High-elasticity skin-friendly material and preparation method thereof
By modifying the surface of polyester fibers, introducing polyether-modified polyester finishing agents and graphene cross-linking agents, and combining them with seaweed polysaccharide cross-linking agents, the problems of poor hydrophilicity and antibacterial properties of polyester materials were solved, and the moisture absorption, antibacterial properties and washability of highly elastic and skin-friendly materials were achieved.
Patent Information
- Application Number
- CN202510965933.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-14
- Publication Date
- 2025-09-23
AI Technical Summary
Traditional polyester materials have poor hydrophilicity and are difficult to absorb sweat, which leads to damp, hot and uncomfortable conditions. They also have poor antibacterial properties, which easily cause bacterial growth and affect skin-friendliness. The finishing agent also has insufficient water resistance, which affects service life and performance stability.
By modifying the surface of polyester fibers, introducing polyether-modified polyester finishing agents and graphene crosslinking agents, and combining them with seaweed polysaccharide crosslinking agents, a composite finishing liquid is formed to improve the hydrophilicity and antibacterial properties of the fibers, and the bonding between the fibers and the finishing agent is enhanced through high-temperature baking.
It improves the moisture absorption, antibacterial and wash resistance of polyester fibers, strengthens the bonding strength of the fibers, and ensures that the material maintains good performance after multiple washes.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of high-performance fibers and discloses a high-elasticity skin-friendly material and a preparation method thereof. Background Art
[0002] Polyester has the advantages of high strength, high elasticity, and resistance to deformation, and is therefore widely used in the field of clothing. However, as consumers' requirements for clothing quality continue to increase, the defects of traditional polyester materials have gradually become prominent. For example, polyester materials have poor hydrophilicity and are difficult to absorb sweat, causing the wearer to feel damp and stuffy and uncomfortable; and polyester fabrics have poor antibacterial properties, which can easily cause bacteria to grow in a humid and hot environment, causing skin itching, resulting in poor skin-friendliness, which limits the application of polyester materials. In order to improve the performance of polyester, the existing technology often applies a finishing agent to its surface. However, the water resistance of commercially available polyester surface finishing agents needs to be improved, resulting in the performance of the finished fibers being reduced after multiple washings, affecting the service life and performance stability of the product. Therefore, it is of great significance to study a high-elastic skin-friendly material with good moisture absorption and antibacterial properties and good water washability and a preparation method thereof. Summary of the Invention
[0003] The object of the present invention is to provide a highly elastic skin-friendly material and a preparation method thereof, so as to solve the problems raised in the above background technology.
[0004] In order to solve the above technical problems, the present invention provides the following technical solution: a method for preparing a highly elastic skin-friendly material, comprising the following steps: S1: using plasma equipment to treat the base fiber to obtain a surface-modified fiber containing active functional groups on the surface; The basic fibers include polyester, recycled polyester, and nylon; S2: adding a polyether-modified polyester finishing agent and a graphene cross-linking agent to tetrahydrofuran to obtain a composite finishing solution; immersing the surface-modified fiber in the composite finishing solution, heating it to 30-40°C and soaking it for 1-2 hours, removing it, washing it, drying it at 100-105°C for 10-15 minutes, and baking it at 188-190°C for 30-60 seconds to obtain a composite modified fiber; S3: Add seaweed polysaccharide crosslinker and initiator into water and stir evenly to obtain seaweed polysaccharide finishing solution, immerse the composite modified fiber in it, heat it to 80-90℃ and soak it for 1-2h, take it out, wash it and dry it to obtain a highly elastic skin-friendly material.
[0005] More optimally, the dyeing process of the highly elastic skin-friendly material is as follows: after pre-treatment, the pre-treated highly elastic skin-friendly material is immersed in a dye solution, slowly heated to 80-85°C and kept warm for 10-15 minutes, then heated to 125-135°C and kept warm for 30-35 minutes, the waste water is discharged, the material is cleaned, and softened, and the dyeing is completed; the pH value of the dye solution is 4-5, and the raw materials include 0.4-0.6wt% of a leveling agent, 0.5-0.7wt% of a dye, and the rest is water; the softening treatment uses a softening treatment liquid, which includes 2-5wt% of a softener and the rest is water; the treatment process: keeping warm at 35-40°C for 20-25 minutes.
[0006] More optimally, the specifications of the basic fiber include 50D, 50D / 2, 100D, 150D, 300D, 450D, and 600D.
[0007] More optimally, the preparation of the polyether-modified polyester finishing agent includes the following steps: Step 1: adding four-arm-polyethylene glycol-hydroxyl and sodium carbonate to tetrahydrofuran and mixing evenly, adding propylene bromide, heating to 50-60° C. and stirring for 3-5 hours, and removing the solvent to obtain double-bond modified polyethylene glycol; Step 2: Take dimethyl terephthalate, ethylene glycol and catalyst tetrabutyl titanate, heat and stir evenly, raise the temperature to 180~190℃ and keep warm for 3~4h, add double bond modified polyethylene glycol, dodecyl bishydroxyethyl methyl ammonium chloride and catalyst tetrabutyl titanate, vacuum and raise the temperature to 180~185℃ for reaction 1~2h, then raise the temperature to 240~260℃ for reaction 1~3h to obtain a polyether modified polyester finishing agent.
[0008] More optimally, the double-bond modified polyethylene glycol comprises the following raw materials, calculated by weight: 10-15 parts of four-arm-polyethylene glycol-hydroxyl, 1-2 parts of sodium carbonate, and 1.2-2.4 parts of propylene bromide; the molecular weight of four-arm-polyethylene glycol-hydroxyl is 1k; The polyether-modified polyester finishing agent comprises the following raw materials, calculated by weight: 20-30 parts of dimethyl terephthalate, 3-5 parts of ethylene glycol, 60-80 parts of double-bond-modified polyethylene glycol, and 4-8 parts of dodecyl bis(hydroxyethyl)methylammonium chloride.
[0009] More optimally, the seaweed polysaccharide crosslinking agent includes the following steps: adding seaweed polysaccharide to water and mixing evenly, adding triethylamine, tetrabutylammonium bromide, and glycidyl methacrylate, reacting at 25-35° C. for 24-30 hours, and removing the solvent to obtain the seaweed polysaccharide crosslinking agent.
[0010] More optimally, the seaweed polysaccharide crosslinking agent includes the following raw materials, calculated by mass: 1-2 parts of seaweed polysaccharide, 80-100 parts of water, 0.1-0.2 parts of triethylamine, 0.5-1 parts of tetrabutylammonium bromide, and 4-6 parts of glycidyl methacrylate.
[0011] More optimally, the preparation of the graphene crosslinker includes the following steps: adding graphene oxide to tetrahydrofuran, mixing evenly, adding benzoyl chloride p-isocyanate, stirring evenly, adding triethylamine, stirring in an ice bath at 5-10°C under nitrogen protection for 3-4 hours, filtering the solid, and drying to obtain the graphene crosslinker.
[0012] More optimally, the graphene cross-linking agent includes the following raw materials, calculated by mass: 10-15 parts of graphene oxide, 1-2 parts of benzoyl chloride p-isocyanate, and 0.2-0.5 parts of triethylamine.
[0013] More optimally, in the composite finishing solution, the concentration of the polyether-modified polyester finishing agent is 15-20 g / L, the concentration of the graphene cross-linking agent is 50-60 g / L, and the balance is tetrahydrofuran; the immersion bath ratio is 1:40-50; The seaweed polysaccharide finishing liquid comprises the following raw materials, in parts by mass: 10-12 parts of a seaweed polysaccharide cross-linking agent, 0.01-0.02 parts of an initiator benzoyl peroxide, and 100-120 parts of water; the immersion bath ratio is 1:40-50.
[0014] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: (1) highly elastic polyester is selected to enhance skin affinity; (2) the basic polyester fiber is surface treated so that its surface has active functional groups such as hydroxyl groups, and is immersed in a composite finishing liquid containing a polyether-modified polyester finishing agent and a graphene crosslinking agent; the polyether-modified polyester finishing agent introduces polyester and polyether segments in a certain proportion to make it both hydrophilic and washable, and at the same time, the introduction of dodecylbis(hydroxyethyl)methylammonium chloride further enhances the hydrophilicity and antibacterial properties; the polyether-modified polyester finishing agent is terminated with hydroxyl groups and can be cross-linked with the surface of the polyester fiber and the hydroxyl groups contained in the polyester fiber under the action of the graphene crosslinking agent containing an isocyanate group, thereby enhancing the bonding force between the fiber and the finishing agent and improving the overall washability; due to the presence of polyester segments that can form a cocrystal with the polyester fiber, the polyester fiber is baked after treatment. Baking to further improve the bonding strength; double-bond modified polyethylene glycol is introduced into the polyether-modified polyester finishing agent, which is obtained by modification of four-arm-polyethylene glycol-hydroxyl. By controlling the molar ratio, a small number of double bonds are contained therein, which improves the cross-linking degree of the polyether-modified polyester finishing agent and can react with the seaweed polysaccharide cross-linker in the subsequent step to further improve the bonding strength; the seaweed polysaccharide cross-linker is a partially double-bond modified kelp polysaccharide, which itself has good hydrophilicity and antibacterial properties, but poor washability. Therefore, it is connected to the polyether-modified polyester finishing agent through a double bond and can be used as a cross-linking agent to improve the overall cross-linking degree and further improve the bonding strength; in summary, this scheme improves the overall bonding strength through the eutectic effect of polyester chain segments and polyester, the synergistic effect of graphene cross-linker and seaweed polysaccharide cross-linker, and prepares a highly elastic skin-friendly material with good moisture absorption, antibacterial properties and water washability. DETAILED DESCRIPTION
[0015] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.
[0016] It should be noted that the raw materials involved in the present invention are purchased from any manufacturer without any special restrictions, and illustratively include: ethanol (CAS: 64-17-5); sodium carbonate (CAS: 497-19-8); seaweed polysaccharide (S11058 source leaf); tetrabutylammonium bromide (CAS: 1643-19-2); glycidyl methacrylate (CAS: 106-91-2); graphene oxide (Kramer 180110132754 graphene oxide powder nanoparticles); m); benzoyl chloride (CAS: 3729-21-3); four-arm polyethylene glycol-hydroxy (SCLP-30009, molecular weight 1k); allyl bromide (CAS: 106-95-6); dimethyl terephthalate (CAS: 120-61-6); tetrabutyl titanate (source S48406); dodecyl bis (hydroxyethyl) methyl ammonium chloride (CAS: 22340-01-8); initiator benzoyl peroxide (CAS: 94-36-0); Unless otherwise specified, the following are parts by mass and mass ratios; Example 1: S1: 2 parts of seaweed polysaccharide were mixed with 100 parts of water, 0.1 parts of triethylamine, 0.8 parts of tetrabutylammonium bromide, and 6 parts of glycidyl methacrylate were added, and the mixture was reacted at 35° C. for 24 hours, and the solvent was removed to obtain a seaweed polysaccharide crosslinker; S2: Add 12 parts of graphene oxide to 100 parts of tetrahydrofuran, mix well, add 1.5 parts of benzoyl chloride p-isocyanate, stir well, then add dropwise 0.4 parts of triethylamine, stir in an ice bath at 5°C under nitrogen protection for 4 hours, filter and collect the solid, and dry to obtain a graphene crosslinker; S3: Add 10 parts of four-arm-polyethylene glycol-hydroxy and 2 parts of sodium carbonate to 100 parts of tetrahydrofuran and mix evenly. Add 2 parts of propylene bromide, heat to 55°C, stir for 4 hours, and remove the solvent to obtain double-bond modified polyethylene glycol; S4: Take 25 parts of dimethyl terephthalate, 5 parts of ethylene glycol and 0.01 parts of tetrabutyl titanate catalyst, heat to 150°C and stir evenly, raise the temperature to 180°C and keep warm for 4 hours, add 70 parts of double-bond modified polyethylene glycol, 6 parts of dodecyl bis (hydroxyethyl) methyl ammonium chloride and 0.01 parts of tetrabutyl titanate catalyst, evacuate and heat to 180°C for reaction for 2 hours, then raise the temperature to 250°C and react for 3 hours to obtain a polyether modified polyester finishing agent; S5: The base fiber was treated with a plasma device at a power of 50 W and a pressure of 15 Pa. The plasma device was first treated with oxygen for 60 seconds and then with nitrogen for 180 seconds to obtain a surface-modified fiber. The base fiber was 50D polyester. S6: adding a polyether-modified polyester finishing agent and a graphene crosslinking agent to tetrahydrofuran to obtain a composite finishing solution, wherein the concentration of the polyether-modified polyester finishing agent is 15 g / L and the concentration of the graphene crosslinking agent is 60 g / L; immersing the surface-modified fiber in the composite finishing solution at a bath ratio of 1:40, heating to 40°C, soaking for 2 hours, removing, washing, drying at 105°C for 12 minutes, and baking at 188°C for 60 seconds to obtain a composite modified fiber; S7: Add 10 parts of seaweed polysaccharide crosslinking agent and 0.01 parts of initiator benzoyl peroxide to 100 parts of water to obtain seaweed polysaccharide finishing solution, immerse the composite modified fiber in it with a bath ratio of 1:40, heat to 90°C and soak for 2 hours, take out, wash and dry to obtain a highly elastic skin-friendly material.
[0017] Example 2: S1: 1 part of seaweed polysaccharide was mixed with 100 parts of water, 0.1 parts of triethylamine, 0.5 parts of tetrabutylammonium bromide, and 4 parts of glycidyl methacrylate were added, and the mixture was reacted at 35° C. for 24 hours, and the solvent was removed to obtain a seaweed polysaccharide crosslinker; S2: Add 10 parts of graphene oxide to 100 parts of tetrahydrofuran, mix well, add 1 part of benzoyl p-isocyanate chloride, stir well, then add dropwise 0.2 parts of triethylamine, stir in an ice bath at 5°C under nitrogen protection for 4 hours, filter and collect the solid, and dry to obtain a graphene crosslinker; S3: Add 10 parts of four-arm-polyethylene glycol-hydroxy and 1.5 parts of sodium carbonate to 100 parts of tetrahydrofuran and mix evenly. Add 1.2 parts of propylene bromide, heat to 55°C, stir for 4 hours, and remove the solvent to obtain double-bond modified polyethylene glycol; S4: Take 20 parts of dimethyl terephthalate, 3 parts of ethylene glycol and 0.01 parts of tetrabutyl titanate catalyst, heat to 150°C and stir evenly, raise the temperature to 180°C and keep warm for 4 hours, add 60 parts of double-bond modified polyethylene glycol, 4 parts of dodecyl bis (hydroxyethyl) methyl ammonium chloride and 0.01 parts of tetrabutyl titanate catalyst, evacuate and heat to 180°C for reaction for 2 hours, then raise the temperature to 250°C and react for 3 hours to obtain a polyether modified polyester finishing agent; S5: The base fiber was treated with a plasma device at a power of 50 W and a pressure of 15 Pa. The plasma device was first treated with oxygen for 60 seconds and then with nitrogen for 180 seconds to obtain a surface-modified fiber. The base fiber was 50D polyester. S6: adding a polyether-modified polyester finishing agent and a graphene crosslinking agent to tetrahydrofuran to obtain a composite finishing solution, wherein the concentration of the polyether-modified polyester finishing agent is 15 g / L and the concentration of the graphene crosslinking agent is 50 g / L; immersing the surface-modified fiber in the composite finishing solution at a bath ratio of 1:40, heating to 40°C, soaking for 2 hours, removing, washing, drying at 105°C for 12 minutes, and baking at 188°C for 60 seconds to obtain a composite modified fiber; S7: Add 12 parts of seaweed polysaccharide crosslinking agent and 0.01 parts of initiator benzoyl peroxide to 100 parts of water to obtain seaweed polysaccharide finishing solution, immerse the composite modified fiber in it with a bath ratio of 1:40, heat to 90°C and soak for 2 hours, take out, wash and dry to obtain a highly elastic skin-friendly material.
[0018] Example 3: S1: 2 parts of seaweed polysaccharide were mixed with 100 parts of water, 0.2 parts of triethylamine, 1 part of tetrabutylammonium bromide, and 6 parts of glycidyl methacrylate were added, and the mixture was reacted at 35° C. for 24 hours, and the solvent was removed to obtain a seaweed polysaccharide crosslinker; S2: Add 15 parts of graphene oxide to 100 parts of tetrahydrofuran, mix well, add 2 parts of benzoyl chloride p-isocyanate, stir well, then add dropwise 0.5 parts of triethylamine, stir in an ice bath at 5°C under nitrogen protection for 4 hours, filter and collect the solid, and dry to obtain a graphene crosslinker; S3: Add 15 parts of four-arm-polyethylene glycol-hydroxy and 2 parts of sodium carbonate to 100 parts of tetrahydrofuran and mix evenly, add 2.4 parts of propylene bromide, heat to 55°C, stir for 4 hours, and remove the solvent to obtain double-bond modified polyethylene glycol; S4: Take 30 parts of dimethyl terephthalate, 5 parts of ethylene glycol and 0.01 parts of tetrabutyl titanate catalyst, heat to 150°C and stir evenly, raise the temperature to 180°C and keep warm for 4 hours, add 80 parts of double-bond modified polyethylene glycol, 8 parts of dodecyl bis (hydroxyethyl) methyl ammonium chloride and 0.01 parts of tetrabutyl titanate catalyst, evacuate and heat to 180°C for reaction for 2 hours, then raise the temperature to 250°C and react for 3 hours to obtain a polyether modified polyester finishing agent; S5: The base fiber was treated with a plasma device at a power of 50 W and a pressure of 15 Pa. The plasma device was first treated with oxygen for 60 seconds and then with nitrogen for 180 seconds to obtain a surface-modified fiber. The base fiber was 50D polyester. S6: adding a polyether-modified polyester finishing agent and a graphene crosslinking agent to tetrahydrofuran to obtain a composite finishing solution, wherein the concentration of the polyether-modified polyester finishing agent is 20 g / L and the concentration of the graphene crosslinking agent is 50 g / L; immersing the surface-modified fiber in the composite finishing solution at a bath ratio of 1:40, heating to 40°C, soaking for 2 hours, taking out, washing, drying at 105°C for 12 minutes, and baking at 188°C for 60 seconds to obtain a composite modified fiber; S7: Add 10 parts of seaweed polysaccharide crosslinking agent and 0.01 parts of initiator benzoyl peroxide to 100 parts of water to obtain seaweed polysaccharide finishing solution, immerse the composite modified fiber in it with a bath ratio of 1:40, heat to 90°C and soak for 2 hours, take out, wash and dry to obtain a highly elastic skin-friendly material.
[0019] Comparative Example 1 (using polyethylene glycol with a molecular weight of 1k instead of double-bond modified polyethylene glycol, and the remaining steps are the same as those in Example 1): S1: 2 parts of seaweed polysaccharide are uniformly mixed with 100 parts of water, 0.1 parts of triethylamine, 0.8 parts of tetrabutylammonium bromide, and 6 parts of glycidyl methacrylate are added, and the mixture is reacted at 35°C for 24 hours. The solvent is removed to obtain a seaweed polysaccharide crosslinker; S2: Add 12 parts of graphene oxide to 100 parts of tetrahydrofuran, mix well, add 1.5 parts of benzoyl chloride p-isocyanate, stir well, then add dropwise 0.4 parts of triethylamine, stir in an ice bath at 5°C under nitrogen protection for 4 hours, filter and collect the solid, and dry to obtain a graphene crosslinker; S3: Take 25 parts of dimethyl terephthalate, 5 parts of ethylene glycol and 0.01 parts of tetrabutyl titanate catalyst, heat to 150°C and stir evenly, raise the temperature to 180°C and keep warm for 4 hours, add 70 parts of polyethylene glycol, 6 parts of dodecyl bis (hydroxyethyl) methyl ammonium chloride and 0.01 parts of tetrabutyl titanate catalyst, evacuate and raise the temperature to 180°C for reaction for 2 hours, then raise the temperature to 250°C and react for 3 hours to obtain a polyether modified polyester finishing agent; S4: The base fiber was treated with a plasma device at a power of 50 W and a pressure of 15 Pa. The plasma device was first treated with oxygen for 60 seconds and then with nitrogen for 180 seconds to obtain a surface-modified fiber. The base fiber was 50D polyester. S5: adding a polyether-modified polyester finishing agent and a graphene crosslinking agent to tetrahydrofuran to obtain a composite finishing solution, wherein the concentration of the polyether-modified polyester finishing agent is 15 g / L and the concentration of the graphene crosslinking agent is 60 g / L; immersing the surface-modified fiber in the composite finishing solution at a bath ratio of 1:40, heating the solution to 40°C, soaking the fiber for 2 h, removing the fiber, washing the fiber, drying the fiber at 105°C for 12 min, and baking the fiber at 188°C for 60 s to obtain a composite modified fiber; S6: Add 10 parts of seaweed polysaccharide crosslinking agent and 0.01 parts of initiator benzoyl peroxide to 100 parts of water to obtain seaweed polysaccharide finishing solution, immerse the composite modified fiber in it with a bath ratio of 1:40, heat to 90°C and soak for 2 hours, take out, wash and dry to obtain a highly elastic skin-friendly material.
[0020] Comparative Example 2 (no seaweed polysaccharide crosslinker was introduced, and the remaining steps were the same as in Example 1): S1: 12 parts of graphene oxide were added to 100 parts of tetrahydrofuran, mixed evenly, 1.5 parts of benzoyl chloride p-isocyanate were added, stirred evenly, and then 0.4 parts of triethylamine were added dropwise. The mixture was stirred in an ice bath at 5°C under nitrogen protection for 4 hours. The solid was filtered and dried to obtain a graphene crosslinker. S2: Add 10 parts of four-arm-polyethylene glycol-hydroxy and 2 parts of sodium carbonate to 100 parts of tetrahydrofuran and mix evenly. Add 2 parts of propylene bromide, heat to 55°C, stir for 4 hours, and remove the solvent to obtain double-bond modified polyethylene glycol; S3: Take 25 parts of dimethyl terephthalate, 5 parts of ethylene glycol and 0.01 parts of tetrabutyl titanate catalyst, heat to 150°C and stir evenly, raise the temperature to 180°C and keep warm for 4 hours, add 70 parts of double-bond modified polyethylene glycol, 6 parts of dodecyl bis (hydroxyethyl) methyl ammonium chloride and 0.01 parts of tetrabutyl titanate catalyst, evacuate and heat to 180°C for reaction for 2 hours, then raise the temperature to 250°C and react for 3 hours to obtain a polyether modified polyester finishing agent; S4: The base fiber was treated with a plasma device at a power of 50 W and a pressure of 15 Pa. The plasma device was first treated with oxygen for 60 seconds and then with nitrogen for 180 seconds to obtain a surface-modified fiber. The base fiber was 50D polyester. S5: adding a polyether-modified polyester finishing agent and a graphene crosslinking agent to tetrahydrofuran to obtain a composite finishing solution, wherein the concentration of the polyether-modified polyester finishing agent is 15 g / L and the concentration of the graphene crosslinking agent is 60 g / L; immersing the surface-modified fiber in the composite finishing solution at a bath ratio of 1:40, heating the solution to 40°C, soaking the fiber for 2 h, removing the fiber, washing the fiber, drying the fiber at 105°C for 12 min, and baking the fiber at 188°C for 60 s to obtain a composite modified fiber; S6: Add 10 parts of seaweed polysaccharide to 100 parts of water to obtain seaweed polysaccharide finishing solution, immerse the composite modified fiber in it with a bath ratio of 1:40, heat to 90°C and soak for 2 hours, take out, wash and dry to obtain a highly elastic skin-friendly material.
[0021] Comparative Example 3 (the surface-modified fiber was replaced by the base fiber, and the remaining steps were the same as those in Example 1): S1: 2 parts of seaweed polysaccharide were uniformly mixed with 100 parts of water, 0.1 parts of triethylamine, 0.8 parts of tetrabutylammonium bromide, and 6 parts of glycidyl methacrylate were added, and the mixture was reacted at 35° C. for 24 hours. The solvent was removed to obtain a seaweed polysaccharide crosslinker; S2: Add 12 parts of graphene oxide to 100 parts of tetrahydrofuran, mix well, add 1.5 parts of benzoyl chloride p-isocyanate, stir well, then add dropwise 0.4 parts of triethylamine, stir in an ice bath at 5°C under nitrogen protection for 4 hours, filter and collect the solid, and dry to obtain a graphene crosslinker; S3: Add 10 parts of four-arm-polyethylene glycol-hydroxy and 2 parts of sodium carbonate to 100 parts of tetrahydrofuran and mix evenly. Add 2 parts of propylene bromide, heat to 55°C, stir for 4 hours, and remove the solvent to obtain double-bond modified polyethylene glycol; S4: Take 25 parts of dimethyl terephthalate, 5 parts of ethylene glycol and 0.01 parts of tetrabutyl titanate catalyst, heat to 150°C and stir evenly, raise the temperature to 180°C and keep warm for 4 hours, add 70 parts of double-bond modified polyethylene glycol, 6 parts of dodecyl bis (hydroxyethyl) methyl ammonium chloride and 0.01 parts of tetrabutyl titanate catalyst, evacuate and heat to 180°C for reaction for 2 hours, then raise the temperature to 250°C and react for 3 hours to obtain a polyether modified polyester finishing agent; S5: adding a polyether-modified polyester finishing agent and a graphene crosslinking agent to tetrahydrofuran to obtain a composite finishing solution, wherein the concentration of the polyether-modified polyester finishing agent is 15 g / L and the concentration of the graphene crosslinking agent is 60 g / L; immersing the base fiber in the composite finishing solution at a bath ratio of 1:40, heating to 40°C, soaking for 2 hours, removing, washing, drying at 105°C for 12 minutes, and baking at 188°C for 60 seconds to obtain a composite modified fiber; S6: Add 10 parts of seaweed polysaccharide crosslinking agent and 0.01 parts of initiator benzoyl peroxide to 100 parts of water to obtain seaweed polysaccharide finishing solution, immerse the composite modified fiber in it with a bath ratio of 1:40, heat to 90°C and soak for 2 hours, take out, wash and dry to obtain a highly elastic skin-friendly material.
[0022] Comparative Example 4 (the preparation method of the composite modified fiber was changed, and the remaining steps were the same as those in Example 1): S1: 2 parts of seaweed polysaccharide were uniformly mixed with 100 parts of water, 0.1 parts of triethylamine, 0.8 parts of tetrabutylammonium bromide, and 6 parts of glycidyl methacrylate were added, and the mixture was reacted at 35° C. for 24 hours. The solvent was removed to obtain a seaweed polysaccharide crosslinker; S2: Add 12 parts of graphene oxide to 100 parts of tetrahydrofuran, mix well, add 1.5 parts of benzoyl chloride p-isocyanate, stir well, then add dropwise 0.4 parts of triethylamine, stir in an ice bath at 5°C under nitrogen protection for 4 hours, filter and collect the solid, and dry to obtain a graphene crosslinker; S3: Add 10 parts of four-arm-polyethylene glycol-hydroxy and 2 parts of sodium carbonate to 100 parts of tetrahydrofuran and mix evenly. Add 2 parts of propylene bromide, heat to 55°C, stir for 4 hours, and remove the solvent to obtain double-bond modified polyethylene glycol; S4: Take 25 parts of dimethyl terephthalate, 5 parts of ethylene glycol and 0.01 parts of tetrabutyl titanate catalyst, heat to 150°C and stir evenly, raise the temperature to 180°C and keep warm for 4 hours, add 70 parts of double-bond modified polyethylene glycol, 6 parts of dodecyl bis (hydroxyethyl) methyl ammonium chloride and 0.01 parts of tetrabutyl titanate catalyst, evacuate and heat to 180°C for reaction for 2 hours, then raise the temperature to 250°C and react for 3 hours to obtain a polyether modified polyester finishing agent; S5: The base fiber was treated with a plasma device at a power of 50 W and a pressure of 15 Pa. The plasma device was first treated with oxygen for 60 seconds and then with nitrogen for 180 seconds to obtain a surface-modified fiber. The base fiber was 50D polyester. S6: adding a polyether-modified polyester finishing agent and a graphene crosslinking agent to tetrahydrofuran to obtain a composite finishing solution, wherein the concentration of the polyether-modified polyester finishing agent is 15 g / L and the concentration of the graphene crosslinking agent is 60 g / L; immersing the surface-modified fiber in the composite finishing solution at a bath ratio of 1:40, heating to 40° C., soaking for 2 h, removing, washing, and drying to obtain a composite modified fiber; S7: Add 10 parts of seaweed polysaccharide crosslinking agent and 0.01 parts of initiator benzoyl peroxide to 100 parts of water to obtain seaweed polysaccharide finishing solution, immerse the composite modified fiber in it with a bath ratio of 1:40, heat to 90°C and soak for 2 hours, take out, wash and dry to obtain a highly elastic skin-friendly material.
[0023] Performance test: (1) Take the highly elastic skin-friendly materials prepared in Examples 1 to 3 and test their mechanical strength; see Table 1 for details; Table 1:
[0024] (2) The highly elastic skin-friendly materials prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were woven into a grid using a loom to form grey fabric samples. The antibacterial properties were tested with reference to GB / T 20944.2. The antibacterial properties were tested again with reference to GB / T 8629 using a C-type standard washing machine with a 4N washing program for 100 times. The hydrophilicity was tested with reference to GB / T 21655.1. See Table 2 for details. Table 2:
[0025] Conclusion: In comparative example 1, polyethylene glycol with a molecular weight of 1k is used instead of double-bond modified polyethylene glycol. There is no double bond that can participate in subsequent reactions and the degree of branching is changed, so the performance is reduced; in comparative example 2, no seaweed polysaccharide cross-linking agent is introduced, and seaweed polysaccharide is directly added to water to obtain a seaweed polysaccharide finishing liquid. The composite modified fiber is immersed in it, and the resultant fiber is taken out, washed, and dried to obtain a highly elastic skin-friendly material. The impregnation effect is poor and the binding force is poor, and the water washing resistance is significantly reduced; in comparative example 3, the surface modified fiber is replaced by the base fiber. Due to the absence of the surface active functional group, the subsequent finishing effect is poor and the performance is reduced; in comparative example 4, the preparation method of the composite modified fiber is changed, and baking is not performed. There is no high-temperature melt eutectic effect between the polyether modified polyester finishing agent and the polyester fiber, the binding force is reduced, and the water washing resistance is not as good as that of the embodiment; in summary, the highly elastic skin-friendly material prepared by this scheme has good elasticity, antibacterial properties, and water resistance.
[0026] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art will be able to modify the technical solutions described in the aforementioned embodiments or substitute equivalents for some of the technical features. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.
Claims
1. A method for preparing a highly elastic skin-friendly material, characterized by: The following steps are involved: S1: using plasma equipment to treat the base fiber to obtain a surface-modified fiber containing active functional groups on the surface; The base fiber includes one of polyester, recycled polyester and nylon; S2: adding a polyether-modified polyester finishing agent and a graphene cross-linking agent to tetrahydrofuran to obtain a composite finishing solution; immersing the surface-modified fiber in the composite finishing solution, heating it to 30-40°C and soaking it for 1-2 hours, removing it, washing it, drying it at 100-105°C for 10-15 minutes, and baking it at 188-190°C for 30-60 seconds to obtain a composite modified fiber; S3: Add seaweed polysaccharide crosslinker and initiator into water and stir evenly to obtain seaweed polysaccharide finishing solution, immerse the composite modified fiber in it, heat it to 80-90℃ and soak it for 1-2h, take it out, wash it and dry it to obtain a highly elastic skin-friendly material.
2. The method for preparing a highly elastic skin-friendly material according to claim 1, characterized in that: The specifications of the basic fiber include one of 50D, 50D / 2, 100D, 150D, 300D, 450D, and 600D.
3. The method for preparing a highly elastic skin-friendly material according to claim 1, characterized in that: The preparation of the polyether-modified polyester finishing agent comprises the following steps: Step 1: adding four-arm-polyethylene glycol-hydroxyl and sodium carbonate to tetrahydrofuran and mixing evenly, adding propylene bromide, heating to 50-60° C. and stirring for 3-5 hours, and removing the solvent to obtain double-bond modified polyethylene glycol; Step 2: Take dimethyl terephthalate, ethylene glycol and catalyst tetrabutyl titanate, heat and stir evenly, raise the temperature to 180~190℃ and keep warm for 3~4h, add double bond modified polyethylene glycol, dodecyl bishydroxyethyl methyl ammonium chloride and catalyst tetrabutyl titanate, vacuum and raise the temperature to 180~185℃ for reaction 1~2h, then raise the temperature to 240~260℃ for reaction 1~3h to obtain a polyether modified polyester finishing agent.
4. The method for preparing a highly elastic skin-friendly material according to claim 3, characterized in that: The double-bond modified polyethylene glycol comprises the following raw materials, calculated by weight: 10 to 15 parts of four-arm-polyethylene glycol-hydroxyl group, 1 to 2 parts of sodium carbonate, and 1.2 to 2.4 parts of allyl bromide; The polyether-modified polyester finishing agent comprises the following raw materials, calculated by weight: 20-30 parts of dimethyl terephthalate, 3-5 parts of ethylene glycol, 60-80 parts of double-bond-modified polyethylene glycol, and 4-8 parts of dodecyl bis(hydroxyethyl)methylammonium chloride.
5. The method for preparing a highly elastic skin-friendly material according to claim 1, characterized in that: The seaweed polysaccharide crosslinking agent comprises the following steps: adding seaweed polysaccharide into water and mixing evenly, adding triethylamine, tetrabutylammonium bromide and glycidyl methacrylate, reacting at 25-35° C. for 24-30 hours, and removing the solvent to obtain the seaweed polysaccharide crosslinking agent.
6. The method for preparing a highly elastic skin-friendly material according to claim 5, characterized in that: The seaweed polysaccharide crosslinking agent comprises the following raw materials, calculated by mass: 1-2 parts of seaweed polysaccharide, 80-100 parts of water, 0.1-0.2 parts of triethylamine, 0.5-1 parts of tetrabutylammonium bromide, and 4-6 parts of glycidyl methacrylate.
7. The method for preparing a highly elastic skin-friendly material according to claim 1, characterized in that: The preparation of the graphene crosslinker comprises the following steps: adding graphene oxide to tetrahydrofuran, mixing uniformly, adding benzoyl p-isocyanate chloride, stirring uniformly, adding triethylamine, stirring in an ice bath at 5-10° C. under nitrogen protection for 3-4 hours, filtering and collecting a solid, and drying to obtain the graphene crosslinker.
8. The method for preparing a highly elastic skin-friendly material according to claim 7, characterized in that: The graphene cross-linking agent includes the following raw materials, calculated by mass: 10-15 parts of graphene oxide, 1-2 parts of benzoyl p-isocyanate chloride, and 0.2-0.5 parts of triethylamine.
9. The method for preparing a highly elastic skin-friendly material according to claim 1, characterized in that: In the composite finishing solution, the concentration of the polyether-modified polyester finishing agent is 15-20 g / L, the concentration of the graphene cross-linking agent is 50-60 g / L, and the balance is tetrahydrofuran; the immersion bath ratio is 1:40-50; The seaweed polysaccharide finishing liquid includes the following raw materials, in parts by mass: 10-12 parts of seaweed polysaccharide cross-linking agent, 0.01-0.02 parts of initiator, and 100-120 parts of water; the immersion bath ratio is 1:40-50.
10. A highly elastic skin-friendly material prepared according to the method for preparing a highly elastic skin-friendly material according to any one of claims 1 to 9.