerated fiber into 15g/L HNO3Soaking in the solution at a fiber bath ratio of 1:10 for 5min, and drying at 50 deg.C for 10min to obtain nitrated PET regenerated fiber.
(2) Then putting the nitrated PET regenerated fiber in 10g/L Na2S and 10g/L of Na2CO3Reacting in the solution for 10min at 80 ℃ to obtain the nitration-reduction PET regenerated fiber.
(3) Placing the nitrated and reduced PET regenerated fiber into a silk fibroin solution with the concentration of 1% for grafting reaction for 5min, wherein the fiber bath ratio is 1:50, after the reaction is finished, pre-drying for 1min at the temperature of 100 ℃, and drying at the temperature of 50 ℃ to obtain the silk fibroin grafted PET regenerated fiber.
Example 2 of the invention:
a preparation process of silk fibroin grafted PET regenerated fibers comprises the following steps:
(1) adding PET regenerated fiber into 20g/L HNO3Soaking in the solution at a fiber bath ratio of 1:10 for 10min, and drying at 60 deg.C for 15min to obtain the regenerated nitrocellulose.
(2) Then putting the nitrated PET regenerated fiber in 20g/L Na2S and 20g/L of Na2CO3Reacting in the solution for 20min at 90 ℃ to obtain the nitration-reduction PET regenerated fiber.
(3) Placing the nitrated and reduced PET regenerated fiber into a silk fibroin solution with the concentration of 2% for grafting reaction for 15min, wherein the fiber bath ratio is 1:60, after the reaction is finished, pre-drying for 2min at the temperature of 120 ℃, and drying at the temperature of 60 ℃ to obtain the silk fibroin grafted PET regenerated fiber.
Example 3 of the invention:
a preparation process of silk fibroin grafted PET regenerated fibers comprises the following steps:
(1) adding PET regenerated fiber into 30g/L HNO3Soaking in the solution at a fiber bath ratio of 1:40 for 15min, and drying at 90 deg.C for 40min to obtain nitrated PET regenerated fiber.
(2) Then the nitrated regenerated PET fiber is placed in 35g/L Na2S and 35g/L of Na2CO3Reacting in the solution for 45min at 110 ℃ to obtain the nitrated and reduced PET regenerated fiber.
(3) And (2) placing the nitrated and reduced PET regenerated fibers into a silk fibroin solution with the concentration of 4% for grafting reaction for 20min, wherein the fiber bath ratio is 1:90, after the reaction is finished, pre-drying for 3min at 145 ℃, and drying at 90 ℃ to obtain the silk fibroin grafted PET regenerated fibers.
The construction, features and functions of the present invention are described in detail in the embodiments illustrated in the drawings, which are only preferred embodiments of the present invention, but the present invention is not limited by the drawings, and all equivalent embodiments modified or changed according to the idea of the present invention should fall within the protection scope of the present invention without departing from the spirit of the present invention covered by the description and the drawings.